N-H center dot center dot center dot pi hydrogen-bonding and large-amplitude tipping vibrations in jet-cooled pyrrole-benzene

The N-H center dot center dot center dot pi hydrogen bond is an important intermolecular interaction in many biological systems. We have investigated the infrared (IR) and ultraviolet (UV) spectra of the supersonic-jet cooled complex of pyrrole with benzene and benzene-d(6) (Pyr center dot Bz, Pyr center dot Bz-d(6)). DFT-D density functional, SCS-MP2 and SCS-CC2 calculations predict a T-shaped and (almost) C(s) symmetric structure with an N-H center dot center dot center dot pi hydrogen bond to the benzene ring. The pyrrole is tipped by omega(S(0)) = +/- 13 degrees relative to the surface normal of Bz. The N center dot center dot center dot ring distance is 3.13 angstrom. In the S(1) excited state, SCS-CC2 calculations predict an increased tipping angle omega(S(1)) = +/- 21 degrees. The IR depletion spectra support the T-shaped geometry: The NH stretch is redshifted by -59 cm(-1), relative to the "free" NH stretch of pyrrole at 3531 cm(-1), indicating a moderately strong N-H center dot center dot center dot pi interaction. The interaction is weaker than in the (Pyr)(2) dimer, where the NH donor shift is -87 cm(-1) [Dauster et al., Phys. Chem. Chem. Phys., 2008, 10, 2827]. The IR C-H stretch frequencies and intensities of the Bz subunit are very similar to those of the acceptor in the (Bz)(2) dimer, confirming that Bz acts as the acceptor. While the S(1) <- S(0) electronic origin of Bz is forbidden and is not observable in the gas-phase, the UV spectrum of Pyr center dot Bz in the same region exhibits a weak 0(0)(0) band that is red-shifted by 58 cm(-1) relative to that of Bz (38 086 cm(-1)). The origin appears due to symmetry-breaking of the p-electron system of Bz by the asymmetric pyrrole NH center dot center dot center dot pi hydrogen bond. This contrasts with (Bz)(2), which does not exhibit a 0(0)(0) band. The Bz moiety in Pyr center dot Bz exhibits a 6a(0)(1) band at 0(0)(0) + 518 cm(-1) that is about 20x more intense than the origin band. The symmetry breaking by the NH center dot center dot center dot pi hydrogen bond splits the degeneracy of the v(6)(e(2g)) vibration, giving rise to 6a' and 6b' sub-bands that are spaced by similar to 6 cm(-1). Both the 0(0)(0) and 6(0)(1) bands of Pyr center dot Bz carry a progression in the low-frequency (10 cm(-1)) excited-state tipping vibration omega', in agreement with the change of the omega tipping angle predicted by SCS-MP2 and SCS-CC2 calculations.

Gas-phase Lifetimes of Nucleobase Analogues by Picosecond Pumpionization and Streak Techniques

The picosecond (ps) timescale is relevant for the investigation of many molecular dynamical processes such as fluorescence, nonradiative relaxation, intramolecular vibrational relaxation, molecular rotation and intermolecular energy transfer, to name a few. While investigations of ultrafast (femtosecond) processes of biological molecules, e.g. nucleobases and their analogues in the gas phase are available, there are few investigations on the ps time scale. We have constructed a ps pump-ionization setup and a ps streak camera fluorescence apparatus for the determination of lifetimes of supersonic jet-cooled and isolated molecules and clusters. The ps pump-ionization setup was used to determine the lifetimes of the nucleobase analogue 2-aminopurine (2AP) and of two 2AP˙(H2O)n water cluster isomers with n=1 and 2. Their lifetimes lie between 150 ps and 3 ns and are strongly cluster-size dependent. The ps streak camera setup was used to determine accurate fluorescence lifetimes of the uracil analogue 2-pyridone (2PY), its self-dimer (2PY)2, two isomers of its trimer (2PY)3 and its tetramer (2PY)4, which lie in the 7–12 ns range.

