Nanoindentation of biodegradable cellulose diacetate‐graft‐poly(L‐lactide) copolymers: Effect of molecular composition and thermal aging on mechanical properties

Nanoindentation of cellulose diacetate‐graft‐poly(lactide)s (CDA‐g‐PLLAs) synthesized by ring opening graft copolymerization of L ‐lactide in bulk onto the residual hydroxyl positions on CDA were conducted to investigate the effect of the molecular composition and thermal aging on mechanical properties and creep behavior. Continuous stiffness measurement (CSM) technique was used to obtained hardness and elastic modulus. These material properties were expressed as a mean value from 100 to 300 nm depths and an unloading value at final indentation depth. The hardness and elastic modulus in all CDA‐g‐PLLAs were higher than those in pure CDA, indicating that the introduction of PLLA increases the hardness and elastic modulus. With an increase of crystallinity by thermal aging, the hardness and elastic modulus were increased in both CDA‐g‐PLLA and PLLA. The creep test performed by CSM showed that the creep strain of CDA was decreased by the grafting of PLLA. Thermal aging decreased the creep strain of CDA‐g‐PLLA and PLLA. With an increase of holding time, hardness was decreased, whereas elastic modulus was kept almost constant. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1114–1121, 2007     

Pressure broadening of the J=5←4 transition of carbon monoxide from 17 to 200 K: A new collisional cooling experiment

A new spectroscopic experiment has been constructed at the Jet Propulsion Laboratory. This experiment employs the collisional cooling technique to study gases at temperatures below their condensation points. Specifically, the experiment has been designed to mimic the temperatures of the interstellar medium for the study of water under these conditions. The ultimate purpose is to measure state-to-state excitation rates under equilibrium conditions to provide insights into the interpretation of interstellar water spectra obtained from space-borne platforms such as the Herschel Space Observatory. This paper presents an overview of the new experiment including a discussion of its design and a detailed explanation of the system. In addition, we report a pressure broadening study of the J=5←4 transition of CO at 576 GHz used as a system validation. The new results are compared with measurements from the literature as a validation of the new experiment. In addition, the non-classical behavior of the pressure broadening of CO at low temperature observed in the measurements will be discussed.     

The influence of N‐vinyl pyrrolidone on polymerization kinetics and thermo‐mechanical properties of crosslinked acrylate polymers

Polymerization of multifunctional acrylate monomers generates crosslinked polymers that are noted for their mechanical strength, thermal stability, and chemical resistance. A common reactive diluent to photopolymerizable formulations is N‐vinyl pyrrolidone (NVP), which is known to reduce the inhibition of free radical photopolymerization by atmospheric oxygen. In this work, the copolymerization behavior of NVP was examined in acrylate monomers with two to five functional groups. At concentrations as low as 2 wt %, NVP increases the polymerization rate in copolymerization with multifunctional acrylate monomer. The relative rate enhancement associated with adding NVP increases dramatically as the number of acrylate double bonds changes from two to five. The influence of NVP on polymerization kinetics is related to synergistic cross‐propagation between NVP and acrylate monomer, which becomes increasingly favorable with diffusion limitations. This synergy extends bimolecular termination into higher double bond conversion through reaction diffusion controlled termination. Copolymerizing concentrations of 5–30 DB% NVP with diacrylate or pentaacrylate monomer also increases Young's modulus and the glass transition temperature (T_g) in comparison to neat acrylate polymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4062–4073, 2007     

Mathematical modelling and simulation of adsorption processes at spherical microparticles.

A model for the adsorption process at spherical microparticles under transient diffusion conditions has been developed and solved using numerical simulation. This model allowed us to demonstrate that the system is controlled by two main dimensionless parameters: the adsorption rate constant ka' and the saturation parameter beta. Analytical models for the adsorption process at spherical microparticles under steady-state mass transport conditions have been derived. These models use previously developed empirical relationships for the calculation of the mass transfer coefficient (kc). The properties of the system were studied for both the case where mass transport is described by diffusion only and the case where it is the result of a coupled diffusion/convection process. These mathematical tools were then used to analyse the results obtained for the uptake of CuII by glassy carbon powder modified with the monomer L-cysteine methyl ester and to extract a minimum value for the adsorption rate constant which was found to be of the order of 10(-4) cm s(-1).     

