Liquid–liquid equilibrium in polymer–fullerene mixtures; an in situ neutron reflectivity study

The composition profiles of a series of model polystyrene/fullerene bilayers are measured, before, during and after thermal annealing, using in situ neutron reflectometry. In combination with grazing-incidence X-ray diffraction measurements, these experiments, which quantify layer compositions as a function of molecular weight using changes in both scattering length density and layer thickness, extend and corroborate recent measurements on ex situ annealed samples and demonstrate that the composition profiles rapidly formed in these systems correspond to two co-existing liquid–liquid phases in thermodynamic equilibrium. The measurements also demonstrate a clear and systematic onset temperature for diffusion of the fullerenes into the PS layer that correlates with the known glass-transition temperatures of both the polymer (as a function of molecular weight) and the fullerene, revealing that the molecular mobility of the fullerenes in these systems is controlled by the intrinsic mobility of the fullerenes themselves and the ability of the polymer to plasticise the fullerenes at the interface. Over the temperature range investigated (up to 145 °C), measurements of equilibrated composition profiles as a function of temperature (during gradual cooling) reveal no significant changes in composition profile, other than those associated with the known thermal expansion/contraction of polystyrene thin-films

Interfacial width and phase equilibrium in polymer-fullerene thin-films

Domain composition and interfacial structure are critical factors in organic photovoltaic performance. Here, we report neutron reflectivity, grazing-incidence X-ray diffraction and atomic force microscopy measurements of polymer/fullerene thin-films to test a hypothesis that these partially miscible blends rapidly develop composition profiles consisting of co-existing phases in liquid-liquid equilibrium. We study a range of polymer molecular weights between 2 and 300 kg mol−1, annealing temperatures between 120 and 170 oC, and timescales up to 10 min, yielding over 50 distinct measurement conditions. Model bilayers of fullerene-derivatives and polystyrene enable a rigorous examination of theoretical predictions of the effect of polymer mass and interaction parameter on the compositions, ϕ, and interfacial width, w, of the coexistent phases. We independently measure ϕ and w and find that both Flory-Huggins mean-field-theory and key aspects of self-consistent-field-theory are remarkably consistent with experiment. Our findings pave the way for predictive composition and interface design in organic photovoltaics based on simple experimental measurements and equilibrium thermodynamic theory

Optical and X-ray correlations during the 2015 outburst of the black hole V404 Cyg

We present a serendipitous multiwavelength campaign of optical photometry simultaneous with Integral X-ray monitoring of the 2015 outburst of the black hole V404 Cyg. Large-amplitude optical variability is generally correlated with X-rays, with lags of order a minute or less compatible with binary light travel time-scales or jet ejections. Rapid optical flaring on time-scales of seconds or less is incompatible with binary light-travel time-scales and has instead been associated with synchrotron emission from a jet. Both this rapid jet response and the lagged and smeared one can be present simultaneously. The optical brightness is not uniquely determined by the X-ray brightness, but the X-ray/optical relationship is bounded by a lower envelope such that at any given optical brightness there is a maximum X-ray brightness seen. This lower envelope traces out a Fopt∝F0.54X relation that can be approximately extrapolated back to quiescence. Rapid optical variability is only seen near this envelope, and these periods correspond to the hardest hard X-ray colours. This correlation between hard X-ray colour and optical variability (and anticorrelation with optical brightness) is a novel finding of this campaign, and apparently a facet of the outburst behaviour in V404 Cyg. It is likely that these correlations are driven by changes in the central accretion rate and geometry

Modelling spectral and timing properties of accreting black holes: the hybrid hot flow paradigm