Variable-density jet flows induced by concentrated sources of momentum and energy

The planar and axisymmetric variable-density flows induced in a quiescent gas by a concentrated source of momentum that is simultaneously either a source or a sink of energy are investigated for application to the description of the velocity and temperature far fields in laminar gaseous jets with either large or small values of the initial jet-to-ambient temperature ratio. The source fluxes of momentum and heat are used to construct the characteristic scales of velocity and length in the region where the density differences are of the order of the ambient density, which is slender for the large values of the Reynolds number considered herein. The problem reduces to the integration of the dimensionless boundary-layer conservation equations, giving a solution that depends on the gas transport properties but is otherwise free of parameters. The boundary conditions at the jet exit for integration are obtained by analysing the self-similar flow that appears near the heat source in planar and axisymmetric configurations and also near the heat sink in the planar case. Numerical integrations of the boundary-layer equations with these conditions give solutions that describe accurately the velocity and temperature fields of very hot planar and round jets and also of very cold plane jets in the far field region where the density and temperature differences are comparable to the ambient values. Simple scaling arguments indicate that the point source description does not apply, however, to cold round jets, whose far field region is not large compared with the jet development region, as verified by numerical integrations

Development and evaluation of a pollution prevention technology for surface cleaning and decontamination : cooperative research and development agreement with Cold Jet, Inc.

Mode of access: Internet.

Gas turbines and jet propulsion, including rocket, hydrogen peroxide, and nuclear power plants: theory and application.

"Portions of this book first published [by the Dept. of Marine Engineering, U. S. Naval Academy] as a part of Combustion engines manual and...of Internal combustion engines."

The flow of a supersonic jet from a vessel with plane walls. Iztecheniye sverhzvookovoy strooi iz sosooda s ploskimi stenkami.

Translation of Istechenie sverkhzvukovoĭ strui iz sosuda s ploskimi stenkami (romanized form)

Modeling of Turbulent Natural Gas and Biogas Flames of the Delft Jet-in-Hot-Coflow Burner: Effects of Coflow Temperature, Fuel Temperature and Fuel Composition on the Flame Lift-Off Height

The structure of a turbulent non-premixed flame of a biogas fuel in a hot and diluted coflow mimicking moderate and intense low dilution (MILD) combustion is studied numerically. Biogas fuel is obtained by dilution of Dutch natural gas (DNG) with CO2. The results of biogas combustion are compared with those of DNG combustion in the Delft Jet-in-Hot-Coflow (DJHC) burner. New experimental measurements of lift-off height and of velocity and temperature statistics have been made to provide a database for evaluating the capability of numerical methods in predicting the flame structure. Compared to the lift-off height of the DNG flame, addition of 30 % carbon dioxide to the fuel increases the lift-off height by less than 15 %. Numerical simulations are conducted by solving the RANS equations using Reynolds stress model (RSM) as turbulence model in combination with EDC (Eddy Dissipation Concept) and transported probability density function (PDF) as turbulence-chemistry interaction models. The DRM19 reduced mechanism is used as chemical kinetics with the EDC model. A tabulated chemistry model based on the Flamelet Generated Manifold (FGM) is adopted in the PDF method. The table describes a non-adiabatic three stream mixing problem between fuel, coflow and ambient air based on igniting counterflow diffusion flamelets. The results show that the EDC/DRM19 and PDF/FGM models predict the experimentally observed decreasing trend of lift-off height with increase of the coflow temperature. Although more detailed chemistry is used with EDC, the temperature fluctuations at the coflow inlet (approximately 100K) cannot be included resulting in a significant overprediction of the flame temperature. Only the PDF modeling results with temperature fluctuations predict the correct mean temperature profiles of the biogas case and compare well with the experimental temperature distributions.

A Strategy to Characterize the LISA-Pathfinder Cold Gas Thruster System

The cold gas micro-propulsion system that will be used during the LISA-Pathfinder mission will be one of the most important component used to ensure the "free-fall" of the enclosed test masses. In this paper we present a possible strategy to characterize the effective direction and amplitude gain of each of the 6 thrusters of this system.

