Model-based analysis of photoinitiated coating degradation under artificial exposure conditions

Coating degradation mechanisms of thermoset coatings exposed to ultraviolet radiation and humidity at constant temperature are investigated. The essential processes, photoinitiated oxidation reactions, intrafilm oxygen permeability, water absorption and diffusion, reduction of crosslink density, and development of a thin surface oxidation zone are quantified and a mathematical model for degrading coatings developed. Front-tracking techniques are used to determine the rate of movement of the oxidation and ablation fronts, the positions of which define the extension of the surface oxidation zone. Three previous and independent experimental investigations with two-component, densely crosslinked, epoxy?Camine model coatings were selected for verification of the mathematical model. Simulations can match and explain transient mass loss and coating thickness reduction data and are in agreement with infrared measurements of carbonyl groups formed in the surface zone. The thickness of the stable surface oxidation zone, which is established after an initial ablation lag time, is estimated by the model to 0.5?C2???m in good agreement with previous measurements. Simulated concentration profiles of active groups, oxygen, and radicals in the stable surface oxidation zone are presented and analyzed. The mathematical model can be used for obtaining a quantitative insight into the degradation of thermoset coatings and has potential, after further development, to complete commercial coatings and dynamic exposure conditions, to become a supplementing tool for predicting in-service coating behavior based on accelerated laboratory measurements.     

How verified (or tested) is my code? Falsification-driven verification and testing

Formal verification has advanced to the point that developers can verify the correctness of small, critical modules. Unfortunately, despite considerable efforts, determining if a “verification” verifies what the author intends is still difficult. Previous approaches are difficult to understand and often limited in applicability. Developers need verification coverage in terms of the software they are verifying, not model checking diagnostics. We propose a methodology to allow developers to determine (and correct) what it is that they have verified, and tools to support that methodology. Our basic approach is based on a novel variation of mutation analysis and the idea of verification driven by falsification. We use the CBMC model checker to show that this approach is applicable not only to simple data structures and sorting routines, and verification of a routine in Mozilla’s JavaScript engine, but to understanding an ongoing effort to verify the Linux kernel read-copy-update mechanism. Moreover, we show that despite the probabilistic nature of random testing and the tendency to incompleteness of testing as opposed to verification, the same techniques, with suitable modifications, apply to automated test generation as well as to formal verification. In essence, it is the number of surviving mutants that drives the scalability of our methods, not the underlying method for detecting faults in a program. From the point of view of a Popperian analysis where an unkilled mutant is a weakness (in terms of its falsifiability) in a “scientific theory” of program behavior, it is only the number of weaknesses to be examined by a user that is important.     

Sulfite Action in Glycolytic Inhibition: In Vivo Real‐Time Observation by Hyperpolarized 13C NMR Spectroscopy

Detecting the molecular targets of xenobiotic substances in vivo poses a considerable analytical challenge. Here, we describe the use of an NMR‐based tracer methodology for the instantaneous in vivo observation of sulfur(IV) action on cellular metabolism. Specifically, we find that glycolytic flux is directed towards sulfite adducts of dihydroxyacetone phosphate and pyruvate as off‐pathway intermediates that obstruct glycolytic flux. In particular, the pyruvate–sulfite association hinders the formation of downstream metabolites. The apparent in vivo association constant of pyruvate and sulfite agrees with the apparent inhibition constant of CO₂ formation, thus supporting the importance of pyruvate interception in disturbing central metabolism and inhibiting NAD regeneration.     

Dairy cows with prolonged calving seek additional isolation

In modern calving facilities, dairy cows either calve in a group pen or are moved to a separate individual pen when calving is imminent. In practice, cows are often moved too close to calving, which poses a health risk to cow and calf. Thus, a need exists for new calving facility designs and management practices that better align with the motivations of the cow. This study examined dairy cow preferences for individual calving pens by offering 3 different levels of isolation (tall and narrow, low and wide, and tall and wide) by analyzing the association between precalving behavior, choice of degree of isolation, and the progress of calving. The hypotheses were that cows would prefer the highest level of isolation when giving birth, and that calving in a high level of isolation would be associated with less restlessness and a shorter calving duration. Contrary to these hypotheses, no specific preference between degrees of isolation or difference in calving behavior in the different calving pens was found. However, cows experiencing a longer calving duration chose to calve in the most secluded calving pen (tall and wide). These results cannot determine cause and effect, but may suggest that interactions between motivation for isolation seeking and calving behavior exist.     

Crosslinking of polybenzimidazole membranes by divinylsulfone post‐treatment for high‐temperature proton exchange membrane fuel cell applications

Phosphoric acid‐doped polybenzimidazole (PBI) has been suggested as a promising electrolyte for proton exchange membrane fuel cells operating at temperatures up to 200 °C. This paper describes the development of a crosslinking procedure for PBI membranes by post‐treatment with divinylsulfone. The crosslinking chemistry was studied and optimized on a low‐molecular‐weight model system and the results were used to optimize the crosslinking conditions of PBI membranes. The crosslinked membranes were characterized with respect to chemical and physiochemical properties, showing improved mechanical strength and oxidative stability compared with their linear analogues. Fuel cell tests were further conducted in order to demonstrate the feasibility of the crosslinked membranes. Copyright © 2011 Society of Chemical Industry     

Unsuccessful retrieval attempts enhance subsequent learning.

Taking tests enhances learning. But what happens when one cannot answer a test question—does an unsuccessful retrieval attempt impede future learning or enhance it? The authors examined this question using materials that ensured that retrieval attempts would be unsuccessful. In Experiments 1 and 2, participants were asked fictional general-knowledge questions (e.g., “What peace treaty ended the Calumet War?”). In Experiments 3–6, participants were shown a cue word (e.g., whale) and were asked to guess a weak associate (e.g., mammal); the rare trials on which participants guessed the correct response were excluded from the analyses. In the test condition, participants attempted to answer the question before being shown the answer; in the read-only condition, the question and answer were presented together. Unsuccessful retrieval attempts enhanced learning with both types of materials. These results demonstrate that retrieval attempts enhance future learning; they also suggest that taking challenging tests—instead of avoiding errors—may be one key to effective learning. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Effect of NiO-to-Ni Transformation on Conductivity and Structure of Yttria-Stabilized ZrO2

The conductivity and structure of 8-mol%-yttria-stabilized zirconia with additions of nickel oxide has been investigated, both in the as-prepared state and after reduction of NiO in hydrogen. During reduction at 1000°C, the conductivity decreases by 40%–50% and most of the NiO dissolved in the zirconia is exsolved in the form of nickel particles. This is accompanied by the formation of tetragonal zirconia precipitates of size 10–40 nm and by an increase in the lattice parameter. On reoxidation in air at 1000°C, the change in lattice parameter is partly reversed, but the conductivity shows no further changes.     

Autogenous deformation and RH-change in perspective

Autogenous deformation and change of the relative humidity (RH-change) have been described and registered for a century. However, it is only within the last decade that these phenomena have received appreciable attention. The reason for this is that autogenous deformation and autogenous RH-change are phenomena of special importance within high-strength (high-performance) concrete technology, and a significant utilisation of these concretes did not take place until the early 1980s. In the present paper an historical overview of autogenous deformation and RH-change is given. In addition, due to the present status of this research field both terminology and measuring techniques are described in detail. Finally, some expectations for future research in this field are given.