Molecular dynamics simulations to compute diffusion coefficients of gases into polydimethylsiloxane and poly{(1,5‐ naphthalene)‐co‐[1,4‐durene‐2,2′‐bis(3,4‐dicarboxyl phenyl)hexafluoropropane diimide]}

Diffusion coefficients of N₂, O₂, CO₂ and CH₄ at 298 K in polydimethylsiloxane (PDMS) and poly{[(1,5‐naphthalene)‐co‐[1,4‐durene‐2,2′‐bis(3,4‐dicarboxyl phenyl)hexafluoropropane diimide]} (6FDA‐1,5‐NDA) polymers have been estimated using molecular dynamics (MD) simulations. Estimated diffusion coefficients in PDMS decrease systematically with increasing size of the penetrant gas molecules following the experimental observations. For 6FDA‐1,5‐NDA polymer, diffusion coefficients decrease in the same order of magnitude, but differ in their sequential order, due to varying side group interactions of the polymer with the gaseous molecules. Cohesive energy density, solubility parameter and free volume of the polymers were determined using MD simulations. Reliability and accuracy of the simulations have been tested typically with the computed values of the diffusion coefficient of O₂ in PDMS polymer, which compare well with the literature data. X‐ray scattering profiles of 6FDA‐1,5‐NDA have been generated to understand the interrelationship between the morphology and diffusion coefficients. The radial distribution function was evaluated to find the contribution of atoms that are important in understanding the molecular interactions during gas diffusion in polymers. Copyright © 2007 Society of Chemical Industry     

A Simple and Accurate Method for High‐Temperature PEM Fuel Cell Characterisation

A set of basic parameters for any polymer electrolyte membrane fuel cell (PEMFC) includes the Tafel slope b and the exchange current density j_* of the cathode catalyst, the oxygen diffusion coefficient D_b in the cathode gas‐diffusion layer and the cell resistivity R_cell. Based on the analytical model of a PEMFC [A. A. Kulikovsky, Electrochim. Acta (2004) 617], we propose a two‐step procedure allowing to evaluate these parameters for a high‐temperature PEMFC. The procedure requires two polarisation curves measured at different oxygen (air) stoichiometries. The method is validated using the experimental data obtained with the in‐house designed cell. High quality of fitting confirms validity and accuracy of this approach. The physical background of the method is discussed.     

Modeling thermodynamic properties of aqueous single‐solute and multi‐solute sugar solutions with PC‐SAFT

The Perturbed‐Chain Statistical Association Fluid Theory is applied to simultaneously describe various thermodynamic properties (solution density, osmotic coefficient, solubility) of aqueous solutions containing a monosaccharide or a disaccharide. The 13 sugars considered within this work are: glucose, fructose, fucose, xylose, maltose, mannitol, mannose, sorbitol, xylitol, galactose, lactose, trehalose, and sucrose. Four adjustable parameters (three pure‐sugar parameters and a k_ij between sugar and water that was allowed to depend linearly on temperature) were obtained from solution densities and osmotic coefficients of binary sugar/water solutions at 298.15 K available in literature. Using these parameters, the sugar solubility in water and in ethanol could be predicted satisfactorily. Further, osmotic coefficients and solubility in aqueous solutions containing two solutes (sugar/sugar, sugar/salt) were predicted (no additional k_ij parameters between the two solutes) reasonably. The model was also applied to predict the solubility of a sugar in a solvent mixture (e.g., water/ethanol) without additional fitting parameters. © 2013 American Institute of Chemical Engineers AIChE J, 59: 4794–4805, 2013     

Excess enthalpy data for the ternary system methane—ethylene—carbon dioxide by flow calorimetry

Excess enthalpy data for the ternary system methane – ethylene – carbon dioxide was obtained utilizing an isothermal flow calorimeter. The measurements were made at three temperatures: 293.15, 305.15 and 313.15 K and pressures of 1.114, 1.520 and 3.445 MPa (11, 15 and 34 atm). The determination of excess enthalpies for the binary systems methane—ethylene, ethylene—carbon dioxide and methane—carbon dioxide has been reported in three preceeding articles, respectively: Gagné et al., 1985; Ba et al., 1979 and Barry et al., 1982a. The binary interaction coefficients k_ij obtained for these systems have been utilized as initial values for the optimization procedure leading to the k_ij for the ternary system. For the case of the ternary system studied in this investigation, two types of binary interaction coefficients k_ij have been determined from experimental data: k_ij independent of temperature and pressure and k_ij adjusted as function of temperature and pressure. Experimental data were compared with the predictions from Benedict—Webb—Rubin and Redlich—Kwong equations of state. In both cases, the coefficients k_ij dependent on temperature and pressure led to better prediction of excess enthalpies.     