Structural and thermal performance of cold-formed steel stud wall systems under fire conditions

Cold-formed steel stud walls are a major component of Light Steel Framing (LSF) building systems used in commercial, industrial and residential buildings. In the conventional LSF stud wall systems, thin steel studs are protected from fire by placing one or two layers of plasterboard on both sides with or without cavity insulation. However, there is very limited data about the structural and thermal performance of stud wall systems while past research showed contradicting results, for example, about the benefits of cavity insulation. This research was therefore conducted to improve the knowledge and understanding of the structural and thermal performance of cold-formed steel stud wall systems (both load bearing and non-load bearing) under fire conditions and to develop new improved stud wall systems including reliable and simple methods to predict their fire resistance rating. Full scale fire tests of cold-formed steel stud wall systems formed the basis of this research. This research proposed an innovative LSF stud wall system in which a composite panel made of two plasterboards with insulation between them was used to improve the fire rating. Hence fire tests included both conventional steel stud walls with and without the use of cavity insulation and the new composite panel system. A propane fired gas furnace was specially designed and constructed first. The furnace was designed to deliver heat in accordance with the standard time temperature curve as proposed by AS 1530.4 (SA, 2005). A compression loading frame capable of loading the individual studs of a full scale steel stud wall system was also designed and built for the load-bearing tests. Fire tests included comprehensive time-temperature measurements across the thickness and along the length of all the specimens using K type thermocouples. They also included the measurements of load-deformation characteristics of stud walls until failure. The first phase of fire tests included 15 small scale fire tests of gypsum plasterboards, and composite panels using different types of insulating material of varying thickness and density. Fire performance of single and multiple layers of gypsum plasterboards was assessed including the effect of interfaces between adjacent plasterboards on the thermal performance. Effects of insulations such as glass fibre, rock fibre and cellulose fibre were also determined while the tests provided important data relating to the temperature at which the fall off of external plasterboards occurred. In the second phase, nine small scale non-load bearing wall specimens were tested to investigate the thermal performance of conventional and innovative steel stud wall systems. Effects of single and multiple layers of plasterboards with and without vertical joints were investigated. The new composite panels were seen to offer greater thermal protection to the studs in comparison to the conventional panels. In the third phase of fire tests, nine full scale load bearing wall specimens were tested to study the thermal and structural performance of the load bearing wall assemblies. A full scale test was also conducted at ambient temperature. These tests showed that the use of cavity insulation led to inferior fire performance of walls, and provided good explanations and supporting research data to overcome the incorrect industry assumptions about cavity insulation. They demonstrated that the use of insulation externally in a composite panel enhanced the thermal and structural performance of stud walls and increased their fire resistance rating significantly. Hence this research recommends the use of the new composite panel system for cold-formed LSF walls. This research also included steady state tensile tests at ambient and elevated temperatures to address the lack of reliable mechanical properties for high grade cold-formed steels at elevated temperatures. Suitable predictive equations were developed for calculating the yield strength and elastic modulus at elevated temperatures. In summary, this research has developed comprehensive experimental thermal and structural performance data for both the conventional and the proposed non-load bearing and load bearing stud wall systems under fire conditions. Idealized hot flange temperature profiles have been developed for non-insulated, cavity insulated and externally insulated load bearing wall models along with suitable equations for predicting their failure times. A graphical method has also been proposed to predict the failure times (fire rating) of non-load bearing and load bearing walls under different load ratios. The results from this research are useful to both fire researchers and engineers working in this field. Most importantly, this research has significantly improved the knowledge and understanding of cold-formed LSF walls under fire conditions, and developed an innovative LSF wall system with increased fire rating. It has clearly demonstrated the detrimental effects of using cavity insulation, and has paved the way for Australian building industries to develop new wall panels with increased fire rating for commercial applications worldwide.

