Influence of heating and cooling rates on the glass transition temperature and the fragility parameter of sorbitol and fructose as measured by DSC

The glass transition temperatures of sorbitol and fructose were characterized by four points determined on DSC heating thermograms (onset, mid-point, peak and end-point), plus the limit fictive temperature. The variations of these temperature values, observed as functions of cooling and heating rates, were used to determine the fragility parameter, as defined by Angell [1] to characterize the temperature dependence of the dynamic behavior of glass-forming liquids in the temperature range above the glass transition. The apparent activation energy values, determined for the different temperatures studied, were similar for fructose and sorbitol. These values were compared to data obtained from other techniques, such as mechanical spectroscopy. The variations of the apparent activation values, observed in experiments involving cooling and heating at the same rate, slow cooling followed by rate-heating, or rate-cooling followed by fast heating, were explained by aging effects occurring during the heating step.     

Dynamic and sub-ambient thermal transition relationships in water–sucrose solutions

This work was undertaken to investigate thermal and dynamic transitions observed in the temperature range close to the bulk ice melting temperature in sucrose solutions. Measurements of thermal (differential calorimetry) and dynamic (neutron scattering) properties were compared in order to give a physical interpretation of the thermal transitions observed during the thawing of amorphous sucrose solutions. In fact, the freezing of biological material leads to the distinction between different pools of water: bulk water which becomes ice after freezing, unfrozen water trapped in the glassy matrix or close to the interface of solutes can be considered, and finally freezable confined water with a lower melting point than bulk water and with properties depending on both the ice presence and the microstructure of the material. The transition temperatures such as glass transition or melting are dependent on the freezing protocol used and examples of annealing effects are presented, in order to underline the necessity of a good temperature control during freezing for the study of biological material with freezable water.     

Load balancing via random local search in closed and open systems

In this paper, we analyze the performance of random load resampling and migration strategies in parallel server systems. Clients initially attach themselves to an arbitrary server, but may switch servers independently at random instants of time in an attempt to improve their service rate. This approach to load balancing contrasts with traditional approaches where clients make smart server selections upon arrival (e.g., Join-the-Shortest-Queue policy and variants thereof). Load resampling is particularly relevant in scenarios where clients cannot predict the load of a server before being actually attached to it. An important example is in wireless spectrum sharing where clients try to share a set of frequency bands in a distributed manner. We first analyze the natural Random Local Search (RLS) strategy. Under this strategy, after sampling a new server randomly, clients only switch to it if their service rate is improved. In closed systems, where the client population is fixed, we derive tight estimates of the time it takes under RLS strategy to balance the load across servers. We then study open systems where clients arrive according to a random process and leave the system upon service completion. In this scenario, we analyze how client migrations within the system interact with the system dynamics induced by client arrivals and departures. We compare the load-aware RLS strategy to a load-oblivious strategy in which clients just randomly switch server without accounting for the server loads. Surprisingly, we show that both load-oblivious and load-aware strategies stabilize the system whenever this is at all possible. We use large-system asymptotics to characterize system performance, and augment this with simulations, which suggest that the average client sojourn time under the load-oblivious strategy is not considerably reduced when clients apply smarter load-aware strategies.     

A performance analysis of channel fragmentation in dynamic spectrum access systems

Dynamic Spectrum Access systems offer temporarily available spectrum to opportunistic users capable of spreading transmissions over a number of non-contiguous subchannels. Such methods can be highly beneficial in terms of spectrum utilization, but excessive fragmentation degrades performance and hence off-sets the benefits. To get some insight into acceptable levels of fragmentation, we present experimental and analytical results derived from a mathematical model. According to the model, a system operates at capacity serving requests for bandwidth by assigning a collection of one or more gaps of unused bandwidth to each request as bandwidth becomes available. Our main result is a proof that, even if fragments can be arbitrarily small, the system remains stable in the sense that the average total number of fragments remains bounded. Within the class of dynamic fragmentation models, including models of dynamic storage allocation that have been around for many decades, this result appears to be the first of its kind. In addition, we provide extensive experimental results that describe behavior, at times unexpected, of fragmentation as parameter values are varied. Different scanning rules for searching gaps of available spectrum, all covered by the above stability result, are also studied. Our model applies to dynamic linked-list storage allocation, and provides a novel analysis in that domain. We prove that, interestingly, a version of the 50?% rule of the classical, non-fragmented allocation model holds for the new model as well. Overall, the paper provides insights into the behavior of practical fragmentation algorithms.     

Mobility can drastically improve the heavy traffic performance from $$\frac{1}{1-\varrho }$$11-ϱ to $$\log (1/(1-\varrho ))$$log(1/(1-ϱ))

Queueing Systems - We study a model of wireless networks where users move at speed $$\theta \ge 0$$, which has the original feature of being defined through a fixed-point equation. Namely, we start...     

Can dynamical mechanical measurements predict brittle fracture behaviour?

The uptake of water by low moisture cereal products can have detrimental effects on their texture, and cause loss of quality. Following the interest in developing techniques suitable for determining texture properties, there has also been a move towards identifying the origins of the observed changes. Although the origins of the hydration effects are not fully understood, dynamic rheology is believed to be a suitable technique for characterising mechanical properties, and for identifying the origins of the features observed after moisture pick-up. In a previous paper, the sensory crispness of white bread and of extruded flat bread were correlated with tan, through the increase in tan resulting from the increased hydration associated with loss of crispness. The present work shows that such a correlation does not exist with extruded starch-sugar samples. This means that tan data cannot be used to predict fracture properties like those covered by crispness. The information revealed by the results did, however, address various questions about the significance of tan. Indeed, the increase in tan with increasing hydration was shown to be particularly acute when the starch was mixed with sugar (sucrose or fructose). In order to interpret these results several hypotheses have been suggested, including increased heterogeneity of the systems, and sensitivity of tan to solute mobility or to localised motions of the matrix.     

Analysis of oligomeric peroxides in synthetic triacetone triperoxide samples by tandem mass spectrometry

Oligomeric peroxides formed in the synthesis of triacetone triperoxide (TATP) have been analyzed by mass spectrometry utilizing both electrospray ionization (ESI) and chemical ionization (CI) to form sodiated adducts (by ESI) and ammonium adducts (by CI and ESI). Tandem mass spectrometry and deuterium isotopic labeling experiments have been used to elucidate the collision‐induced dissociation (CID) mechanisms for the adducts. The CID mechanisms differ for the sodium and ammonium adducts and vary with the size of the oligoperoxide. The sodium adducts of the oligoperoxides, H[OOC(CH₃)₂]_nOOH, do not cyclize under CID, whereas the ammonium adducts of the smaller oligoperoides (n < 6) do form the cyclic peroxides under CID. Larger oligoperoxide adducts with both sodium and ammonium undergo dissociation through cleavage of the backbone under CID to form acyl‐ and hydroperoxy‐terminated oligomers of the general form CH₃C(O)[OOC(CH₃)₂]_xOOH, where x is an integer less than the original oligoperoxide degree of oligomerization. The oligoperoxide distribution is shown to vary batch‐to‐batch in the synthesis of TATP and the post‐blast distribution differs slightly from the distribution in the uninitiated material. The oligoperoxides are shown to be decomposed under gentle heating. Copyright © 2009 John Wiley & Sons, Ltd.