Thermodynamic perturbation theory for fused sphere hard chain fluids using nonadditive interactions

A model is developed for the equation of state of fused chains based on Wertheim thermodynamic perturbation theory and nonadditive size interactions. The model also assumes that the structure (represented by the radial distribution function) of the fused chain fluid is the same as that of the touching hard sphere chain fluid. The model is completely based on spherical additive and nonadditive size interactions. The model has the advantage of offering good agreement with simulation data while at the same time being independent of fitted parameters. The model is most accurate for short chains, small values of Delta (slightly fused spheres) and at intermediate (liquidlike) densities.     

Towards understanding the critical heat flux for industrial applications

Understanding CHF is of an upmost importance in many industries, especially in the design and operation of boilers, nuclear power plants, cryogenic systems, etc. Due to safety issues related to the nuclear power plants, and the adaptation of CHF as the limiting criterion of power generation, it is important to understand the mechanisms of CHF relevant to nuclear systems operation. Moreover, CHF is expected to occur during transients than steady-state conditions. Therefore, knowledge of transient CHF is of great importance for the safety evaluation of nuclear reactors under transient condition. In this paper, the existing CHF experimental and modeling studies are discussed in order to understand the phenomena leading to CHF. Also, the effect of transient conditions on CHF for nuclear fuels has been evaluated.     

Influence of branch content on the microstructure of blends of linear and octene-branched polyethylene: a MD simulation study

Microstructure of linear low-density polyethylene (LLDPE) with linear high-density polyethylene (HDPE) is investigated by molecular dynamics (MD) simulation. The branch content of LLDPE was varied from 10 to 60 branches/1000 C. An equimolar mixture of each of the two polymers is simulated in the NVT ensemble at 500 K and at average experimental densities of the two polymer melts. Initially, chains of LLDPE and HDPE were completely mixed and evolution of conformations with time was monitored. The blends were found to microphase separate when the branch content of LLDPE exceeded 30 branches/1000 C. At 40 branches/1000 C, the two polymers displayed partial microphase separation and complete microphase separation was observed at 60 branches/1000 C. Substantial short-range order and mismatch of molecular conformations is observed in the microphase-separated systems.     

Modelling the CPI using a lognormal diffusion process and implications on forecasting inflation

The Maximum Likelihood estimator is used within a lognormaldiffusion process and closed form analytical solutions are obtained.The monthly CPI forecasts are estimated for the period between1970 and 2002. The quarterly estimates of inflation rates areobtained from monthly forecasts rather than from quarterly data.This has significantly improved the estimates of inflation rates.The model also produced a superior fit as compared to randomwalk and GARCH(p,q)-M models. The adopted approach is foundto be simple, economical and generally suitable for modellingstochastic processes that reflect aggregation over time stemmingfrom many factors, and in which the transition path betweenconsecutive states is relatively smooth.     

A study of hand vibration on chipping and grinding operators,part I: Vibration acceleration levels measured on pneumatic tools used in chipping and grinding operations

This paper describes the acceleration measurements and data analysis aspect of a comprehensive multidisciplined field study of several hundred chipper and grinder workers using pneumatic hand-held tools. Engineering testing of a sampling of these tools indicated that for a frequency range of 6·3 Hz to 1000 Hz, overall acceleration levels between 2000 m/s² and 24 000 m/s² were measured on the chisels and levels between 37 m/s² and 350 m/s² were measured on the handles of chipping hammers. Hand grinder acceleration levels ranged from 6 m/s² to 21 m/s².     

A study of hand vibration on chipping and grinding operators,part III: Power levels into the hands of operators of pneumatic tools used in chipping and grinding operations

This paper presents a method for calculating power transmitted to the hands of operators who use vibrating hand tools. Results that relate to a comprehensive multidisciplined NIOSH field study of several hundred chipper and grinder workers who used pneumatic hand tools are presented. The results of this study indicated that the power in the frequency range of 6·3 Hz to 1000 Hz transmitted to the hand ranged from 1·08 × 10³ to 7·23 × 10³ J/s for the chisel and from 8·52 × 10^?1 to 1·57 × 10² J/s for the handle of chipping hammers. For pneumatic grinders the power transmitted to the hands of the tool operators was in the range of 6·58 × 10^?3 to 2·35 × 10^?3 J/s over the same frequency range.     

Column robustness case study for a liquid chromatographic method validated in compliance with ICH, VICH, and GMP guidelines

This article presents a case study in dealing with robustness investigations and attempts by our analytical laboratory to address these issues without sacrificing valuable time in revamping the method validation prior to submission. A liquid chromatographic method is developed for the analysis of a novel triazinetrione anticoccidial product. The method effectively separates the active pharmaceutical ingredient (API), impurities, and preservatives in the API and product formulation. For much of the validation, the method holds up to the rigorous guidelines of the International Conference of Harmonization, the International Cooperation on Harmonization of Technical Requirements for Registration of Veterinary Medicinal Products, and the Good Manufacturing Practices. However, in analyzing a base-degraded sample one of the impurity peaks yields inconsistent retention times (RTs) during a series of injections. When switching the system to another analytical column from the same supplier, this impurity peak elutes at a different retention window and the remaining peaks in the chromatographic profile remain essentially the same. This RT variation of a single peak in the chromatographic profile is observed with additional columns from the same supplier and from different manufacturing lots. This suitability problem is not encountered with the columns used in the method development stage. The method no longer meets the robustness criteria established for pharmaceutical methods. An investigation is commenced and it is discovered that with the addition of tetrabutylammonium hydroxide to the mobile phases, the impurity peak gives a consistent RT in relation to the active peak. The peak shows comparable RTs relative to that of the API peak with columns of different silica lots and bond lots. All peaks, including the aforementioned impurity peak, are well-resolved under the revised high-performance liquid chromatographic conditions. This temporary solution enables continued submission work for FDA, but the robustness of this method is still a concern. After further investigation, it is determined that inhomogeneity of the active sites on the column's stationary phase is the likely culprit. Fortunately, a new column is found to be more suitable for this method and a column qualification study is initiated.     

A General Strategy to Enhance Donor-Acceptor Molecules Using Solvent-Excluding Substituents

While organic donor-acceptor (D-A) molecules are widely employed in multiple areas, the application of more D-A molecules could be limited because of an inherent polarity sensitivity that inhibits photochemical processes. Presented here is a facile chemical modification to attenuate solvent-dependent mechanisms of excited-state quenching through addition of a β-carbonyl-based polar substituent. The results reveal a mechanism wherein the β-carbonyl substituent creates a structural buffer between the donor and the surrounding solvent. Through computational and experimental analyses, it is demonstrated that the β-carbonyl simultaneously attenuates two distinct solvent-dependent quenching mechanisms. Using the β-carbonyl substituent, improvements in the photophysical properties of commonly used D-A fluorophores and their enhanced performance in biological imaging are shown.