Effect of chemical structure on the subglass relaxation dynamics of biobased polyesters as revealed by dielectric spectroscopy: 2,5-furandicarboxylic acid vs. trans-1,4-cyclohexanedicarboxylic acid.

The chemical structure-dynamics relationship for poly(trimethylene 2,5-furanoate) and poly(trimethylene 1,4-cyclohexanedicarboxylate) was investigated via dielectric spectroscopy and compared with that of poly(trimethylene terephthalate) in order to evaluate the impact on the subglass dynamics of the chemical nature of the ring. Further comparison was accomplished with the neopentyl glycol containing counterparts: poly(neopentyl 2,5-furanoate) and poly(neopentyl 1,4-cyclohexanedicarboxylate). Our study reveals a multimodal nature of the subglass ß process. For the more flexible polymers (containing cyclohexane rings) three modes for the ß process were detected. The faster mode was assigned to the relaxation of the oxygen linked to the aliphatic carbon, the slower one to the link between the aliphatic ring and the ester group, and the third mode to the aliphatic ring. For stiffer polymers (containing aromatic rings), the local modes appear more coupled. This effect is more evident in the polymers with the furan ring where essentially a single ß mode can be resolved.

Tunable dielectric constant of water at the nanoscale.

Using molecular dynamics simulations, the influence of the surface charge density of a nanotube on the static dielectric permittivity ε of confined water was reported. Whereas the dielectric anisotropy between the radial and axial directions of water confined in hydrophilic and hydrophobic membranes and the increase in axial dielectric permittivity with respect to the bulk value have previously been described, we found that an increase in the surface charge density leads to a drastic decrease in ε into the axial direction. The decrease in ε is accompanied by a strong slowdown in the rotational dynamics of water molecules. We show that this effect is due to the strong orientation of water molecules induced by the surface charge. Thus, by controlling the surface charge in nanotubes and nanocavities, it is possible to tune the dielectric permittivity of confined fluids at the nanoscale.

Anomalous dielectric behavior of nanoconfined electrolytic solutions.

We report an anomalous dielectric effect of electrolytes under cylindrical nanoconfinement. In bulk phase, the decrease in the water dielectric constant (ε) with increasing salt concentration is well known, and is due to dielectric saturation. From molecular dynamic simulations of confined water and NaCl solutions, we show a dielectric anisotropy and an unexpected increase in ε(perpendicular) of NaCl solutions with respect to the confined pure liquid until a critical concentration is reached. We infer that this striking dielectric behavior results from the interplay between the effect of confinement and that of ions on the water hydrogen bonding network.

Laser-induced periodic surface structures nanofabricated on poly(trimethylene terephthalate) spin-coated films.

Here we present a precise morphological description of laser-induced periodic surface structures (LIPSS) nanofabricated on spin-coated poly(trimethylene terephthalate) (PTT) films by irradiation with 266 nm, 6 ns laser pulses and by using a broad range of fluences and number of pulses. By accomplishing real and reciprocal space measurements by means of atomic force microscopy and grazing incidence wide- and small-angle X-ray scattering respectively on LIPSS samples, the range of optimum structural order has been established. For a given fluence, an increase in the number of pulses tends to improve LIPSS in PTT. However, as the pulse doses increase above a certain limit, a distortion of the structures is observed and a droplet-like morphology appears. It is proposed that this effect could be related to a plausible decrease of the molecular weight of PTT due to laser-induced chain photo-oxidation by irradiation with a high number of pulses. A concurrent decrease in viscosity enables destabilization of LIPSS by the formation of droplets in a process similar to surface-limited dewetting.

Membrane potential in multi-ionic mixtures.