Structural behaviour and design of cold-formed steel wall systems under fire conditions

In recent times, light gauge steel framed (LSF) structures, such as cold-formed steel wall systems, are increasingly used, but without a full understanding of their fire performance. Traditionally the fire resistance rating of these load-bearing LSF wall systems is based on approximate prescriptive methods developed based on limited fire tests. Very often they are limited to standard wall configurations used by the industry. Increased fire rating is provided simply by adding more plasterboards to these walls. This is not an acceptable situation as it not only inhibits innovation and structural and cost efficiencies but also casts doubt over the fire safety of these wall systems. Hence a detailed fire research study into the performance of LSF wall systems was undertaken using full scale fire tests and extensive numerical studies. A new composite wall panel developed at QUT was also considered in this study, where the insulation was used externally between the plasterboards on both sides of the steel wall frame instead of locating it in the cavity. Three full scale fire tests of LSF wall systems built using the new composite panel system were undertaken at a higher load ratio using a gas furnace designed to deliver heat in accordance with the standard time temperature curve in AS 1530.4 (SA, 2005). Fire tests included the measurements of load-deformation characteristics of LSF walls until failure as well as associated time-temperature measurements across the thickness and along the length of all the specimens. Tests of LSF walls under axial compression load have shown the improvement to their fire performance and fire resistance rating when the new composite panel was used. Hence this research recommends the use of the new composite panel system for cold-formed LSF walls. The numerical study was undertaken using a finite element program ABAQUS. The finite element analyses were conducted under both steady state and transient state conditions using the measured hot and cold flange temperature distributions from the fire tests. The elevated temperature reduction factors for mechanical properties were based on the equations proposed by Dolamune Kankanamge and Mahendran (2011). These finite element models were first validated by comparing their results with experimental test results from this study and Kolarkar (2010). The developed finite element models were able to predict the failure times within 5 minutes. The validated model was then used in a detailed numerical study into the strength of cold-formed thin-walled steel channels used in both the conventional and the new composite panel systems to increase the understanding of their behaviour under nonuniform elevated temperature conditions and to develop fire design rules. The measured time-temperature distributions obtained from the fire tests were used. Since the fire tests showed that the plasterboards provided sufficient lateral restraint until the failure of LSF wall panels, this assumption was also used in the analyses and was further validated by comparison with experimental results. Hence in this study of LSF wall studs, only the flexural buckling about the major axis and local buckling were considered. A new fire design method was proposed using AS/NZS 4600 (SA, 2005), NAS (AISI, 2007) and Eurocode 3 Part 1.3 (ECS, 2006). The importance of considering thermal bowing, magnified thermal bowing and neutral axis shift in the fire design was also investigated. A spread sheet based design tool was developed based on the above design codes to predict the failure load ratio versus time and temperature for varying LSF wall configurations including insulations. Idealised time-temperature profiles were developed based on the measured temperature values of the studs. This was used in a detailed numerical study to fully understand the structural behaviour of LSF wall panels. Appropriate equations were proposed to find the critical temperatures for different composite panels, varying in steel thickness, steel grade and screw spacing for any load ratio. Hence useful and simple design rules were proposed based on the current cold-formed steel structures and fire design standards, and their accuracy and advantages were discussed. The results were also used to validate the fire design rules developed based on AS/NZS 4600 (SA, 2005) and Eurocode Part 1.3 (ECS, 2006). This demonstrated the significant improvements to the design method when compared to the currently used prescriptive design methods for LSF wall systems under fire conditions. In summary, this research has developed comprehensive experimental and numerical thermal and structural performance data for both the conventional and the proposed new load bearing LSF wall systems under standard fire conditions. Finite element models were developed to predict the failure times of LSF walls accurately. Idealized hot flange temperature profiles were developed for non-insulated, cavity and externally insulated load bearing wall systems. Suitable fire design rules and spread sheet based design tools were developed based on the existing standards to predict the ultimate failure load, failure times and failure temperatures of LSF wall studs. Simplified equations were proposed to find the critical temperatures for varying wall panel configurations and load ratios. The results from this research are useful to both structural and fire engineers and researchers. Most importantly, this research has significantly improved the knowledge and understanding of cold-formed LSF loadbearing walls under standard fire conditions.