A hybrid heuristic ordering and variable neighbourhood search for the nurse rostering problem

This paper is concerned with the development of intelligent decision support methodologies for nurse rostering problems in large modern hospital environments. We present an approach which hybridises heuristic ordering with variable neighbourhood search. We show that the search can be extended and the solution quality can be significantly improved by the careful combination and repeated use of heuristic ordering, variable neighbourhood search and back-tracking. The amount of computational time that is allowed plays a significant role and we analyse and discuss this. The algorithms are evaluated against a commercial Genetic Algorithm on commercial data. We demonstrate that this methodology can significantly outperform the commercial algorithm. This paper is one of the few in the scientific nurse rostering literature which deal with commercial data and which compare against a commercially implemented algorithm.     

The behavior of higher order mode shape derivatives in damaged,beam-like structures

This work considers the effect that damage has upon the higher order derivatives of mode shapes of structures having primarily beam-like vibration. Via numerical investigations, the sensitivity of various damage related parameters in inducing changes in these higher order modal derivatives is determined, leading to a more complete understanding of what factors make the most contribution to significant changes in these derivatives. It is concluded that higher order mode shape derivatives (e.g., modal curvature, third derivative, and fourth derivative) are better indicators of damage than the mode shapes. Three distinct types of response for the damage-induced higher order derivative discontinuities are identified as three key parameters (the mass loss, stiffness loss, and damage radius scale) vary. From this, formal approximations are obtained for the expected forms of the higher order derivative discontinuities based upon the underlying behavior predicted by a simple relation among these three parameters. These approximations are checked with numerical simulations, and an excellent level of agreement is observed under appropriate conditions. Finally, the potential of these higher order derivative changes for indicating the presence and location of damage in a global setting is examined.     

A singular control model with application to the goodwill problem

We consider a stochastic system whose uncontrolled state dynamics are modelled by a general one-dimensional Itô diffusion. The control effort that can be applied to this system takes the form that is associated with the so-called monotone follower problem of singular stochastic control. The control problem that we address aims at maximising a performance criterion that rewards high values of the utility derived from the system’s controlled state but penalises any expenditure of control effort. This problem has been motivated by applications such as the so-called goodwill problem in which the system’s state is used to represent the image that a product has in a market, while control expenditure is associated with raising the product’s image, e.g., through advertising. We obtain the solution to the optimisation problem that we consider in a closed analytic form under rather general assumptions. Also, our analysis establishes a number of results that are concerned with analytic as well as probabilistic expressions for the first derivative of the solution to a second-order linear non-homogeneous ordinary differential equation. These results have independent interest and can potentially be of use to the solution of other one-dimensional stochastic control problems.     

Novel michael addition networks containing urethane hydrogen bonding

Covalently crosslinked networks based on poly(propylene glycol) bis(acetoacetate) with either neopentyl glycol diacrylate or hydroxyethyl acrylate derivatized bis(4‐isocyanatocyclohexyl)methane (HMDI) were prepared utilizing the Michael addition reaction in the presence of catalytic quantities of diazabicyclo[5.4.0]undec‐7‐ene (DBU). These networks were prepared in the absence of solvent at 23 °C without the formation of byproducts. Mechanical and thermal analyses of the networks were performed utilizing DMA, tensile testing, and TGA. Tensile analysis revealed that the introduction of hydrogen‐bonding urethane linkages in the diacrylate segment resulted in higher tensile strengths and elongation to break compared with nonhydrogen‐bonding analogs. All crosslinked products exhibited high gel fractions and excellent thermomechanical properties. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4118–4128, 2007