The membrane potential arising through charged porous membranes separating electrolyte mixtures at identical hydrostatic pressures but different concentrations was investigated theoretically by means of the steric, electric, and dielectric exclusion (SEDE) model. Transport phenomena were described through the Nernst-Planck formalism, while ion partitioning at the membrane/solution interfaces was accounted for by means of modified Donnan equations including steric and dielectric effects. The high concentration limit of the membrane potential depends on the mixture composition and the pore size as well. A specific feature of membrane potential in multi-ionic systems is the dependence at high concentration on the effective dielectric constant of the solution confined inside pores. Indeed, the effective dielectric constant inside pores does not affect the high concentration limit of the membrane potential in the case of single salt solutions. The low concentration limit of the membrane potential is independent of the mixture composition, the effective dielectric constant inside pores, and the pore radius, but it is ruled by counterions with the highest charge number. The membrane potential measured at high salt concentration with single salt solutions and electrolyte mixtures could be used to determine the pore size and the effective dielectric constant inside pores, respectively. This may constitute an alternative way for membrane characterization with the advantage of avoiding the need for additional rejection rate measurements.

Evaluation of the steric, electric, and dielectric exclusion model on the basis of salt rejection rate and membrane potential measurements.

The current work focuses on the application of the steric, electric, and dielectric exclusion (SEDE) model to the study of both the ion rejection rate and the membrane potential of a nanofiltration polyamide membrane. The aim of this study was to evaluate the performance of the SEDE model and to compare it with steric/electric exclusion theory. Experiments were conducted with CaCl(2) solutions at various concentrations. The SEDE model is a four-parameter model because the effective pore size (r(p)), the effective thickness-to-porosity ratio (Delta x/A(k)), the effective volume charge density of the membrane (X), and the dielectric constant of the solution inside the pores (epsilon(p)) have to be known to predict the rejection rate and the membrane potential. The first parameter was estimated from membrane potential measurements performed at high salt concentrations and the second from water permeability. In the case of single salt solutions, experimental rejection rates and membrane potentials can be described by a number of couples of values (X,epsilon(p)) because both electric and dielectric exclusion contribute to reject ions. A set of couples (X,epsilon(p)) were first estimated by fitting membrane potentials. One of the couples was found to provide a good description of experimental rejection rates as well. Results showed that the polyamide membrane is negatively charged in CaCl(2) solutions at natural pH and that the membrane charge increases with the salt concentration. A decrease in the effective dielectric constant inside the pores with respect to its bulk value was found. This is indirect evidence that dielectric exclusion plays a major role in the transport phenomena of the studied NF membrane. The standard steric/electric theory was also used to fit experimental rejection rates and membrane potentials, the effective volume charge density being the single adjustable parameter in this case. Unlike the SEDE model, the steric/electric exclusion theory was unable to account simultaneously for both rejection rate and membrane potential data by using a unique choice for X and epsilon(p). This highlights the global coherence of the SEDE model and the nonappropriateness of the description of transport in NF membranes by the classical steric/electric exclusion theory.

Contribution of convection, diffusion and migration to electrolyte transport through nanofiltration membranes.

Transport mechanisms through nanofiltration membranes are investigated in terms of contribution of convection, diffusion and migration to electrolyte transport. A Donnan steric pore model, based on the application of the extended Nernst-Planck equation and the assumption of a Donnan equilibrium at both membrane-solution interfaces, is used. The study is focused on the transport of symmetrical electrolytes (with symmetric or asymmetric diffusion coefficients). The influence of effective membrane charge density, permeate volume flux, pore radius and effective membrane thickness to porosity ratio on the contribution of the different transport mechanisms is investigated. Convection appears to be the dominant mechanism involved in electrolyte transport at low membrane charge and/or high permeate volume flux and effective membrane thickness to porosity ratio. Transport is mainly governed by diffusion when the membrane is strongly charged, particularly at low permeate volume flux and effective membrane thickness to porosity ratio. Electromigration is likely to be the dominant mechanism involved in electrolyte transport only if the diffusion coefficient of coions is greater than that of counterions.

Evaluation of the "DSPM" model on a titania membrane: measurements of charged and uncharged solute retention, electrokinetic charge, pore size, and water permeability.

