Thermodynamic analysis of high-temperature regenerative organic Rankine cycles using siloxanes as working fluids

A recent novel adjustment of the Span-Wagner equation of state for siloxanes, used as working fluids in high-temperature organic Rankine cycles, is applied in a mathematical model to solve cycles under several working conditions. The proposed scheme includes a thermo-oil intermediate heat circuit between the heat source and the organic Rankine cycle. Linear and cyclic siloxanes are assayed in saturated, superheated and supercritical cycles. The cycle includes an internal heat exchanger (regenerative cycle), although a non-regenerative scheme is also solved. In the first part of the study, a current of combustion gases cooled to close to their dew point temperature is taken as the reference heat source. In the second part, the outlet temperature of the heat source is varied over a wide range, determining appropriate fluids and schemes for each thermal level. Simple linear (MM, MDM) siloxanes in saturated regenerative schemes show good efficiencies and ensure thermal stability of the working fluid.     

Particle-induced network formation in linear PDMS filled with silica

We study the formation of permanent elastomers from linear PDMS chains by solution blending with up to 25 wt% fumed silica. The physical networks are characterized by time-domain multiple-quantum NMR. Based upon dynamic parameters measured for the linear precursor polymer, we develop a reliable strategy for component separation in this complex heterogeneous system, providing information on the amount of monomers involved in network-like material, in elastically inactive yet entangled linear chains, and isotropically mobile chain ends, as well as on the effective network chain length as measured via the average residual dipolar coupling constant. The use of untreated silica leads to permanent networks, for which the NMR results correlate well with macroscopic determinations of the relaxed Young modulus and the degree of swelling. Surface-modified silicas do not lead to percolated network structures, but still lead to the formation of 20–40% network-like material, with effective network chain lengths that depend on the surface functionalization and thus on the nanoparticle dispersion. Characteristic changes in the mobile chain end fraction with temperature, in particular its decrease with increasing degree of filling are interpreted as a consequence of altered contour-length fluctuations. An aging experiment conducted on a sample prepared by melt blending reveals the microscopic changes in the network structure occurring over many months.     

A molecular dynamics study of siloxane diffusion in a polyester-melamine solution

This study examines the diffusion of small methylated and hydroxylated siloxanes through solutions of polymer and crosslinker molecules. The diffusivity of the siloxanes was calculated for bulk diffusion and for surface segregation. Our simulations demonstrate that there is significant interaction between 3,3-dimethylhexahydroxytrisiloxane (hexa-OH-TS) and the polar solvent components of the paint matrix at 298 K. The nature of these associations is largely due to hydrogen bonding between the siloxane and the polar solvent molecules. At 573 K the diffusivity of solvent molecules is sufficiently high to disrupt interactions. The smaller number of hydroxyl groups in 1,5-dihydroxyhexamethyltrisiloxane (hexa-Me-TS) results in a weaker interaction with the polar solvent. Surface segregation studies indicate that there is a slight increase in the concentration of hexa-OH-TS in the surface layer of the system as a result of curing and relaxation processes. However, for hexa-Me-TS there is in fact a decrease in the surface concentration of the siloxane relative to the bulk concentration.     

The effects of hydrogen addition on silica aggregate growth in atmospheric-pressure, 1-D methane/air flames with hexamethyldisiloxane admixture

The effect of hydrogen addition on silica growth in burner-stabilized methane/air flames with trace amounts of hexamethyldisiloxane are reported. Profiles of the aggregates' radius of gyration $R_g$ and monomer radius $a$ versus residence time were measured by laser light scattering. Experiments were performed at equivalence ratios of 0.8, 1.0 and 1.3, with mole fractions of 0–0.4 of hydrogen in the fuel. At equal mass flux, the addition of hydrogen was found to result in decreasing $R_g$ and $a$. However, keeping the flame temperature rather than the mass flux constant upon hydrogen addition resulted in the same measured profiles.