Equilibrium and transport properties of CO2+N2O and CO2+NO mixtures : a molecular simulation and equation of state modelling study.

International audienceIn the present study, the thermodynamic behaviour and transport properties of CO2+N2O and CO2+NO mixtures have been investigated using molecular simulation and equation of state modelling. Molecular simulations were based on Monte Carlo and Molecular Dynamics calculations using force fields calibrated from pure component properties and no adjustment of mixture properties was performed. Original force fields were proposed for N2O, NO and N2O2 molecules. Special attention must be paid when studying nitric oxide containing systems because this compound can exist as a mixture of monomers (NO) and dimers (N2O2) under certain pressure and temperature conditions. Liquid-vapour coexistence properties of the reacting NO-N2O2 system were thus first investigated using combined reaction ensemble and Gibbs ensemble Monte Carlo methods. Using the new force fields proposed, phase compositions, phase densities and phase viscosities were determined for CO2+NOx mixtures. Due to the strong similarities between carbon dioxide and nitrous oxide (Tc(CO2) = 304.21 K; Tc(N2O) = 309.57 K; Pc(CO2) = 7.38 MPa; Pc(N2O) = 7.24 MPa), the obtained thermodynamic and transport properties for a CO2+N2O mixture with 10 mol% of N2O are similar to pure CO2 properties in the whole range of studied temperatures (273 - 293 K), in agreement with available experimental data. Calculations of CO2+NO equilibrium and transport properties were also performed at three different temperatures in the range of 253 - 273 K. At these temperatures, only the monomer form of the nitric oxide (NO) has to be accounted for. The performed calculations are pure predictions since no experimental data are available in the open literature for this system. For a mixture containing 10 mol% of NO, the simulation results show a decrease of the liquid densities and viscosities of 9% and 24% with respect to corresponding pure CO2 values, respectively. The new pseudo-experimental data generated in this work were finally used to calibrate binary interaction parameters required in standard cubic equations of states. Both Peng-Robinson and Soave-Redlich-Kwong equations of state have been considered and after the regression, they display a decent match with experimental and pseudo-experimental data of the vapour-liquid equilibrium for the two studied mixtures

NEW DESCRIPTORS TO CHARACTERIZE POROUS MATERIALS

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Molecular weight effects on chain pull-out fracture of reinforced polymeric interfaces

Using Brownian dynamics, we simulate the fracture of polymer interfaces reinforced by diblock connector chains. We find that for short chains the interface fracture toughness depends linearly on the degree of polymerization $N$ of the connector chains, while for longer chains the dependence becomes $N^{3/2}$. Based on the geometry of initial chain configuration, we propose a scaling argument that accounts for both short and long chain limits and crossover between them.Comment: 5 pages, 3 figure

Continuous EB welding of the reinforcement of the CMS conductor

The Compact Muon Solenoid (CMS) is one of the general-purpose detectors to be provided for the LHC project at CERN. The design field of the CMS superconducting magnet is 4 T, the magnetic length is 12.5 m and the free bore is 6 m. In order to withstand the electro-mechanical forces during the operation of the CMS magnet, the superconducting cable embedded in a 99.998% pure aluminum matrix is reinforced with two sections of aluminum alloy EN AW-6082 assembled by continuous Electron Beam Welding (EBW). A dedicated production line has been designed by Techmeta, a leading company in the field of EBW. The production line has a total length of 70 m. Non-stop welding of each of the 20 lengths of 2.5 km, required to build the coil, will last 22 hours. EBW is the most critical process involved in the production line. The main advantage of the EBW process is to minimize the Heat Affected Zone; this is particularly important for avoiding damage to the superconducting cable located only 4.7 mm from the welded joints. Two welding guns of 20 kW each operate in parallel in a vacuum chamber fitted with dynamic airlocks. After welding, the conductor is continuously machined on the four faces and on each corner to obtain the required dimensions and surface finish. Special emphasis has been put on quality monitoring. All significant production parameters are recorded during operation and relevant samples are taken from each produced length for destructive testing purposes. In addition, a continuous phased array ultrasonic checking device is located immediately after the welding unit for the continuous welding quality control, along with a dimension laser measurement unit following the machining. (8 refs)

On the nature of surface roughness with application to contact mechanics, sealing, rubber friction and adhesion

Surface roughness has a huge impact on many important phenomena. The most important property of rough surfaces is the surface roughness power spectrum C(q). We present surface roughness power spectra of many surfaces of practical importance, obtained from the surface height profile measured using optical methods and the Atomic Force Microscope. We show how the power spectrum determines the contact area between two solids. We also present applications to sealing, rubber friction and adhesion for rough surfaces, where the power spectrum enters as an important input.Comment: Topical review; 82 pages, 61 figures; Format: Latex (iopart). Some figures are in Postscript Level

Tensile Fracture of Welded Polymer Interfaces: Miscibility, Entanglements and Crazing

Large-scale molecular simulations are performed to investigate tensile failure of polymer interfaces as a function of welding time $t$. Changes in the tensile stress, mode of failure and interfacial fracture energy $G_I$ are correlated to changes in the interfacial entanglements as determined from Primitive Path Analysis. Bulk polymers fail through craze formation, followed by craze breakdown through chain scission. At small $t$ welded interfaces are not strong enough to support craze formation and fail at small strains through chain pullout at the interface. Once chains have formed an average of about one entanglement across the interface, a stable craze is formed throughout the sample. The failure stress of the craze rises with welding time and the mode of craze breakdown changes from chain pullout to chain scission as the interface approaches bulk strength. The interfacial fracture energy $G_I$ is calculated by coupling the simulation results to a continuum fracture mechanics model. As in experiment, $G_I$ increases as $t^{1/2}$ before saturating at the average bulk fracture energy $G_b$. As in previous simulations of shear strength, saturation coincides with the recovery of the bulk entanglement density. Before saturation, $G_I$ is proportional to the areal density of interfacial entanglements. Immiscibiltiy limits interdiffusion and thus suppresses entanglements at the interface. Even small degrees of immisciblity reduce interfacial entanglements enough that failure occurs by chain pullout and $G_I \ll G_b$

SNPs in DNA repair or oxidative stress genes and late subcutaneous fibrosis in patients following single shot partial breast irradiation

<p>Abstract</p> <p>Background</p> <p>The aim of this study was to evaluate the potential association between single nucleotide polymorphisms related response to radiotherapy injury, such as genes related to DNA repair or enzymes involved in anti-oxidative activities. The paper aims to identify marker genes able to predict an increased risk of late toxicity studying our group of patients who underwent a Single Shot 3D-CRT PBI (SSPBI) after BCS (breast conserving surgery).</p> <p>Methods</p> <p>A total of 57 breast cancer patients who underwent SSPBI were genotyped for SNPs (single nucleotide polymorphisms) in XRCC1, XRCC3, GST and RAD51 by Pyrosequencing technology. Univariate analysis (ORs and 95% CI) was performed to correlate SNPs with the risk of developing ≥ G2 fibrosis or fat necrosis.</p> <p>Results</p> <p>A higher significant risk of developing ≥ G2 fibrosis or fat necrosis in patients with: polymorphic variant <it>GSTP1 </it>(Ile105Val) (OR = 2.9; 95%CI, 0.88-10.14, <it>p </it>= 0.047).</p> <p>Conclusions</p> <p>The presence of some SNPs involved in DNA repair or response to oxidative stress seem to be able to predict late toxicity.</p> <p>Trial Registration</p> <p>ClinicalTrials.gov: <a href="http://www.clinicaltrials.gov/ct2/show/NCT01316328">NCT01316328</a></p