The DSPM (Donnan steric partitioning pore model) was evaluated in the case of a titania membrane with "nanofiltration properties" by measuring the electrokinetic charge, pore size, and water permeability of the membrane, along with charged and uncharged solute retention. The zeta potential values (zeta) were determined from measurements of the electrophoretic mobility (EM) of titania powder forming the filtering layer of the membrane. Zeta potential values were converted into membrane volume charge (X) by assuming two limiting cases: a constant surface charge (sigma(s)(cst)) and a constant surface potential (psi(s)(cst)). The mean pore radius and thickness/porosity ratio of the membrane were determined by permporometry and from water permeability measurements, respectively. Retention measurements were carried out as a function of the permeate volume flux for both neutral solutes (polyethylene glycol PEG of different size) and salts (KCl, MgSO4, K2SO4, and MgCl2) at various pH values. Ionic retentions showed minimum values near the IEP of the membrane. Retention data were analyzed using the DSPM. Very good agreement was found between the pore radius calculated by the model and that determined by permporometry. X values calculated from fitting retention data using the DSPM were also in satisfactorily agreement with X values calculated from EM measurements assuming a constant surface potential for a large pH range. Furthermore, the DSPM leads to X values (X(DSPM)) between those calculated from EM (X(EM)) using the two limiting bounds. In other words, X(DSPM) was higher than X(EM) assuming psi(s)(cst) at pH values far from the isoelectric point (IEP) and lower than X(EM) assuming sigma(s)(cst). These results show that the DSPM is in qualitative agreement with the charge regulation theory (increase of the pore surface potential and decrease of the pore surface charge density with decreasing the pore size). On the other hand, the thickness/porosity ratio of the membrane calculated from solute retention data differed significantly from that determined from water permeability measurements. Moreover, a single value of Deltax/Ak could not be determined from PEG and salt retention data. This means that the Deltax/Ak parameter loses its physical meaning and includes physical phenomena which are not taken into account by the DSPM. Nevertheless, the model satisfactorily predicted the limiting retention, as this is not influenced by the Deltax/Ak parameter.

Electrokinetic characterization of porous plugs from streaming potential coupled with electrical resistance measurements.

The zeta potential of mixed nickel-iron oxide particles is evaluated by a new laboratory instrument. This latter allows the measurement of streaming potential together with the electrical resistance of porous plugs. The conductivity of electrolyte inside plug (pore conductivity) is deduced from electrical resistance measurements and is used together with streaming potential to evaluate the zeta potential by accounting for the surface conduction phenomenon. It is shown that neglecting the surface conduction phenomenon leads to a substantial underestimation of the zeta potential. The coupled measurements of streaming potential and plug electrical resistance yield zeta potential values that are in very good agreement with those obtained by electrophoresis. The densification of the porous plug with increasing pressure increments is put in evidence by the decrease in measured streaming potentials. Electrical resistance measurements make it possible to account for the increase in surface conductivity resulting from the more compacted structure of the plug. By doing so, the calculated zeta potential is found to be virtually independent of the pressure difference involved in streaming potential experiments, whereas the negligence of surface conduction phenomenon leads to a decrease in the apparent zeta potential with increasing pressure level.

Determining the Zeta Potential of Porous Membranes Using Electrolyte Conductivity inside Pores.

The zeta potential is an important and reliable indicator of the surface charge of membranes, and knowledge of it is essential for the design and operation of membrane processes. The zeta potential cannot be measured directly, but must be deduced from experiments by means of a model. The possibility of determining the zeta potential of porous membranes from measurements of the electrolyte conductivity inside pores (lambda(pore)) is investigated in the case of a ceramic microfiltration membrane. To this end, experimental measurements of the electrical resistance in pores are performed with the membrane filled with KCl solutions of various pHs and concentrations. lambda(pore) is deduced from these experiments. The farther the pH is from the isoelectric point and/or the lower the salt concentration is, the higher the ratio of the electrolyte conductivity inside pores to the bulk conductivity is, due to a more important contribution of the surface conduction. Zeta potentials are calculated from lambda(pore) values by means of a space charge model and compared to those calculated from streaming potential measurements. It is found that the isoelectric points are very close and that zeta potential values for both methods are in quite good agreement. The differences observed in zeta potentials could be due to the fact that the space charge model does not consider the surface conductivity in the inner part of the double layer. Measurements of the electrolyte conductivity within the membrane pores are proved to be a well-adapted procedure for the determination of the zeta potential in situations where the contribution of the surface conduction is significant, i.e., for small and charged pores. Copyright 2001 Academic Press.

