SAXS analysis of a linear polyester and a linear polyether urethane—interfacial thickness determination

A small-angle x-ray scattering (SAXS) investigation of two linear segmented polyurethanes was carried out to learn about the respective domain structure (morphology). Both urethanes had a hard segment of methylene-bis(4)phenyl isocyanate (MDI) and butanediol. These two components comprised 28% by weight of each system. The soft segments differed in that one was a polyether (tetramethylene oxide, molecular weight 1000), while the other was a polyester (polytetramethylene adipate, molecular weight 1000). Both of these segmented urethanes were stored at room temperature for over 6 months prior to investigation. Using an automated Kratky camera, SAXS scans were made. By detailed analysis (using the computer program of Vonk) the average interfacial thickness E of the domains was determined by two approaches. The value of E for the polyester was 10–12 Å, while it was 5–7 Å for the polyether. Within the limits of the assumptions used for analysis, these data directly support the conjecture that polyether urethanes generally lead to better phase separation. Other aspects of the analysis provided further information on the morphological structure. Some cautionary comments are provided on the use of quantitative SAXS data obtained from these or similar systems.     

A clinical study of failure in microchannel cooled diodes used in large laser systems

In this paper we investigate the source of failure in commercial, microchannel cooled CW diode bars placed in 12 bar horizontal arrays. The arrays were used to pump Nd:YAG rods in our 10 kW developmental laser. The laser was operated at low duty factor over a period of over 2 years. Experimental evidence indicated that the sudden, catastrophic failure was because of degraded cooling. We used optical microscopes, an X-ray microfocus imager, and a thermal neutron scattering camera to look inside the microcoolers. Our investigations revealed only one possible failure mechanism: cooling flow reduction because of delamination of the Au coating the walls of the microcoolers and the entrapment of Au flakes within the microchannel structures. We observed blisters in the microcoolers under working bars, and flake-like structures in the microcoolers under burnt-out bars (all taken from the laser). We observed no evidence of either massive blockages because of electrochemical deposits, or of corrosion/erosion in the microchannel walls. Integral operation times of the high flow-rate cooling system and of the diodes themselves were too short by one and two orders of magnitude, respectively, to explain the observed failures. Microchannel immersion times in the deionized water were, however, long enough to allow for corrosion of metals that may have been exposed through defects in the Au coatings. Three-dimensional heat flow simulations showed that blockage of multiple microchannels towards the edge of a bar can easily lead to catastrophic temperature increases.     

Stable aromatic dianion in water

Perylene diimide (PDI) bearing polyethylene glycol substituents at the imide positions was reduced in water with sodium dithionite to produce an aromatic dianion. The latter is stable for months in deoxygenated aqueous solutions, in contrast to all known aromatic dianions which readily react with water. Such stability is due to extensive electron delocalization and the aromatic character of the dianion, as evidenced by spectroscopic and theoretical studies. The dianion reacts with oxygen to restore the parent neutral compound, which can be reduced again in an inert atmosphere with sodium dithionite to give the dianion. Such reversible charging renders PDIs useful for controlled electron storage and release in aqueous media. Simple preparation of the dianion, reversible charging, high photoredox power, and stability in water can lead to development of new photofunctional and electron transfer systems in the aqueous phase.     

Synergism in multicomponent self-propagating molecular assemblies

Multicomponent self-propagating molecular assemblies (SPMAs) have been generated from an organic chromophore, a redox-active polypyridyl complex, and PdCl(2). The structure of the multicomponent SPMA is not a linear combination of two assemblies generated with a single molecular constituent. Surface-confined assemblies formed from only the organic chromophore and PdCl(2) are known to follow linear growth, whereas the combination of polypyridyl complexes and PdCl(2) results in exponential growth. The present study demonstrates that an iterative deposition of both molecular building blocks with PdCl(2) results in an exponentially growing assembly. The nature of the assembly mechanism is dictated by the polypyridyl complex and overrides the linear growth process of the organic component. Relatively smooth, multicomponent SPMAs have been obtained with a thickness of ～20 nm on silicon, glass, and indium-tin oxide (ITO) coated glass. Detailed information of the structure and of the surface-assembly chemistry were obtained using transmission optical (UV/Vis) spectroscopy, ellipsometry, atomic force microscopy (AFM), synchrotron X-ray reflectivity (XRR), and electrochemistry.     

The time evolution of the size distribution of droplets effects on the thermal explosion of polydisperse fuel spray

In this paper we investigate the problem of thermal explosion in a two-phase polydisperse combustible mixture (oxygen and fuel concentrations are takes into account). The current work presents a new, simplified model of the thermal explosion in a combustible gaseous mixture containing vaporizing fuel droplets of different radii (polydisperse). The polydispersity is modeled using a probability density function (PDF). The evolution of the size distribution of droplets due to the evaporation process is described by the kinetic equation for the PDF. An explicit expression of the critical condition for thermal explosion limit is derived analytically and represents a generalization of the critical parameter of the classical Semenov theory.     

The rule for a subdiffusive particle in an extremely diverse environment

We consider a subdiffusive continuous time random walker in an inhomogeneous environment. Each microscopic random time is drawn from a waiting time probability density function (WT-PDF) of the form: , 0<β?1. The parameter k is a random quantity also, and is drawn from a PDF, , 0?γ<1, for a cutoff parameter . We show that the effective WT-PDF, ψ(t), obtained by averaging φ(t;k) with p(k), exhibits a transition in the rule that governs the power of ψ(t). ψ(t) obeys, , and μ is given by two different formula. When, 1−γ>β, μ=β, but otherwise, μ=1−γ. The rule for the scaling of ψ(t) reflects the competition between two different mechanisms for subdiffusion: subdiffusion due to the heavily tailed φ(t;k) for individual jumps, and subdiffusion due to the collective effect of an environment made of many slow local regions. These two different mechanisms for subdiffusion are not additive, and compete each other. The reported transition is dimension independent, and disappears when the power β is also distributed, in the range, 0<β?1. Simulations exemplified the transition, and implications are discussed.