Thiol–norbornene materials: Approaches to develop high Tg thiol–ene polymers

The ability to prepare high T_g low shrinkage thiol–ene materials is attractive for applications such as coatings and dental restoratives. However, thiol and nonacrylated vinyl materials typically consist of a flexible backbone, limiting the utility of these polymers. Hence, it is of importance to synthesize and investigate thiol and vinyl materials of varying backbone chemistry and stiffness. Here, we investigate the effect of backbone chemistry and functionality of norbornene resins on polymerization kinetics and glass transition temperature (T_g) for several thiol–norbornene materials. Results indicate that T_gs as high as 94 °C are achievable in thiol–norbornene resins of appropriately controlled chemistry. Furthermore, both the backbone chemistry and the norbornene moiety are important factors in the development of high T_g materials. In particular, as much as a 70 °C increase in T_g was observed in a norbornene–thiol specimen when compared with a sample prepared using allyl ether monomer of analogous backbone chemistry. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5686–5696, 2007     

Use of dynamic trees in a network simplex algorithm for the maximum flow problem

Goldfarb and Hao (1990) have proposed a pivot rule for the primal network simplex algorithm that will solve a maximum flow problem on ann-vertex,m-arc network in at mostnm pivots and O(n ² m) time. In this paper we describe how to extend the dynamic tree data structure of Sleator and Tarjan (1983, 1985) to reduce the running time of this algorithm to O(nm logn). This bound is less than a logarithmic factor larger than those of the fastest known algorithms for the problem. Our extension of dynamic trees is interesting in its own right and may well have additional applications.Research partially supported by a Presidential Young Investigator Award from the National Science Foundation, Grant No. CCR-8858097, an IBM Faculty Development Award, and AT&T Bell Laboratories.Research partially supported by the Office of Naval Research, Contract No. N00014-87-K-0467.Research partially supported by the National Science Foundation, Grant No. DCR-8605961, and the Office of Naval Research, Contract No. N00014-87-K-0467.     

Lieb–Thirring Inequalities for Schrödinger Operators with Complex-valued Potentials

Inequalities are derived for power sums of the real part and the modulus of the eigenvalues of a Schrödinger operator with a complex-valued potential.     

Staffing Rosters with Breaks — A Case Study

A complex manual rostering system for directory assistance, telephone operators has been rationalized and the technique of integer programming used to automatically generate staff rosters. These rosters can be generated by relatively unskilled clerical staff. They result in operator costs comparable to manually generated rosters and can be produced in a fraction of the time taken to produce their manual counterparts. Implementation is reported.     

Ab initio potential energy surface and pressure broadening coefficients for the He-CH3F complex

Symmetry-adapted perturbation theory has been applied to compute the He-CH₃F potential with the CH₃F molecule assumed rigid. The potential has a global minimum of −48.9 cm⁻¹ at the center of mass separation of 7.2 bohr with the helium atom lying along the C-F bond on the hydrogen’s side. The computed points were fitted to an analytic energy surface with a correct asymptotic behaviour. This potential has been used to compute the pressure broadening (PB) coefficients for the (j, k) = (0, 0) → (1, 0) and (1, 0) → (2, 0) rotational transitions of CH₃F perturbed by helium for a wide range of temperatures. Close-coupling results are compared with the experimental data of Willey et al. [J. Chem. Phys. 97 (1992) 4723], Beaky et al. [J. Mol. Struct. 352/353 (1995) 245] and infinite order sudden results are compared with those of Grigoriev et al. [J. Mol. Struct. 186 (1997) 48] for the ν₆ band of CH₃F perturbed by helium at room temperature. To our knowledge, present work is the first attempt of making fully ab initio calculations of collisional cross-sections and pressure broadening coefficients for this simple symmetric top system at low and room temperature.     

Dimensionally and thermally stable polymer,containing disordered graphitic structure and adamantane

In an attempt to develop a low‐k interlayer dielectric, adamantane‐diphenyldiethynyl moiety containing oligomer is prepared. Oligomerization of 1,3,5,7‐tetrakis[3/4‐ethynylphenyl]adamantane ( 4 ) is accomplished by a Glaser–Hay oxidative coupling with 1,3,5‐triethynylbenzene and phenylacetylene end‐capping agent. The CHCl₃ soluble oligomer is then thermally treated by step‐curing at 200, 300, 380, and 450 °C for 30 min at each temperature under nitrogen flow to render a shiny void‐free black polymer. TGA analysis indicates that the polymer is stable under nitrogen up to 500 °C with a marginal decomposition up to 800 °C. Solid‐state ¹³C NMR, Raman scattering, and FTIR are used to characterize the structure of the polymer. The polymer consists of amorphous carbon networks with the adamantane moieties and nanosized graphitic regions (clusters), which are generated from the thermal crosslinking of the diphenyldiethynyl units. It shows a remarkably low linear coefficient of thermal expansion (～25 ppm/°C), presumably due to the presence of the disordered graphitic structure. Its high density (～1.21 g/cm³), refractive index (～1.80 at 632 nm), and Young's modulus (～17.0 GPa) are also consistent with the interpretation. This study reveals important details about the effect of microscopic structure on the macroscopic properties of the highly crosslinked polymer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6909–6925, 2006     

Selection and Scheduling of Advanced Missions for NASA Using 0-1 Integer Linear Programming

A 0-1 integer linear programme for the selection and scheduling of US National Aeronautics and Space Administration (NASA) missions over a long planning horizon is presented. This model was formulated to allow a higher-level user-interaction with an advanced missions database currently being developed. The model implicitly considers the multi-objective nature of the problem, which results from the desire to maximize benefits in several categories as well as from the desire to minimize cost. In addition, the model allows the planner much flexibility in the selection process. This is accomplished by allowing the planner the ability to specify long- or short-term budget constraints, precursor/follow-on mission requirements, or any number of other idiosyncratic constraints which might be of importance in the decision process. Small example problems are solved in order to illustrate the approach, and areas for further research are discussed.     

Photopolymers for Rapid Prototyping of Soluble Mold Materials and Molding of Cellular Biomaterials

To substitute cross-linked photopolymers in rapid prototyping of mold materials and therefore extend the range of materials which can be casted, organo-soluble photopolymers were developed. Branched bisalkylacrylamides were suitable as base component for such formulations, due to their high reactivity, good mechanical properties, and excellent solubility of the formed polymers. These molding materials were used to prepare cellular biocompatible materials which could be used as bone replacement materials. Biocompatible crosslinkers based on methacrylates from hydrolyzed gelatine or lactic acid ethyleneglycol blockcopolymers and commercially available reactive diluents are the base components of such a formulation. Biocompatibility was investigated by osteoblast-like cells. Cellular biocompatible parts were obtained by thermal polymerization in soluble mould materials prepared by 3D-photoshaping.