Thermal Degradation and Fire Behavior of High Performance Polymers

Abstract

High performance and high temperature polymers are a class of polymeric materials exhibiting high thermal stability and their resistance to fire makes them valuable assets for many applications. Those applications include as typical examples high temperature gas separation membranes, automotive and aerospace industry as well as the construction industry. The high performance polymers have been synthesized since the early 1960s, and have developed rapidly over the past few decades. Most high performance polymers comprise a highly aromatic backbone, linear chains, and strong inter-chain interactions. This review deals mostly with commercial polymeric materials. Studies regarding their thermal behavior, degradation mechanism and their reaction to fire have been synthetically combined in order to bring out potential insight concerning the effect of the thermal decomposition and thermal behavior on the fire properties of those polymers.     

Impact of drifts in the ASDEX upgrade upper open divertor using SOLPS-ITER

SOLPS-ITER L-mode-like simulations with the full set of currents and drift velocities activated, and fluid neutrals have been carried out to interpret experimental results obtained in AUG. Drifts are critical to quantitatively reproduce the experimental results; however, simulations without drifts can also reproduce some trends qualitatively. The magnitude and dependence of the peak heat flux onto both targets on the upstream collisionality are, in general, in quantitative agreement within uncertainties with infrared thermography measurements in favourable field direction. The onset of power detachment is observed. In unfavourable toroidal field direction, a more symmetrical inner/outer target solution with regards to the power distribution is predicted, in agreement with experimental observations. However, also in unfavourable toroidal field direction, insufficient power is dissipated in the simulations and therefore q_{peak, inn} is overpredicted by up to a factor of 4 and q_{peak, out} by up to a factor of 1.5. The largest contribution to the sources due to radial transport in the energy balance equation is the radial divergence of the energy flux due to V_{E × B}.     

An optimal asymptotic-numerical method for convection dominated systems having exponential boundary layers

The convection dominated diffusion problems are studied. Higher order accurate numerical methods are presented for problems in one and two dimensions. The underlying technique utilizes a superposition of given problem into two independent problems. The first one is the reduced problem that refers to the outer or smooth solution. Stretching transformation is used to obtain the second problem for inner layer solution. The method considered for outer or degenerate problems are based on higher order Runge–Kutta methods and upwind finite differences. However, inner problem is solved analytically or asymptotically. The schemes presented are proved to be consistent and stable. Possible extensions to delay differential equations and to nonlinear problems are outlined. Numerical results for several test examples are illustrated and a comparative analysis is presented. It is observed that the method presented is highly accurate and easy to implement. Moreover, the numerical results obtained are not only comparable with the exact solution but also in agreement with the theoretical estimates.     

Virtually epimerization-free synthesis of peptide-alpha-thioesters

Under slightly basic or neutral reaction conditions peptide-alpha-thioesters are photochemically synthesized from peptide-alpha-nitroindoline precursors, either in solution, or by direct photorelease from a solid support.     

Specificity of sites within eight-membered ring zeolite channels for carbonylation of methyls to acetyls

The acid-catalyzed formation of carbon-carbon bonds from C1 precursors via CO insertion into chemisorbed methyl groups occurs selectively within eight-membered ring (8-MR) zeolite channels. This elementary step controls catalytic carbonylation rates of dimethyl ether (DME) to methyl acetate. The number of O-H groups within 8-MR channels was measured by rigorous deconvolution of the infrared bands for O-H groups in cation-exchanged and acid forms of mordenite (M,H-MOR) and ferrierite (H-FER) after adsorption of basic probe molecules of varying size. DME carbonylation rates are proportional to the number of O-H groups within 8-MR channels. Na+ cations selectively replaced protons within 8-MR channels and led to a disproportionate decrease in carbonylation turnover rates (per total H+). These conclusions are consistent with the low or undetectable rates of carbonylation on zeolites without 8-MR channels (H-BEA, H-FAU, H-MFI). Such specificity of methyl reactivity upon confinement within small channels appears to be unprecedented in catalysis by microporous solids, which typically select reactions by size exclusion of bulkier transition states.     