Electrokinetic Phenomena in Homogeneous Cylindrical Pores.

The electrokinetic phenomena occurring in homogeneous cylindrical pores containing symmetric electrolytes are studied. The local relations for flow in the pores (Nernst-Planck and Navier-Stokes equations) are developed. The analysis includes a numerical solution of the nonlinear Poisson-Boltzmann equation. The integral expressions of the phenomenological coefficients coupling the solvent flow and the electrical current with the hydrostatic pressure and the electrical potential gradients are established and calculated numerically. The mobilities of anions and cations are individually specified and the electroviscous effects as well as the surface conductance are taken into account. Streaming potentials obtained from numerical calculations are compared with results given by classical relations in a range of zeta potentials and electrokinetic radii that may commonly occur in experimental investigation of micro- and ultrafiltration membranes. In this work, it is shown that classical approximated relations can give rise to very misleading conclusions and that the determination of the true zeta potential requires a full analysis (including numerical calculations) of the basic relations for flow and potential distribution in charged pores. Copyright 1999 Academic Press.

[Sonohysterography in the diagnosis of endometrial abnormalities]. / Sonohisterografia w róznicowaniu zmian w jamie macicy--doniesienie wstepne.

OBJECTIVES: The purpose of this study was to evaluate the usefulness of sonohisterography in the diagnosis of endometrial abnormalities. MATERIALS AND METHODS: The study included 28 pre- and postmenopausal women with abnormal vaginal bleeding scheduled for diagnostic curettage. We confronted the ultrasound findings and sonohysterography results with the histopathological diagnosis of the curettage specimens. RESULTS: Obtained data confirmed usefulness of sonohysterography in the differential diagnosis and topography of abnormalities in the uterine cavity. CONCLUSIONS: We believe that it's more precise to evaluate a single endometrial line using the sonohysterography technique. We can also suggest that sonohysterography may be a useful method in the early diagnosis of endometrial abnormalities and may be an alternative method for hospitals lacking hysteroscopic facilities.

[Evaluation of endometrial thickness by transvaginal ultrasonography as a screening method in early diagnosis of endometrial cancer]. / Ocena grubosci endometrium przy wykorzystaniu ultrasonografii przezpochwowej jako propozycja badania przesiewowego we wczesnym wykrywaniu raka endometrium.

OBJECTIVES: We analyzed the usefulness of transvaginal ultrasonography in the detection of early endometrial cancer. DESIGN: The purpose of the study was to compare histopathologic diagnosis of the curettage specimens with transvaginal ultrasound findings. MATERIALS AND METHODS: The study included 129 women with postmenopausal bleeding scheduled for curettage. Before the curettage was performed, the thickness of the endometrium was measured using double layer technique and the thickest part was identified in the longitudinal plane. RESULTS: In our study we didn't find endometrial hyperplasia or cancer when the endometrium was < 5 mm thick. CONCLUSIONS: We believe that transvaginal ultrasonography in women with or without postmenopausal bleeding may be a useful method in screening for endometrial cancer as the Papanicolaou screening test for the prophylaxies of cervical cancer.

[Evaluation of medical care at a delivery suite and maternity ward in the rooming-in system according to a survey of birthing mothers]. / Ocena opieki w bloku porodowym i oddziale pologowym w systemie "matka-dziecko" na podstawie przeprowadzonej ankiety wsród kobiet rodzacych.

We analysed 352 opinions of the quality of medical services to delivering women, puerperants and neonates. Every opinion was willingly done and anonymous. Over 75% of women found the medical care of nurses, accoucheuses and doctors as well done. More than half of patients positively expressed their opinion on health conditions, and their stay in hospital. This survey helped us to improve our behaviour and services to a single patient.