Drying of glassy polymer varnishes: A quartz resonator study

We report on desorption measurements on polymeric thin films coated onto quartz crystal resonators. Due to the high sensitivity of quartz crystal microbalances, the experiments can be performed on very thin films, which have small diffusion time constants even in the glassy state. When drying is performed slowly enough, diffusion equilibrium can be maintained through the whole process of desorption, including the glassy domain. From these quasi-stationary pressure ramps, we derived the solvent chemical potential as a function of polymer volume fraction μ(ϕ). The results fit well to a model recently proposed by Leibler and Sekimoto.¹ In addition, we have derived the mutual diffusion coefficient D(ϕ) from pressure step experiments. We observe a strong decrease of D(ϕ) for high polymer concentrations typical of hypodiffusive systems like polymers. We investigated the drying of an industrial varnish that is a blend of 2 copolymers as well as the drying of its components separately. Both the solvent chemical potential μ(ϕ) and the mutual diffusion coefficient D(ϕ) of the blend interpolate between the respective quantities of the components. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2235–2246, 1998     

Some aspects of isotactic polypropylene crystallization in an ethylene–propylene–diene rubber matrix

Crystallization of isotactic polypropylene (iPP) in an ethylene–propylene–diene rubber matrix (EPDM), crosslinked with dicumyl peroxide (DCP), has been studied. A discrepancy concerning the degree of crystallinity of the blends determined using different experimental techniques, has been discovered and an effort to explain it is made. iPP was found to recrystallize in EPDM in a manner, depending on the amount of plastomer added. Nucleation, being predominantly homogeneous for ‘pure’ iPP, becomes predominantly hetero-geneous for its blends with EPDM. The smaller the polypropylene content the more a defect crystalline phase is formed. The defects, as well as an orientation were shown to be responsible for the higher, in comparison with other methods, degree of crystallinity determined by wide-angle X-ray scattering. ©1997 SCI     

Design and characterization of a lamellar nanostructure in a low C steel

A fully lamellar ferrite/cementite nanostructure was designed in a low C steel by using a specific thermal treatment. The strengthening of such microstructure has been investigated as a function of prestrain by rolling up to a deformation of 300%. As in usual pearlitic structure, its work-hardening shows no saturation and its elongation to fracture remains rather constant instead of decreasing drastically as conventional steels. The hardening by a similitude effect is thus not the privilege of pearlitic steels. Nevertheless, its lower initial work-hardening rate at low strain compared to an equivalent pearlitic steel and a lower hardening potential at high strain let us suspect major differences in the nature and the behaviour of ferrite channels in relation to the morphogenesis of the microstructure. This study opens a new way to obtain low carbon ultra-high strength steel by a nanostructuration process using severe plastic deformations.     

Characterization of the Absorption of Theophylline From Immediate- and Controlled-Release Dosage Forms With a Numerical Approach Using the In Vitro Dissolution-Permeation Process Using Caco-2 Cells

After oral administration, drug absorption rate is recognized to be dependent on two major factors: dissolution and intestinal cells permeability. Caco-2 monolayer cells have been largely used as a permeation study model. In this study, a numerical approach funded on an exponential first-order time relationship was tested to compare immediate- and controlled-release tablets of theophylline using a dissolution-permeation system. The dissolution performance using USP II paddle apparatus was coupled to the permeability studies investigated in Caco-2 cell monolayers. The dissolved samples were taken at different times; their pH and osmolarity were adjusted to render them suitable to Caco-2 permeability studies (osmolarity = 300 mosm, pH = 7.4). The experimental data show that the dissolution fits the exponential first-order relationship rate. The permeability values were in a range of 4.45 10^{? 6}–5.28 10^{? 6} cm/s, and percentages of absorbed drug dose were dependent on the fraction initially present in the donor compartment, indicating that absorption of theophylline was dissolution rate limited. Plotting experimental absorbed fractions (F_a) against experimental dissolved fractions (F_d) show that permeation is the rate-limiting step in drug absorption process in the extended release form of theophylline. Our results demonstrate a general agreement between observed F_a/F_d relationships and theoretical F_a/F_d relationships obtained with our approach funded on dissolution and permeation behavior. We concluded that the couple dissolution-caco-2 system could be a useful tool to characterize intestinal permeation for a new formulation of a drug compared with the conventional one.     