Water sorption kinetics in light‐cured poly‐HEMA and poly(HEMA‐co‐TEGDMA); determination of the self‐diffusion coefficient by new iterative methods

The present investigation is concerned with the determination of self‐diffusion coefficient (D) of water in methacrylate‐based biomaterials following Fickian sorption by two new methods: the Iterative and the Graphical methods. The D value is traditionally determined by means of the initial slope of the corresponding sorption curve and the so‐called Stefan's approximation. The proposed methods using equations without approximations and data resulting from the whole sorption range reach to accurate values of D, even when the sorption curve does not present an initial linear portion. In addition to D, the Graphical method allows the extrapolation of the mass of the sorbed water at equilibrium (M_∞), even when the equilibrium specimen's mass fluctuates around its limited value (m_∞). The test of the proposed procedures by means of ideal and Monte Carlo simulated data revealed that these methods are fairly applicable. The obtained D values compared with those determined by means of the Stephan's method revealed that the proposed methods provide more accurate results. Finally, the proposed methods were successfully applied to the experimental determination of the diffusion coefficient of water (50°C) in the homopolymer of 2‐hydroxyethyl methacrylate (HEMA) and in the copolymer of HEMA with triethylene glycol dimethacrylate (98/2 mol/mol). These polymers were prepared by light curing (λ = 470 nm) at room temperature in presence of camphorquinone and N,N‐dimethylaminoethyl methacrylate as initiator. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Distribution and diffusion coefficients of NaCl in polyamide (nylon‐6,6 and polyxylyleneadipamide) membranes

Thin membranes of an aliphatic polyamide (nylon‐6,6) and an aromatic polyamide (polyxylyleneadipamide) (PXAP) were prepared, and their distribution (K) and overall diffusion (D) coefficients of sodium chloride were measured with the unsteady‐state and steady‐state dialysis method. The overall diffusion coefficients at a zero concentration [D⁽⁰⁾] of sodium chloride for nylon‐6,6 and PXAP were 1.3–0.8 μm²/s (from 2 min of interfacial polymerization to 4 min) and 0.078, respectively. D⁽⁰⁾ for PXAP was about 3 times greater than that of a cellulose acetate (CA) membrane (0.024 μm²/s). The K values for nylon‐6,6 and PXAP were 0.7–0.5 from 2 to 4 min and 0.05, respectively. K for PXAP was almost the same as K for CA (0.06). A two‐part (dense and porous) model of the membrane structure was applied to obtain D_d (the diffusion coefficient in the dense part of the membrane) and D_p (the diffusion coefficient in the porous part of the membrane) for CA, PXAP, and nylon‐6,6 thin membranes. The values of D_d were almost the same for both nylon‐6,6 and PXAP (0.05–0.061 μm²/s) and about 10 times greater than the value for the CA membrane (5.6 × 10^?3 μm²/s). D_p for PXAP was almost the same as D_p for CA. However, D_p for the nylon‐6,6 membrane was 10–16 times greater than D_p for the PXAP membrane. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2605–2612, 2002     

Evaluation of the shrinking‐core model for examining the kinetics of film formation in a reactive latex blend

We prepared reactive latex blends from two copolymer latices comprised of n‐butyl methacrylate (n‐BMA) with acetoacetoxyethyl methacrylate and n‐BMA/dimethylaminoethyl methacrylate to study the kinetics of film formation. We generated thin films by blending equal weights of the two latices. The films were then cured at temperatures ranging from 50 to 90°C. The extent of the crosslinking reaction was calculated from the crosslink density, which was determined from swelling measurements of the films in toluene. The shrinking‐core model, a diffusion/reaction model, which was originally derived for combustion reactions of coal particles, was adopted to calculate the diffusion coefficient (D_e) and reaction rate constants from the extent of the reaction with time data. This model system exhibited a diffusion‐controlled regime above 70°C and a reaction‐controlled regime at temperatures below 70°C. In the reaction‐controlled regime, the shrinking‐core model predicted D_e for the system, which was in agreement with literature values for n‐BMA. In the diffusion‐controlled regime, the model predicted a lower apparent value for D_e but with an activation energy that was close to that obtained for n‐BMA. The model was also used to examine the kinetics of the crosslinking reaction. The kinetic rate constants for the crosslinking reaction were also determined. The activation energy for the crosslinking reaction was 18.8 kcal/mol, which compared reasonably with the activation energy of 22.8 kcal/mol determined for the reaction between the functional monomers as small molecules. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3659–3665, 2006     

