BECOOL: Ballooning eigensolver with COOL finite elements

An incompressible variational ideal ballooning mode equation is discretized with the COOL finite element discretization scheme using basis functions composed of variable order Legendre polynomials. This reduces the second order ordinary differential equation to a special block pentadiagonal matrix equation that is solved using an inverse vector iteration method. A benchmark test of BECOOL (Ballooning Eigensolver using COOL finite elements) with second order Legendre polynomials recovers precisely the eigenvalues computed by the VVBAL shooting code. Timing runs reveal the need to determine an optimal lower order case. Eigenvalue convergence runs show that cubic Legendre polynomials construct the optimal ballooning mode equation for intensive computations.     

Oxygen‐barrier properties of copolymers based on ethylene terephthalate

The oxygen‐barrier properties of amorphous polyethylene terephthalate‐based copolymers with various acid comonomers were examined. The incorporation of increasing amounts of isophthalate, phthalate, or naphthalate gradually reduced the permeability P toward the low values obtained for the corresponding homopolymers. The permeability of poly(ethylene 3,4′‐bibenzoate) homopolymer was only slightly lower than that of polyethylene terephthalate, and the copolymers correspondingly exhibited a very gradual decrease in P as the amount of 3,4′‐bibenzoate (3,4′BB) increased. In contrast, copolymerization with the linear isomer, 4,4′BB, produced a substantial increase in P. Generally, comonomer affected the solubility S less than the diffusivity D, and therefore changes in P reflected primarily changes in D for the polymers studied. The diffusivity and solubility depended on the copolymer composition in accordance with static and dynamic free‐volume concepts of gas permeability in glassy polymers. The solubility S correlated with the amount of free volume as determined by the glass‐transition temperature. Correlation of the diffusivity D with the magnitude of the subambient γ relaxation identified dynamic free volume with thermally activated conformational changes and segmental motions. Correspondence in the activation energy confirmed the relationship. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1889–1899, 2001     

Group theoretic properties of Rijndael-like ciphers

We provide conditions for which the round functions of an ?-bit Rijndael-like block cipher generate the alternating group on the set {0,1}^?. These conditions show that the class of Rijndael-like ciphers whose round functions generate the alternating group on their message space is large, and includes both the actual Rijndael and the block cipher used by the compression function of the Whirlpool hash function. The result indicates that there is no trapdoor design for a Rijndael-like cipher based on the imprimitivity of the group action of its proper round functions which is difficult to detect.     

Interfacial change on morphological transitions in styrene-isoprene diblock copolymer

The specific interfacial area (S/V) and interfacial thickness in each microstructure of styrene-isoprene diblock copolymer were estimated by analyzing the deviations from Porod’s law. The thermally induced phase transitions proceeded from lamellae (L) to hexagonally ordered cylinder (HEX), via hexagonally perforated layer (HPL) and gyroid (G). The S/V ratio increased stepwise at the order-order transition (OOT) from L to HEX, via HPL and G. The S/V data can be utilized for OOT determination.     

Synthesis and characterization of a novel water-soluble mid-chain macrophotoinitiator of polyacrylamide by Ce(IV)/HNO3 redox system

A new water-soluble mid-chain macrophotoinitiator of polyacrylamide (PAAm) has been synthesized by redox polymerization. The polymerization of acrylamide (AAm) initiated by dihydroxy functional photoinitiator namely, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl propan-1-one (HE-HMPP), Irgacure 2959, in combination with cerium(IV) ammonium nitrate has been investigated in aqueous nitric acid. The effects of HE-HMPP, AAm, and Ce(IV) concentrations on the polymerization rate were investigated. The photodegradation and IR, ¹H NMR, UV, and fluorescence spectroscopic studies revealed that polyacrylamide with desired photoinitiator functionality in the middle of the chain were obtained. This prepolymer was used in photoinduced free radical polymerization of methyl methacrylate (MMA) to produce PAAm-PMMA block copolymer.     

Flow-shop scheduling with setup and assembly operations

A scheduling model for a production system including machining, setup and assembly operations is considered. Production of a number of single-item products is ordered. Each product is made by assembling a set of several different parts. First, the parts are manufactured in a flow-shop consisting of multiple machines. Then, they are assembled into products on a single assembly stage. Setup operation and setup time are needed when a machine starts processing the parts or it changes items. The operations are partitioned into several blocks. Each block consists of the machining operations, the setup operations, and the assembly operation(s) for one or several products. The parts of the same item in a block are processed successively. The objective function is the mean completion time for all products. We consider a problem to partition the operations into blocks and sequence the parts in each block so as to minimize the objective function. Solution procedures using pseudo-dynamic programming and a branch-and-bound method are proposed. Computational experiments are carried out to evaluate the performance of the solution procedures. It has been found that a good near-optimal schedule is obtained efficiently by the proposed solution procedures.     