White-light-induced fragmentation of methane

We experimentally probe molecular ionization and dissociation of methane molecules in the gas phase upon their irradiation by intense pulses of white light that spans the wavelength range 500-850 nm. White light pulses are generated upon irradiation of BK7 glass by 36-fs-long pulses of intense 820 nm laser light. Comparison is made of the molecular fragmentation patterns obtained using white light that is depolarized with those obtained using single-color (820 nm) light that is highly chirped. On the basis of such comparison, we make hitherto-unavailable estimates of the in situ intensity of white light pulses. Results obtained using white light also indicate that resonances apparently do not play any role in the ionization dynamics that ensue upon irradiation by intense, broadband light; neither are the dynamics affected by the polarization properties of the 820 nm light that is used to generate the white light.     

The bulk electroviscous effect

Electroviscous stresses arise as hydrodynamic flows disturb the ionic (Debye) clouds that screen charged surfaces in electrolyte solutions. The contribution thereof to the effective bulk viscosity (also known as the second or volume viscosity) of two-phase suspensions is quantified here. Specifically, the bulk viscosity of two model suspensions is calculated: (1) a dilute dispersion of rigid charged spherical particles immersed in a compressible electrolyte that undergoes uniform dilatation and (2) a dilute suspension of charged gas bubbles expanding uniformly in an incompressible electrolyte. In both cases, it is assumed that the fluid flow only slightly drives the Debye cloud out of equilibrium, which formally requires that the ratio of the ion diffusion to flow time scales—a Péclet number—is small. For a suspension of rigid particles, the electroviscous contribution to the effective bulk viscosity is proportional to the particle volume fraction and decreases monotonically as the ratio of the particle radius to the Debye length increases. Similar behavior is well known for the electroviscous contribution to the effective shear viscosity of a dilute hard-sphere suspension; a quantitative comparison between the bulk and shear viscosities is made. In contrast, the electroviscous contribution to the bulk viscosity of a dilute suspension of bubbles is independent of the bubble volume fraction and attains a finite value in the limit of vanishing Debye length.     

Pendant polymer:amino-β-cyclodextrin:siRNA guest:host nanoparticles as efficient vectors for gene silencing

A novel siRNA delivery vector has been developed, based on the self-assembly of monosubstituted cationic β-CD derivatives with a poly(vinyl alcohol)MW27kD (PVA) main-chain polymer bearing poly(ethylene glycol)MW2000 (PEG) and acid-labile cholesterol-modified (Chol) grafts through an acid-sensitive benzylidene acetal linkage. These components were investigated for their ability to form nanoparticles with siRNA using two different assembly schemes, involving either precomplexation of the pendant Chol-PVA-PEG polymer with the cationic β-CD derivatives before siRNA condensation or siRNA condensation with the cationic β-CD derivatives prior to addition of Chol-PVA-PEG to engage host:guest complexation. The pendant polymer:amino-β-CD:siRNA complexes were shown to form nanoparticles in the size range of 120-170 nm, with a slightly negative zeta potential. Cell viability studies in CHO-GFP cells shows that these materials have 10(3)-fold lower cytotoxicities than 25 kD bPEI, while maintaining gene-silencing efficiencies that are comparable to those of benchmark transfection reagents such as bPEI and Lipofectamine 2000. These results suggest that the degradable Chol-PVA-PEG polymer is able to self-assemble in the presence of siRNA and cationic-β-CD to form nanoparticles that are an effective and low-toxicity vehicle for delivering siRNA cargo to target cells.     

Performance study and assessment of phase noise suppression by incoherent addition in a mode-locked fiber laser system

This paper investigates the effectiveness of phase noise suppression by incoherent addition in a passively mode-locked fiber laser. Incoherent addition is achieved by using an interferometer external to the mode-locked laser. Two different types of interferometers, Mach–Zehnder and ring, are investigated experimentally for different background phase noise levels. Measurements show that both types of interferometers can achieve good phase noise reduction for a background phase noise level above ? 130 dBc/Hz. Effects of dispersion management and pulse train intensity ratio in the interferometers are also discussed. Multi-stage cascaded interferometers are proposed for supermode noise suppression of harmonically actively mode-locked lasers.