Structural and emission properties of Eu3+‐doped alkaline earth zinc‐phosphate glasses for white LED applications

Quaternary alkaline earth zinc‐phosphate glasses in molar composition (40 ? x)ZnO – 35P₂O₅ – 20RO – 5TiO₂ – xEu₂O₃ (where x=1 and R=Mg, Ca, Sr, and Ba) were prepared by melt quenching technique. These glasses were studied with respect to their thermal, structural, and photoluminescent properties. The maximum value of the glass transition temperature (T_g) was observed for BaO network modifier mixed glass and minimum was observed for MgO network modifier glass. All the glasses were found to be amorphous in nature. The FT‐IR suggested the glasses to be in pyrophosphate structure, which matches with the theoretical estimation of O/P atomic ratio and the maximum depolymerization was observed for glass mixed with BaO network modifier. The intense emission peak was observed at 613 nm (⁵D₀→⁷F₂) under excitation of 392 nm, which matches well with excitation of commercial n‐UV LED chips. The highest emission intensity and quantum efficiency was observed for the glass mixed with BaO network modifier. Based on these results, another set of glass samples was prepared with molar composition (40 ? x)ZnO – 35P₂O₅ – 20BaO – 5TiO₂ – xEu₂O₃ (x=3, 5, 7, and 9) to investigate the optimized emission intensity in these glasses. The glasses exhibited crystalline features along with amorphous nature and a drastic variation in asymmetric ratio at higher concentration (7 and 9 mol%) of Eu₂O₃. The color of emission also shifted from red to reddish orange with increase in the concentration of Eu₂O₃. These glasses are potential candidates to use as a red photoluminsecent component in the field of solid‐state lighting devices.     

Critical gas velocity in a three‐phase internal loop airlift reactor with low‐density particles

In the present investigation the effects of the addition of organic additives (propanol, benzoic acid, iso‐amyl alcohol and carboxymethyl cellulose) on the critical gas velocity, (U_sg)_c, in an internal airlift loop reactor with low‐density particles (Nylon‐6 and polystyrene) were reported. Whereas the (U_sg)_c was reduced by adding the above additives, it increased with solids loading and density of the particles. The draft tube‐to‐reactor diameter ratio (D_E/D) in the range of 0.5–0.6 gave minimum (U_sg)_c values. The proposed dimensionless correlation predicted the experimental data well. Copyright © 2004 Society of Chemical Industry     

Anticancer Potency Studies of Coordination Driven Self‐Assembled Arene–Ru‐Based Metalla‐Bowls

New tetranuclear cationic metalla‐bowls 5 – 7 with the general formula [Ru₄(p‐cymene)₄(N∩N)₂(OO∩OO)₂]⁴⁺ (N∩N=2,6‐bis(N‐(4‐pyridyl carbamoyl)pyridine, OO∩OO=2,5‐dihydroxy‐1,4‐benzoquinonato ( 5 ), OO∩OO=5,8‐dioxydo‐1,4‐naphthaquinonato ( 6 ), OO∩OO=hoxonato ( 7 )) were prepared by the reaction of the respective dinuclear ruthenium complexes 2 – 4 with a bispyridine amide donor ligand 1 in methanol in the presence of AgO₃SCF₃.These new molecular metalla‐bowls were fully characterized by analytical techniques including elemental analysis as well as ¹H and ¹³C NMR and HR‐ESI‐MS spectroscopy. The structure of metalla‐bowl 6 was determined from X‐ray crystal diffraction data. A UV/visible study was also carried out for the entire suite of new complexes. As with recent studies of similar arene–Ru complexes, the inhibition of cell growth by metalla‐bowls was established against SK‐hep‐1 (liver cancer), AGS (gastric cancer), and HCT‐15 (colorectal cancer) human cancer cell lines. Inhibition of cell growth by 6 was found to be considerably stronger against all cancer cell lines than the anticancer drugs, doxorubicin and cisplatin. In particular, in colorectal cancer cells, expression of the cancer suppressor genes APC and p53 was increased following exposure to 6 .     