Effects of cationic head groups of ionic liquid on micellization in aqueous solution of PEO-PPO-PEO triblock copolymer

The interaction of ionic liquids (ILs) with non-ionic triblock copolymer, Pluronic® P123 in aqueous solutions has been investigated using DLS, surface tension, and viscosity measurements. The addition of ILs increased the Critical Micelle Concentration (CMC) of P123, which appears to be logistic. As the added IL enhances the solubility of PPO moiety (and PEO), which makes them to behave like a more hydrophilic block copolymer that would be micellized at high copolymer concentration. The DLS data is in good agreement to the results observed from surface tension measurements. Viscosity results show the propensity in micellar size reduction upon addition of ILs, and hence, intrinsic viscosity decreases as compared to pure P123 aqueous solution. The results are studied and discussed as a function of cationic head groups of N-octyl-pyridinium/imidazolium chloride based ILs.     

Synthesis and MALDI-TOF-MS of PS-PMA and PMA-PS block copolymers

The synthesis of well-defined block copolymers from styrene and methyl acrylate via ATRP is discussed in this contribution. Kinetic studies on these block copolymerizations as well as characterization studies were performed to investigate the monomer composition in the respective PS and PMA blocks. MALDI-TOF-MS was performed to clarify the exact number of repeating units of each block and the total number of units in the block copolymer. Block copolymers up to 22 kDa could be analyzed by MALDI-TOF-MS, whereby polymers with PMA as first block showed a large second distribution corresponding to PMA homopolymers. However, SEC demonstrated that only a small amount of homopolymer was present indicating that care needs to be taken with interpreting MALDI-TOF-MS data, which is a qualitative rather than a quantitative technique.     

Effect of sequence distribution on the isothermal crystallization kinetics and successive self-nucleation and annealing (SSA) behavior of poly(ε-caprolactone-co-ε-caprolactam) copolymers

Two types of miscible poly(ε-caprolactone-co-ε-caprolactam) copolymers were studied. In both cases catalyzed hydrolytic ring-opening polymerization was employed. For the first type, the comonomers were added simultaneously to obtain random copolymers. For the second type, the comonomers were added sequentially to obtain block copolymers. Successive self-nucleation and annealing (SSA) and isothermal crystallization studies were performed to both types of copolymers. The SSA results reflect the differences in molecular microstructure: block versus random copolymers. In a wide composition range only the polycaprolactam sequences were capable of crystallization in the random copolymers. Avrami indexes of approximately 3-4 were obtained corresponding to the spherulitic crystallization of these units within the copolymers. The block copolymer samples experienced a relatively small reduction of crystallization kinetics with composition, and this was attributed to the dilution effect caused by the miscible non-crystalline polycaprolactone units. On the other hand, for the random copolymers, the rate of crystallization strongly increased with polycaprolactam content while the energy barrier for secondary nucleation decreased exponentially. The comparison between miscible block and random copolymers provides a unique opportunity to distinguish the dilution effect of the polycaprolactone units (a moderate effect) on the isothermal crystallization and melting of the polyamide phase from the molecular microstructural effect in the random copolymers case (a dramatically strong effect), where the polycaprolactam sequences are interrupted statistically by polycaprolactone sequences.     

Effects of ozone in surface modification and thermal stability of SEBS block copolymers

SEBS block copolymers were treated under mild conditions in an ozone atmosphere, producing very slightly chemically-modified surfaces. The thermal stability was analysed by chemiluminescence and related to morphological changes observed by AFM. The intrinsic thermal stability was diminished by ozone exposure, but the oxidation induction times were delayed which indicates an enhancement of thermal stability under oxidative conditions. Also, chemiluminescence analysis showed the presence of a typical order-disorder transition at temperatures around 120 °C. Two different sets of samples which showed different morphological patterns were imaged by AFM. The effects of micro-domain separation and inter-domain structure on thermal properties are discussed and explained by a coarsening of the internal interface induced by ozone. A detailed 2D Fourier transformed analysis of AFM images allowed us to identify a regular wrinkled nano-pattern induced by uniaxial strain combined with ozone treatment, offering new opportunities in applications ranging from organic electronics to bio-patterning.