Octreotide acts on anorectal physiology: a dynamic study in healthy subjects

To evaluate the normal development of functional hand motor skill, the kinematics of prehension movements were analyzed in 54 healthy children (age 4-12 years). The subjects repeatedly reached out for cylindrical target objects and grasped them with a precision grip of their dominant hand. The trajectory of the reaching hand and the finger aperture were monitored by optoelectronic motion analysis. To obtain comparable conditions for the different age groups, the experimental setup was scaled according to the individual body proportions of each subject. Within the investigated age range, neither the movement duration nor the normalized (according to body proportions) peak spatial velocity of the reaching hand changed significantly. However, the hand trajectory straightened and the coordination between hand transport and grip formation improved, resulting in smooth and stereotyped kinematic profiles at the age of 12 years. The younger children opened their grip relatively wider than the older ones, thus grasping with a higher safety margin. The dependence on visual control of the movement declined during motor development. Only the oldest children were able to scale the grip aperture adequately, according to various sizes of the target objects, when visual control of the movement was lacking. The results suggest that the development of prehensile skills during childhood lasts until the end of the first decade of life. This functional maturation is discussed in relation to the development of neuronal pathways.     

From Zr-Rich to Ce-Rich: Thermal Stability of OSC Materials on the Whole Range of Composition

Car manufacturers use close coupled three way catalysts to reduce cold start emissions. These close coupled catalysts must show long term durability and thermal stability at temperatures higher than 1000 °C. Thus, during the past 10 years, a significant amount of attention has been paid to the design of CeO₂-ZrO₂ OSC materials with improved surface area, phase and OSC stability. Solid solutions of Ce/Zr mixed oxides are now commonly available on industrial scale. Recent studies have demonstrated that the introduction of rare earth oxides promoters such as La, Pr, Nd, Y, Sm [ENGELHARD WO patent o2 30546; OMG-DMC² EP Patent 1 181 970; DAIHATSU EP Patent 1 174 174; DELPHI US Patent 6 387 338; ENGELHARD WO Patent 02 22242] or aluminium oxide [TOYOTA EP Patent 1 172 139; Kanzawa et al. SAE Technical Paper 2003-01-0811] in the Ce/Zr matrix is a very good way to improve the thermal stability and the redox properties of these materials. Positive interactions between PGM and these 'promoters' are also claimed. Nevertheless, not only the composition but the optimization of the manufacturing processes is a key factor to obtain both high thermal stability (expressed as surface area and XRD phase purity) and OSC. To meet the increasingly stringent emission limits, Rhodia has developed a new generation of CeZr based mixed oxides. These materials show phase stability and thermal stability at temperatures higher than 1100 °C in a wide composition range: from Zr-rich to Ce-rich mixed oxides. These characteristics have been obtained with a new manufacturing process which leads to highly porous materials. The controlled morphology at microscopic and macroscopic scale prevents particle sintering under severe ageing conditions. Such materials are preferred PGM supports for cost effective catalysts with low PGM loading     

Experimental characterization of buoyancy- and surface tension-driven convection during the drying of a polymer solution

Within the framework of convection induced by evaporation, an experimental study of the drying of a polymer solution has been performed. Several visualisations of convective pattern development are presented: top view with a video camera and an IR camera, as well as visualisation in a vertical section. The appearance and origin (buoyancy- and/or surface tension-driven instabilities) of the convective structures are analysed as a function of the initial thickness and viscosity. Different regimes are obtained when comparing the lifetime of the convective patterns to the thermal transient regime induced by evaporation and to the formation of a thin viscous skin at the surface.     

Causal assessment of drug-induced acute colitis. A prospective study of 58 consecutive cases

AIMS: The causal effect of drugs is underestimated in patients with inflammatory bowel disease. The aim of this study was to assess the causal implication of drugs in acute colitis. METHODS: A prospective study was conducted in 58 consecutive patients with an acute inflammation of the colonic mucosa. Recent drug intake was recorded and possible causal effects were analyzed exhaustively with respect to both intrinsic and bibliographic criteria. RESULTS: Causal assessment scores were high for 57 drugs and 41 patients. Drug-induced acute colitis was diagnosed in 35 cases. In 7 patients, physician practice had not taken into account drug use despite probable drug involvement. The main drugs implicated were antibiotics (n = 42) and non steroidal anti-inflammatory drugs (n = 10). CONCLUSION: Acute colitis is mainly induced by drugs.     

High-performance liquid chromatographic determination of 4-methylpyrazole in plasma and in dialysate

A rapid method for the determination of 4-methylpyrazole (4-MP) levels in plasma and in dialysate by isocratic reversed-phase high-performance liquid chromatography with UV detection is described. The internal standard was the 3-methylpyrazole (3-MP). Plasma sample preparation consisted of a protein precipitation. Dialysate samples were injected without preparation. The method was linear up to 30 mg l(-1) in plasma and up to 5 mg l(-1) in dialysate. The within-day precisions (C.V.) were less than 4% in plasma and were less than 2% in dialysate. The day-to-day precisions (C.V.) were less than 7% in plasma and were less than 3% in dialysate. This method is easy to perform and has practical interest for clinicians who need to monitor in emergency 4-MP levels in ethylene glycol and methanol poisonings.