Diffusion and solubility of commercial poly(methyl methacrylate) denture base material modified with dimethyl itaconate and di‐n‐butyl itaconate during water absorption/desorption cycles

This study evaluated the water absorption, solubility, kinetics of water diffusion and residual monomer content of commercial poly(methyl methacrylate) (PMMA) denture base material modified with dimethyl itaconate (DMI) and di‐n‐butyl itaconate (DBI). Water absorption and solubility were measured gravimetrically while the residual monomer content was analysed using high‐performance liquid chromatography with ultraviolet detection. It was found that the addition of di‐n‐alkyl itaconates significantly decreases the residual methyl methacrylate (MMA) content in the polymerized material. Maximum uptake (M_∞) and loss (M′_∞), and diffusion coefficients for absorption (D_a) and desorption (D_d) of water through all materials were established. M_∞ shows a linear decrease with increasing amount of itaconate in the system while D_a shows a linear increase with increasing amount of itaconate, both of these effects being more pronounced when DBI is present compared to DMI. M_∞ is a linear function of the value of Hoy's solubility parameter. The reduction in residual MMA promoted by addition of a small amount of di‐n‐alkyl itaconates can improve the applicative properties and biocompatibility of the PMMA denture base material. Also, it is shown that modification of the denture base material with di‐n‐alkyl itaconates can enable precise control of water absorption in the system. Copyright © 2012 Society of Chemical Industry     

A DFT Study on the Structures and Energies of Isomers of 4‐Amino‐1,3‐dinitro‐1,2,4‐triazol‐5‐one‐2‐oxide: New High Energy Density Compounds

Isomers of 4‐amino‐1,3‐dinitrotriazol‐5‐one‐2‐oxide (ADNTONO) are of interest in the contest of insensitive explosives and were found to have true local energy minima at the DFT‐B3LYP/aug‐cc‐pVDZ level. The optimized structures, vibrational frequencies and thermodynamic values for triazol‐5‐one N‐oxides were obtained in their ground state. Kamlet‐Jacob equations were used to evaluate the performance properties. The detonation properties of ADNTONO (D=10.15 to 10.46 km s⁻¹, P=50.86 to 54.25 GPa) are higher compared with those of 1,1‐diamino‐2,2‐dinitroethylene (D=8.87 km s⁻¹, P=32.75 GPa), 5‐nitro‐1,2,4‐triazol‐3‐one (D=8.56 km s⁻¹, P=31.12 GPa), 1,2,4,5‐tetrazine‐3,6‐diamine‐1,4‐dioxide (D=8.78 km s⁻¹, P=31.0 GPa), 1‐amino‐3,4,5‐trinitropyrazole (D=9.31 km s⁻¹, P=40.13 GPa), 4,4′‐dinitro‐3,3′‐bifurazan (D=8.80 km s⁻¹, P=35.60 GPa) and 3,4‐bis(3‐nitrofurazan‐4‐yl)furoxan (D=9.25 km s⁻¹, P=39.54 GPa). The  NH₂ group(s) appears to be particularly promising area for investigation since it may lead to two desirable consequences of higher stability (insensitivity), higher density, and thus detonation velocity and pressure.     

Diffusion of mineral oil in styrene‐butadiene polymer films

Mineral oil diffusion in styrene‐butadiene polymer films was investigated with a simple gravimetric sorption method. Over the selected range of temperatures and film thicknesses for which sorption tests were performed, the diffusion process is described in terms of Fick's third law. Polymer dissolution was found to compete with the diffusion process especially at high temperature. Possible interference due to dissolution on data generated using a gravimetric method, resulted in an estimation of apparent activation energy using diffusion coefficient set calculated with Crank's half‐time relationship. The mineral oil diffusion activation energy was found to be relatively high compared with those of hydrocarbons diffusing in natural and synthesized rubbers or crosslinked polybutadiene as reported in the literature. The influence of polymer T_g, crosslinking density, and polarity on mineral oil ability to penetrate polymer film was evaluated in terms of percent weight increase over time. Maximum absorption after 60‐min sorption time linearly correlates with mineral oil absorption rate for polymers prepared with different structures. This linear relationship suggests that diffusion of solvent in styrene‐butadiene polymers reveals the macroscopic composition and structural polymer modification rather than local changes. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Determination of the Initiating Capability of Detonators Containing TKX‐50, MAD‐X1, PETNC,DAAF, RDX,HMX or PETN as a Base Charge,by Underwater Explosion Test

