Multiply Nitrated High‐Energy Dense Oxidizers Derived from the Simple Amino Acid Glycine

Various energetic polynitro esters, carbamates, and nitrocarbamates that were derived from the amino acid glycine were fully characterized by single‐crystal X‐ray diffraction, vibrational spectroscopy (IR and Raman), multinuclear NMR spectroscopy, elemental analysis, and differential scanning calorimetry (DSC). Owing to their positive oxygen balance, the suitability of these compounds as potential oxidizers in energetic formulations was investigated and discussed. In addition, the heats of formation of the products were calculated by using the Gaussian 09 program package at the CBS‐4M level of theory. From these values and the calculated densities (from the X‐ray data), several detonation parameters, such as detonation pressure, velocity, energy, and temperature, were computed by using the EXPLO5 code. Furthermore, their sensitivities towards impact, friction, and electrostatic discharge were tested by using a drop hammer, a friction tester (both BAM certified), and a small‐scale electrical‐discharge device, respectively.     

Synthesis of diblock methylcellulose derivatives with regioselective functionalization patterns

This article describes a new synthesis strategy to prepare diblock copolymers as model compounds for industrially produced cellulose ethers exemplified with methylcellulose (MC). To elucidate a key structure for thermoreversible gelation of MC, five regioselectively methylated celluloses 1 – 5 (236, 23, 26, 3, and 6 MC), five corresponding methyl‐β‐D‐glucopyranosyl‐(1→4)‐cellulosides 6 – 10 , and five equiv methyl‐β‐D‐glucopyranosyl‐(1→4)‐β‐D‐glucopyranosyl‐(1→4)‐cellulosides 11 – 15 were synthesized for the first time via combination of the glycosyl trichloroacetimidate method and the acid‐catalyzed methanolysis method. The structure of compounds 1 – 15 was confirmed by means of NMR spectroscopy and MALDI‐TOF MS. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Evaluation of steerable filter for detection of fibers in flowing suspensions

Steerable filters are concluded to be useful in order to determine the orientation of fibers captured in digital images. The fiber orientation is a key variable in the study of flowing fiber suspensions. Here, digital image analysis based on a filter within the class of steerable filters is evaluated for suitability of finding the position and orientation of fibers suspended in flowing suspensions. In sharp images with small noise levels, the steerable filter succeeds in determining the orientation of artificially generated fibers with well-defined angles. The influence of reduced image quality on the orientation has been quantified. The effect of unsharpness and noise is studied and the results show that the error in orientation is less than 1° for moderate levels. Images from two flow cases, one laminar shear flow and one turbulent, are also analyzed. The fiber orientation distribution is determined in the flow-vorticity plane. For the laminar case a comparison is made to a robust, but computationally more expensive, method involving convolutions with an oriented elliptic filter. A good agreement is found when comparing the resulting fiber orientation distributions obtained with the two methods. For the turbulent case, it is demonstrated that correct results are obtained and that the method can handle overlapping fibers.     

Demand dispersion and logistics costs in one-to-many distribution systems

When an organization decides on which groups of consumers it should target, the locations of these target consumers often play a role. Methods from the field of market segmentation are able to identify target groups with high benefit levels, but the expected costs of supplying products to the target groups are less well understood. These costs can play a large role if the locations of the customers, the demand locations, are geographically widely dispersed. This paper focuses on one-to-many distribution systems in which a central facility serves all demand points. We derive accurate logistics cost estimates from the dispersion of demand points for such systems, enabling a comparison of the expected logistics costs of different candidate target groups. The most accurate measure combines the average distance from the demand locations to a central location and the mutual distances between neighboring demand locations. The average of the distances between all pairs of locations forms a good alternative measure.     

On the application of a single‐crystal κ‐diffractometer and a CCD area detector for studies of thin films

A multipurpose six‐axis κ‐diffractometer, together with the brilliance of the ESRF light source and a CCD area detector, has been explored for studying epitaxial relations and crystallinity in thin film systems. The geometrical flexibility of the six‐axis goniometer allows measurement of a large volume in reciprocal space, providing an in‐depth understanding of sample crystal relationships. By a set of examples of LaAlO₃ thin films deposited by the atomic layer deposition technique, the possibilities of the set‐up are presented. A fast panoramic scan provides determination of the crystal orientation matrices, prior to more thorough inspection of single Bragg nodes. Such information, in addition to a broadening analysis of families of single reflections, is shown to correlate well with the crystallinity, crystallite size, strain and epitaxial relationships in the thin films. The proposed set‐up offers fast and easy sample mounting and alignment, along with crucial information on key features of the thin film structures.     

Viscoelastic phase diagram of fluorinated and grafted polymer films and proton‐exchange membranes for fuel cell applications

The influence of temperature and moisture activity on the viscoelastic behavior of fluorinated membranes for fuel cell applications was investigated. Uncrosslinked and crosslinked ethylene tetrafluoroethylene (ETFE)‐based proton‐conducting membranes were prepared by radiation grafting and subsequent sulfonation and their behavior was compared with ETFE base film and commercial Nafion^® NR212 membrane. Uniaxial tensile tests and stress relaxation tests at controlled temperature and relative humidity (RH) were carried out at 30 and 50 °C for 10% < RH < 90%. Grafted films were stiffer and exhibited stronger strain hardening when compared with ETFE. Similarly, both uncrosslinked and crosslinked membranes were stiffer and stronger than Nafion^®. Yield stress was found to decrease and moisture sensitivity to increase on sulfonation. The viscoelastic relaxation of the grafted films was found to obey a power‐law behavior with exponent equal to ?0.04 ± 0.01, a factor of almost 2 lower than ETFE, weakly influenced by moisture and temperature. Moreover, the grafted films presented a higher hygrothermal stability when compared with their membranes counterparts. In the case of membranes, a power‐law behavior at RH < 60% was also observed. However, a markedly different behavior was evident at RH > 60%, with an almost single relaxation time exponential. An exponential decrease of relaxation time with RH from 60 s to 10 s was obtained at RH ≥ 70% and 30 °C. The general behavior of grafted films observed at 30 °C was also obtained at 50 °C. However, an anomalous result was noticed for the membranes, with a higher modulus at 50 °C when compared with 30 °C. This behavior was explained by solvation of the sulfonic acid groups by water absorption creating hydrogen bonding within the clusters. A viscoelastic phase diagram was elaborated to map critical conditions (temperature and RH) for transitions in time‐dependent behavior, from power‐law scaling to exponential scaling. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1139–1148     

Choiceless polynomial time

Turing machines define polynomial time (PTime) on strings but cannot deal with structures like graphs directly, and there is no known, easily computable string encoding of isomorphism classes of structures. Is there a computation model whose machines do not distinguish between isomorphic structures and compute exactly PTime properties? This question can be recast as follows: Does there exist a logic that captures polynomial time (without presuming the presence of a linear order)? Earlier, one of us conjectured a negative answer. The problem motivated a quest for stronger and stronger PTime logics. All these logics avoid arbitrary choice. Here we attempt to capture the choiceless fragment of PTime. Our computation model is a version of abstract state machines (formerly called evolving algebras). The idea is to replace arbitrary choice with parallel execution. The resulting logic expresses all properties expressible in any other PTime logic in the literature. A more difficult theorem shows that the logic does not capture all of PTime.