673 research outputs found
Loss of solutions in shear banding fluids in shear banding fluids driven by second normal stress differences
Edge fracture occurs frequently in non-Newtonian fluids. A similar
instability has often been reported at the free surface of fluids undergoing
shear banding, and leads to expulsion of the sample. In this paper the
distortion of the free surface of such a shear banding fluid is calculated by
balancing the surface tension against the second normal stresses induced in the
two shear bands, and simultaneously requiring a continuous and smooth meniscus.
We show that wormlike micelles typically retain meniscus integrity when shear
banding, but in some cases can lose integrity for a range of average applied
shear rates during which one expects shear banding. This meniscus fracture
would lead to ejection of the sample as the shear banding region is swept
through. We further show that entangled polymer solutions are expected to
display a propensity for fracture, because of their much larger second normal
stresses. These calculations are consistent with available data in the
literature. We also estimate the meniscus distortion of a three band
configuration, as has been observed in some wormlike micellar solutions in a
cone and plate geometry.Comment: 23 pages, to be published in Journal of Rheolog
Free volume dilatation in polymers by ortho-positronium
The possibility of positronium induced free volume cavity expansion in some polymers above the glass transition temperature was investigated using experimental positron annihilation lifetime data from the literature for polydimethylsiloxane, polyisobutylene, and polybutadiene as function of temperature. The results suggest that free volume sites can expand towards an equilibrium size, determined as the equilibrium Ps-bubble size defined earlier for low-molecular-weight liquids. The expansion can be explained by the increase of molecular mobility and hence decrease of relaxation times, which at the higher temperatures approach the o-Ps lifetimes. Nanoscale viscosities were estimated using Navier-Stokes equation and were found to be several orders of magnitude lower than the macroscopic viscosity at the same temperature
Phase Behavior of Polyelectrolyte Block Copolymers in Mixed Solvents
We have studied the phase behavior of the poly(n-butyl
acrylate)-b-poly(acrylic acid) block copolymer in a mixture of two miscible
solvents, water and tetrahydrofuran (THF). The techniques used to examine the
different polymers, structures and phases formed in mixed solvents were static
and dynamic light scattering, small-angle neutron scattering, nuclear magnetic
resonance and fluorescence microscopy. By lowering the water/THF mixing ratio
X, the sequence unimers, micron-sized droplets, polymeric micelles was
observed. The transition between unimers and the micron-sized droplets occurred
at X = 0.75, whereas the microstructuration into core-shell polymeric micelles
was effective below X = 0.4. At intermediate mixing ratios, a coexistence
between the micron-sized droplets and the polymeric micelles was observed.
Combining the different aforementioned techniques, it was concluded that the
droplet dispersion resulted from a solvent partitioning that was induced by the
hydrophobic blocks. Comparison of poly(n-butyl acrylate) homopolymers and
poly(n-butyl acrylate)-b-poly(acrylic acid) block copolymers suggested that the
droplets were rich in THF and concentrated in copolymers and that they were
stabilized by the hydrophilic poly(acrylic acid) moieties.Comment: 11 pages, 12 figures, to appear in Macromolecule
Non-Equilibrium in Adsorbed Polymer Layers
High molecular weight polymer solutions have a powerful tendency to deposit
adsorbed layers when exposed to even mildly attractive surfaces. The
equilibrium properties of these dense interfacial layers have been extensively
studied theoretically. A large body of experimental evidence, however,
indicates that non-equilibrium effects are dominant whenever monomer-surface
sticking energies are somewhat larger than kT, a common case. Polymer
relaxation kinetics within the layer are then severely retarded, leading to
non-equilibrium layers whose structure and dynamics depend on adsorption
kinetics and layer ageing. Here we review experimental and theoretical work
exploring these non-equilibrium effects, with emphasis on recent developments.