A comprehensive investigation to determine the initiation power of detonators containing as a base charge the novel explosives: dihydroxylammonium 5,5′‐bis(tetrazolate‐1N‐oxide) – TKX‐50, dihydroxylammonium 5,5′‐bis(3‐nitro‐1,2,4‐triazolate‐1N‐oxide) – MAD‐X1, pentaerythritol tetranitrocarbamate – PETNC and 3,3′‐diamino‐4,4′‐azoxyfurazan – DAAF in comparison with RDX, HMX and PETN was undertaken. In order to estimate the initiation power of the detonators, the underwater initiating capability test was used. The total energy as a sum of the primary shock wave energy and the bubble gas energy was determined for each of these explosives, by measuring the overpressure of the shock waves generated in water. Moreover, the complete synthesis for novel explosives is presented. The thermal behavior of the explosives was investigated using DSC (differential scanning calorimetry). The gas phase absolute molar enthalpies at 298 K and 10⁵ Pa were calculated theoretically using the modified complete basis set method (CBS‐4M; M referring to the use of minimal population localization) with the Gaussian 09 software. Gas phase standard molar enthalpies of formation (ΔH_f°_(g)) at 298 K were computed using the atomization energy method. Standard molar enthalpies of formation (▵H_(s)°) were calculated using ΔH_f°_(g) and the standard molar enthalpies of sublimation by applying Trouton’s rule. The Chapman‐Jouguet (CJ) characteristics based on calculated ▵H_(s)° values were computed using the EXPLO5 V6.01 thermochemical computer code. For the calculations the theoretical maximum densities and densities obtained during the experiments presented in this work were used.     

Transport characteristics of carboxylic acids based chain extended PU membranes with n‐alkane penetrants

Castor oil based chain extended polyurethanes (PUs) have been prepared using citric acid and maleic acid as chain extenders. Molecular transport of n‐alkanes into prepared carboxylic acid chain extended PUs has been studied at different temperatures, viz., 25, 40, and 60°C using a gravimetric sorption method. The sorption (S), the diffusion (D), and the permeation (P) coefficients for n‐alkane penetrants have been calculated. Transport data are affected by the nature of the interacting solvent molecules, molar volume, solubility parameters, temperature, and the structural variation of the chain extended PUs. The temperature dependence of the transport coefficient has been used to estimate the kinetic parameters for the processes of diffusion (E_D) and permeation (E_P) from the Arrhenius plots. The van't Hoff relation was used to obtain enthalpy (ΔH) and entropy (ΔS) of sorption process. POLYM. ENG. SCI., 47:2057–2064, 2007. © 2007 Society of Plastics Engineers     

Ternary diffusion coefficients of monoethanolamine and N-methyldiethanolamine in aqueous solutions

Ternary diffusion coefficients of monoethanolamine (MEA) and N-methyldiethanolamine (MDEA) in aqueous solutions have been measured at 303.2, 313.2, and 323.2 K. The systems studied are aqueous solutions containing total amine concentrations of 2.5 and 4.0 kmol/m³ and each solution prepared with four different amine molar ratios. The main diffusion coefficients (D₁₁ and D₂₂) and cross-diffusion coefficients (D₁₂ and D₂₁) and the density and viscosity of the aqueous amine solutions are discussed and analyzed as a function of temperature and their concentration.     

