Predicting enhanced absorption of light gases in polyethylene using simplified PC-SAFT and SAFT-VR

International audienceAbsorption of light gases in polyethylene (PE) is studied using two versions of the Statistical Associating Fluid Theory (SAFT): SAFT for chain molecules with attractive potentials of variable range (VR) and simplified perturbed-chain (PC) SAFT. Emphasis is placed on the light gases typically present during ethylene polymerisation in the gas-phase reactor (GPR) process. The two approaches are validated using experimental binary-mixture data for gas absorbed in PE, and predictions are made for mixtures of more components. For most cases studied both SAFT versions perform equally well. For the case of ternary mixtures of two gases with PE, it is predicted that the less-volatile of the two gases acts to enhance the absorption of the more-volatile gas, while the more-volatile gas inhibits the absorption of the less-volatile gas. This general behaviour is also predicted in mixtures containing more gases, such as typical reactor mixtures. The magnitude of the effect may vary considerably, depending on the relative proximity of the gas-mixture saturation pressure to the reactor pressure; for example it is predicted that the absorption of ethylene may be approximately doubled if diluent gases, propane or nitrogen, are partially or completely replaced by less-volatile butane or pentane for a reactor pressure similar to 2 MPa. In the case of a co-polymerisation reaction, it is predicted that increases in absorption of both co-monomers may be obtained in roughly equal proportion. Our findings cast light on the so-called co-monomer effect, in which substantial increases in the rate of ethylene polymerisation are observed in the presence of hexene co-monomer, while suggesting that the effect is more general and not restricted to co-monomer. For example, similar rate increases may be expected in the presence of, e.g., pentane instead of hexene, but without the change in the branch structure of the produced polymer that is inevitable when the amount of co-monomer is increased

Characteristics of a cohort of high-risk men who have sex with men on pre-exposure prophylaxis reporting transgender sexual partners.

Transgender people continue to be at high-risk for HIV acquisition, but little is known about the characteristics of their sexual partners. To address this gap, we examined sociodemographic and sexual characteristics of cisgender men who have sex with men (MSM) on pre-exposure prophylaxis (PrEP) reporting transgender sexual partners.A cohort of 392 MSM in southern California in a randomized clinical trial for PrEP adherence were followed from 2013 to 2016. Multivariable generalized estimating equation and logistic models identified characteristics of MSM reporting transgender sexual partners and PrEP adherence.Only 14 (4%) MSM reported having transgender sexual partners. MSM were more likely to report transgender partners if they were African American, had incident chlamydia, reported injection drug-using sexual partners, or received items for sex. Most associations remained significant in the multivariable model: African American (adjusted odds ratio [AOR] 11.20, P = .01), incident chlamydia (AOR 3.71, P = .04), and receiving items for sex (AOR 5.29, P = .04). There were no significant differences in PrEP adherence between MSM reporting transgender partners and their counterpart.MSM who report transgender sexual partners share characteristics associated with individuals with high HIV prevalence. Identifying this group distinct from larger cohorts of MSM could offer new HIV prevention opportunities for this group of MSM and the transgender community

Criticality in strongly correlated fluids

In this brief review I will discuss criticality in strongly correlated fluids. Unlike simple fluids, molecules of which interact through short ranged isotropic potential, particles of strongly correlated fluids usually interact through long ranged forces of Coulomb or dipolar form. While for simple fluids mechanism of phase separation into liquid and gas was elucidated by van der Waals more than a century ago, the universality class of strongly correlated fluids, or in some cases even existence of liquid-gas phase separation remains uncertain.Comment: Proceedings of Scaling Concepts and Complex Systems, Merida, Mexic

Ordering of droplets and light scattering in polymer dispersed liquid crystal films

We study the effects of droplet ordering in initial optical transmittance through polymer dispersed liquid crystal (PDLC) films prepared in the presence of an electrical field. The experimental data are interpreted by using a theoretical approach to light scattering in PDLC films that explicitly relates optical transmittance and the order parameters characterizing both the orientational structures inside bipolar droplets and orientational distribution of the droplets. The theory relies on the Rayleigh-Gans approximation and uses the Percus-Yevick approximation to take into account the effects due to droplet positional correlations.Comment: revtex4, 18 pages, 8 figure

The Structure of the Vortex Liquid at the Surface of a Layered Superconductor

A density-functional approach is used to calculate the inhomogeneous vortex density distribution in the flux liquid phase at the planar surface of a layered superconductor, where the external magnetic field is perpendicular to the superconducting layers and parallel to the surface. The interactions with image vortices are treated within a mean field approximation as a functional of the vortex density. Near the freezing transition strong vortex density fluctuations are found to persist far into the bulk liquid. We also calculate the height of the Bean-Livingston surface barrier.Comment: 8 pages, RevTeX, 2 figure

Self Consistent Molecular Field Theory for Packing in Classical Liquids

Building on a quasi-chemical formulation of solution theory, this paper proposes a self consistent molecular field theory for packing problems in classical liquids, and tests the theoretical predictions for the excess chemical potential of the hard sphere fluid. Results are given for the self consistent molecular fields obtained, and for the probabilities of occupancy of a molecular observation volume. For this system, the excess chemical potential predicted is as accurate as the most accurate prior theories, particularly the scaled particle (Percus-Yevick compressibility) theory. It is argued that the present approach is particularly simple, and should provide a basis for a molecular-scale description of more complex solutions.Comment: 6 pages and 5 figure

Paramagnetic Phase of a Heavy-Fermion Compound, CeFePO, Probed by 57Fe M\"{o}ssbauer Spectroscopy

57Fe M\"{o}ssbauer spectroscopy was applied to an iron-based layered compound CeFePO. At temperatures from 9.4 to 293 K, no magnetic splitting was observed in the M\"ossbauer spectra of CeFePO indicating a paramagnetic phase of the Fe magnetic sublattice. All the spectra were fitted with a small quadrupole splitting, and the Debye temperature of CeFePO was found to be \sim448 K. The isomer shift at room temperature, 0.32 mm/s, was almost equal to those of LnFeAsO (Ln = La, Ce, Sm). Comparing s-electron density using the isomer shifts and unit cell volumes, it was found that the Fe of CeFePO has a similar valence state to other layered iron-based quaternary oxypnictides except LaFePO

Effective Magnetic Hamiltonian and Ginzburg Criterion for Fluids

We develop further the approach of Hubbard and Schofield (Phys.Lett., A40 (1972) 245), which maps the fluid Hamiltonian onto a magnetic one. We show that all coefficients of the resulting effective Landau-Ginzburg-Wilson (LGW) Hamiltonian may be expressed in terms of the compressibility of a reference fluid containing only repulsive interactions, and its density derivatives; we calculate the first few coefficients in the case of the hard-core reference fluid. From this LGW-Hamiltonian we deduce approximate mean-field relations between critical parameters and test them on data for Lennard-Jones, square-well and hard-core-Yukawa fluids. We estimate the Ginzburg criterion for these fluids.Comment: 4 pages, LaTeX, To appear in Phys.Rev.

Ninth and Tenth Order Virial Coefficients for Hard Spheres in D Dimensions

We evaluate the virial coefficients B_k for k<=10 for hard spheres in dimensions D=2,...,8. Virial coefficients with k even are found to be negative when D>=5. This provides strong evidence that the leading singularity for the virial series lies away from the positive real axis when D>=5. Further analysis provides evidence that negative virial coefficients will be seen for some k>10 for D=4, and there is a distinct possibility that negative virial coefficients will also eventually occur for D=3.Comment: 33 pages, 12 figure