The discussion addresses the structure and dynamics in non-equilibrium polymer
layers adsorbed from dilute polymer solutions and from polymer melts and more
concentrated solutions. Two distinct classes of behaviour arise, depending on
whether physisorption or chemisorption is involved. A given adsorbed chain
belonging to the layer has a certain fraction of its monomers bound to the
surface, f, and the remainder belonging to loops making bulk excursions. A
natural classification scheme for layers adsorbed from solution is the
distribution of single chain f values, P(f), which may hold the key to
quantifying the degree of irreversibility in adsorbed polymer layers. Here we
calculate P(f) for equilibrium layers; we find its form is very different to
the theoretical P(f) for non-equilibrium layers which are predicted to have
infinitely many statistical classes of chain. Experimental measurements of P(f)
are compared to these theoretical predictions.Comment: 29 pages, Submitted to J. Phys.: Condens. Matte
Replication of Association between ADAM33 Polymorphisms and Psoriasis
Polymorphisms in ADAM33, the first gene identified in asthma by positional cloning, have been recently associated with psoriasis. No replication study of this association has been published so far. Data available in the French EGEA study (Epidemiological study on Genetics and Environment of Asthma, bronchial hyperresponsivensess and Atopy) give the opportunity to attempt to replicate the association between ADAM33 and psoriasis in 2002 individuals. Psoriasis (n = 150) has been assessed by questionnaire administered by an interviewer and a sub-sample of subjects with early-onset psoriasis (n = 74) has been identified based on the age of the subjects at time of interview (<40 years). Nine SNPs in ADAM33 and 11 SNPs in PSORS1 were genotyped. Association analysis was conducted by using two methods, GEE regression-based method and a likelihood-based method (LAMP program). The rs512625 SNP in ADAM33 was found associated with psoriasis at p = 0.01, the usual threshold required for replication (OR [95% CI] for heterozygotes compared to the reference group of homozygotes for the most frequent allele = 0.61 [0.42;0.89]). The rs628977 SNP, which was not in linkage disequilibrium with rs512625, was significantly associated with early-onset psoriasis (p = 0.01, OR [95% CI] for homozygotes for the minor allele compared to the reference group = 2.52 [1.31;4.86]). Adjustment for age, sex, asthma and a PSORS1 SNP associated with psoriasis in the EGEA data did not change the significance of these associations. This suggests independent effects of ADAM33 and PSORS1 on psoriasis. This is the first study that replicates an association between genetic variants in ADAM33 and psoriasis. Interestingly, the 2 ADAM33 SNPs associated with psoriasis in the present analysis were part of the 3-SNPs haplotypes showing the strongest associations in the initial study. The identification of a pleiotropic effect of ADAM33 on asthma and psoriasis may contribute to the understanding of these common immune-mediated diseases
Cancer risk in hospitalised psoriasis patients: a follow-up study in Sweden
We examined overall and specific cancer risks among Swedish subjects who had been hospitalised one or more times for psoriasis. A database was created by identifying such patients from the Swedish Hospital Discharge Register and linking them with the Cancer Registry. Follow-up of patients was carried out from the last hospitalisation through 2004. A total of 15 858 patients were hospitalised for psoriasis during 1965–2004, of whom 1408 developed cancer, giving an overall standardised incidence ratios (SIRs) of 1.33. A significant excess was noted for squamous cell skin cancer, and for cancers of the upper aerodigestive tract, oesophagus, stomach, liver, pancreas, lung, kidney and bladder as well as non-Hodgkin lymphoma. Many of these may reflect the effects of alcohol drinking and tobacco smoking. Patients with multiple hospitalisations showed high risk, particularly for oesophageal (SIR 6.97) and skin (SIR 4.76) cancers
Collecting a set of psoriasis family material through a patient organisation; clinical characterisation and presence of additional disorders
BACKGROUND: The aim of the present study was to describe the clinical characteristics of a population of psoriatics sampled from a patient organisation and not from hospitals or out-patient clinics. Furthermore, we wanted to compare siblings with and without psoriasis regarding the occurrence of other diseases. METHODS: At the end of 1991, we initiated a project which aimed to study genetic factors leading to psoriasis. Firstly, we sent questionnaires to all the members of the Swedish Psoriasis Association. We then examined 1,217 individuals (570 with psoriasis) from 310 families, in their homes in the southern part of Sweden. All the available family members were examined clinically and asked about the course of the skin disease and the occurrence of other diseases. The eight hundred members of the proband generation were divided into two groups, with or without psoriasis, and their clinical features were compared. RESULTS: Most individuals in this study population had a mild form of psoriasis. The siblings with psoriasis had joint complaints significantly more frequently than their siblings without the skin disease and those with joint complaints had more widespread skin disease. Among the other studied concomitant diseases (iritis, heart or hypertension disease, endocrine disease, inflammatory bowel disease and neurological disease), we were not able to find any difference. Seventy-seven of 570 persons were found to be in remission (13.5%). Females had a mean onset 2.5 years earlier than males. We were not able to find any correlation between the extent of the skin disease and age at onset. Twice as many persons with joint complaints were found among those with psoriasis than among those without, 28% versus 13%. Almost half (48%) the psoriatics who also had joint complaints had psoriasis lesions on their nails. Endocrine disorders were found in 9% of those without any allele for Cw6, but only in 1% of those who had Cw6. In fact, none of 183 Cw6 carriers had diabetes, as compared to the population prevalence of 3–5% in Sweden. CONCLUSION: With the exception of joint complaints, persons with psoriasis, collected from a patient organisation, did not have an increased frequency of (studied) co-existing diseases
Conformation and interactions of polystyrene and fullerenes in dilute to semidilute solutions
Mechanical Properties of Glassy Polyethylene Nanofibers via Molecular Dynamics Simulations
The extent to which the intrinsic mechanical properties of polymer fibers depend on physical size has been a matter of dispute that is relevant to most nanofiber applications. Here, we report the elastic and plastic properties determined from molecular dynamics simulations of amorphous, glassy polymer nanofibers with diameter ranging from 3.7 to 17.7 nm. We find that, for a given temperature, the Young’s elastic modulus E decreases with fiber radius and can be as much as 52% lower than that of the corresponding bulk material. Poisson’s ratio ν of the polymer comprising these nanofibers was found to decrease from a value of 0.3 to 0.1 with decreasing fiber radius. Our findings also indicate that a small but finite stress exists on the simulated nanofibers prior to elongation, attributable to surface tension. When strained uniaxially up to a tensile strain of ε = 0.2 over the range of strain rates and temperatures considered, the nanofibers exhibit a yield stress σy between 40 and 72 MPa, which is not strongly dependent on fiber radius; this yield stress is approximately half that of the same polyethylene simulated in the amorphous bulk.DuPont MIT AllianceDuPont (Firm) (Young Professor Award
Chemical resistance of core-shell particles (PS/PMMA) polymerized by seeded suspension
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