Swelling mechanism of porous P(VP‐co‐MAA)/PNIPAM semi‐IPN hydrogels with various pore sizes prepared by a freeze treatment

BACKGROUND: The objective of the work reported was to investigate the effect of gel microstructure on the swelling mechanism. A series of porous gels with various pore sizes were prepared by freeze‐treating a conventional hydrogel that contained various amounts of water at ? 20 °C. Scanning electron microscopy and differential scanning calorimetry were used to characterize the microstructure of the porous gels. RESULTS: The experimental results showed that the water content during freezing was the key factor controlling the microstructure. Measurement of swelling kinetics showed that a greater amount of water during the freezing process would lead to a rapid swelling rate. The apparent diffusion coefficients (D_p) at all times during the swelling process were obtained by fitting the experimental data to the diffusion equation. The values of D_p suggested that the swelling mechanism of the gels depends on the pore size. The diffusion exponent (n) obtained by fitting the fractional mass change (M_t/M_∞) to equation of Fick's law further confirmed that the swelling mechanism of the gels is determined by the pore size. CONCLUSION: The swelling mechanism of the gels is determined by the microstructure related to the pore size and the thickness of struts. The microstructure can be controlled by adjusting the water content of the hydrogels by changing the pH of the swelling medium prior to freezing. Copyright © 2008 Society of Chemical Industry     

Temperature effect on the swelling of PAAm‐κ‐carrageenan composites

The steady‐state fluorescence (SSF) technique was used for studying swelling of disc‐shaped polyacrylamide (PAAm)‐κ‐carrageenan (κC) composites which were prepared by free‐radical crosslinking copolymerization at 80°C. Pyranine was introduced as a fluorescence probe during polymerization. Swelling experiments were performed in water at various temperatures by real‐time monitoring of the pyranine (Py) fluorescence intensity, I which decreased as swelling proceeded. Stern–Volmer equation is modified for low quenching efficiencies to interpret the behavior of Py intensity during the swelling of PAAm‐κC composites. The Li‐Tanaka equation was used to determine the swelling time constants, τ₁, and cooperative diffusion coefficients, D₀, from fluorescence intensity, weight, and volume variations of the composites at various temperatures. It was observed that τ₁ first decreased up to 40°C and then increased; naturally, D₀ increased up to 40°C and then decrease for all κC content gels. Swelling activation energies, ΔE, were measured for the swelling composites, which are found to be exothermic and endothermic in between 30–40 and 40–60°C, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Carbon dioxide sorption and diffusion in poly(3‐hydroxybutyrate) and poly(3‐hydroxybutyrate‐CO‐3‐hydroxyvalerate)

CO₂ sorption and diffusion in poly(3‐hydroxybutyrate) and three poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) copolymers were investigated gravimetrically at temperatures from 25° to 50°C and pressures up to 1 atm. The sorption behavior proved to be linear for all the copolymers studied. An additional set of measurements performed in a pressure decay apparatus at 35°C showed that the linearity could be extrapolated to pressures up to 25 atm. The sorption results obtained from both techniques were in good agreement. The poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) sorption kinetics were increasingly non‐Fickian at the higher temperatures, thus preventing the calculation of diffusion coefficients above 35°C. Interestingly, this was not the case for poly(3‐hydroxybutyrate), and diffusion coefficients and permeabilities could be calculated at all of the investigated temperatures. The 35°C permeabilities were fairly low, which is attributed to the high degree of crystallinity of this polyester family. Finally, the poly(3‐hydroxybutyrate) barrier properties against CO₂ are successfully compared with those of some selected common thermoplastics. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2391–2399, 1999     

Diffusion of semi‐flexible polyelectrolyte through nanochannels

The diffusion of sodium polystyrene sulfonate through polycarbonate nanochanels was studied in salt‐free dilute aqueous solution. A stronger molecular weight dependence of diffusion was observed compared to free diffusion in dilute solution. Scaling exponentials relating polymer size to diffusivity were between Flory's theory (D_eff ∝ N^?0.6) and Rouse's model (D_eff ∝ N^?1), revealing a crossover regime from 3‐D diffusion to 1‐D diffusion. Diffusion was less hindered for the polyelectrolyte (D_eff/D₀), than for a rigid sphere, when the polymer/channel size ratio exceeded 0.2. This is attributed to elongated chains with reduced frictional hindrance. Simulation of the confined diffusion based on an elongated cigar model gave D ∝ N^?1 ${R_{\rm t}^{2/3}}$ while the experimental results agree with D ∝ N^?0.94${R_{\rm t}^{ 2/3}}$ . For charged polyelectrolytes, the transition to 1‐D diffusion therefore begins before the polymer radius of gyration exceeds the channel size contrary to model assumptions. We attribute this to the charged nature of the polyelectrolytes causing extended chain conformations. © 2009 American Institute of Chemical Engineers AIChE J, 2010