The general picture that emerged by the end of 1990s from a large set of optical and X-ray, spectral and timing data was that the X-rays are produced in the innermost hot part of the accretion flow, while the optical/infrared (OIR) emission is mainly produced by the irradiated outer thin accretion disc. Recent multiwavelength observations of Galactic black hole transients show that the situation is not so simple. Fast variability in the OIR band, OIR excesses above the thermal emission and a complicated interplay between the X-ray and the OIR light curves imply that the OIR emitting region is much more compact. One of the popular hypotheses is that the jet contributes to the OIR emission and even is responsible for the bulk of the X-rays. However, this scenario is largely ad hoc and is in contradiction with many previously established facts. Alternatively, the hot accretion flow, known to be consistent with the X-ray spectral and timing data, is also a viable candidate to produce the OIR radiation. The hot-flow scenario naturally explains the power-law like OIR spectra, fast OIR variability and its complex relation to the X-rays if the hot flow contains non-thermal electrons (even in energetically negligible quantities), which are required by the presence of the MeV tail in Cyg X-1. The presence of non-thermal electrons also lowers the equilibrium electron temperature in the hot flow model to <100 keV, making it more consistent with observations. Here we argue that any viable model should simultaneously explain a large set of spectral and timing data and show that the hybrid (thermal/non-thermal) hot flow model satisfies most of the constraints.Comment: 26 pages, 13 figures. To be published in the Space Science Reviews and as hard cover in the Space Sciences Series of ISSI - The Physics of Accretion on to Black Holes (Springer Publisher

Infrared Observations of XTE J1118+480

Infrared observations of the outbursting black hole XTE J1118+480 (ATEL #383) were performed using SQIID on the Kitt Peak National Observatory 2.1m telescope. Observations spanning 2005 January 15.42-15.58 found it somewhat fainter than the previous outburst (IAUC # 7394 , # 7407 ), at average brightness J=12.91+/-0.03, H=12.50+/-0.03, K=11.95+/-0.03. The colors again correspond to an approximately flat spectrum in F_nu. No orbital variation is apparent, but there is substantial unresolved rapid variability with rms amplitude 22% in K (between 2s exposures). Further observations are planned nightly until Jan 21

Multiwavelength Observations of EXO 0748-676. I. Reprocessing of X-Ray Bursts

We present the first high time-resolution simultaneous X-ray, ultraviolet, and optical observations of X-ray bursts in UY Vol, the optical counterpart of the low mass X-ray binary EXO 0748-676, obtained with RXTE, HST, and Gemini-S. Strong reprocessed signals are present in the ultraviolet (a factor of 4) and optical (a factor of 2.5). These signals are lagged with respect to the X-rays and appear significantly smeared as well. The addition of far-ultraviolet coverage for one burst, together with the high quality of the dataset, allow much tighter constraints upon the temperature and geometry of the reprocessing region than previously possible. A single-zone black body reprocessing model for this burst suggests a rise in temperatures during the burst from 18,000 to 35,000K and an emitting area comparable to that expected for the disk and/or irradiated companion star. The lags, a mean of 4.0s and range of 2.5s, are consistent with those expected within the binary. The single-zone black body model cannot reproduce the ratio of optical to ultraviolet flux during the burst, however. The discrepancy, corresponding to underpredicting the optical by more than a factor of two, seems too large to explain with deviations from a local black body spectrum and more likely indicates that a range of reprocessing temperatures are required, as would be expected, with cooler regions not contributing to the UV. Comparable results are derived from other bursts, and in particular the lag and smearing both appear shorter when the companion star is on the near side of the disk as predicted. The burst observed by HST also yielded a spectrum of the reprocessed light. [Abridged]Comment: 15 pages, accepted for publication in the Astrophysical Journa

Disentangling X-ray Reprocessing Sites in EXO 0748-676

Presentamos los primeros resultados de un estudio coordinado en m ultiples longitudes de onda de la estrella de\ud neutrones de la binaria de baja masa de rayos X, EXO 0748-676 (UY Vol). Se obtuvieron datos UV r apidos,\ud de rayos X y opticos, incluyendo tanto informaci on espectral como temporal. Discutimos c omo este estudio\ud nos permite indagar sobre cu al es la distribuci on de temperatura dentro de la binaria y por lo tanto, sobre la\ud geometr a y la e ciencia de la irradiaci on de rayos