Numerical and experimental studies of cold-formed steel floor systems under standard fire conditions

Light gauge cold-formed steel frame (LSF) structures are increasingly used in industrial, commercial and residential buildings because of their non-combustibility, dimensional stability, and ease of installation. A floor-ceiling system is an example of its applications. LSF floor-ceiling systems must be designed to serve as fire compartment boundaries and provide adequate fire resistance. Fire rated floor-ceiling assemblies formed with new materials and construction methodologies have been increasingly used in buildings. However, limited research has been undertaken in the past and hence a thorough understanding of their fire resistance behaviour is not available. Recently a new composite panel in which an external insulation layer is used between two plasterboards has been developed at QUT to provide a higher fire rating to LSF floors under standard fire conditions. But its increased fire rating could not be determined using the currently available design methods. Research on LSF floor systems under fire conditions is relatively recent and the behaviour of floor joists and other components in the systems is not fully understood. The present design methods thus require the use of expensive fire protection materials to protect them from excessive heat increase during a fire. This leads to uneconomical and conservative designs. Fire rating of these floor systems is provided simply by adding more plasterboard sheets to the steel joists and such an approach is totally inefficient. Hence a detailed fire research study was undertaken into the structural and thermal performance of LSF floor systems including those protected by the new composite panel system using full scale fire tests and extensive numerical studies. Experimental study included both the conventional and the new steel floor-ceiling systems under structural and fire loads using a gas furnace designed to deliver heat in accordance with the standard time- temperature curve in AS 1530.4 (SA, 2005). Fire tests included the behavioural and deflection characteristics of LSF floor joists until failure as well as related time-temperature measurements across the section and along the length of all the specimens. Full scale fire tests have shown that the structural and thermal performance of externally insulated LSF floor system was superior than traditional LSF floors with or without cavity insulation. Therefore this research recommends the use of the new composite panel system for cold-formed LSF floor-ceiling systems. The numerical analyses of LSF floor joists were undertaken using the finite element program ABAQUS based on the measured time-temperature profiles obtained from fire tests under both steady state and transient state conditions. Mechanical properties at elevated temperatures were considered based on the equations proposed by Dolamune Kankanamge and Mahendran (2011). Finite element models were calibrated using the full scale test results and used to further provide a detailed understanding of the structural fire behaviour of the LSF floor-ceiling systems. The models also confirmed the superior performance of the new composite panel system. The validated model was then used in a detailed parametric study. Fire tests and the numerical studies showed that plasterboards provided sufficient lateral restraint to LSF floor joists until their failure. Hence only the section moment capacity of LSF floor joists subjected to local buckling effects was considered in this research. To predict the section moment capacity at elevated temperatures, the effective section modulus of joists at ambient temperature is generally considered adequate. However, this research has shown that it leads to considerable over- estimation of the local buckling capacity of joist subject to non-uniform temperature distributions under fire conditions. Therefore new simplified fire design rules were proposed for LSF floor joist to determine the section moment capacity at elevated temperature based on AS/NZS 4600 (SA, 2005), NAS (AISI, 2007) and Eurocode 3 Part 1.3 (ECS, 2006). The accuracy of the proposed fire design rules was verified with finite element analysis results. A spread sheet based design tool was also developed based on these design rules to predict the failure load ratio versus time, moment capacity versus time and temperature for various LSF floor configurations. Idealised time-temperature profiles of LSF floor joists were developed based on fire test measurements. They were used in the detailed parametric study to fully understand the structural and fire behaviour of LSF floor panels. Simple design rules were also proposed to predict both critical average joist temperatures and failure times (fire rating) of LSF floor systems with various floor configurations and structural parameters under any given load ratio. Findings from this research have led to a comprehensive understanding of the structural and fire behaviour of LSF floor systems including those protected by the new composite panel, and simple design methods. These design rules were proposed within the guidelines of the Australian/New Zealand, American and European cold- formed steel structures standard codes of practice. These may also lead to further improvements to fire resistance through suitable modifications to the current composite panel system.

Chemiluminescence imaging in supersonic combustors operating in radical-farming mode

Emission spectroscopy was used to investigate ignition and combustion characteristics of supersonic combustion ramjet engines. Two-dimensional scramjet models with inlet injection, fuelled with hydrogen gas, were used in the study. The scramjet engines were configured to operate in radical farming mode, where combustion radicals are formed behind shock waves reflected at the walls. The chemiluminescence emission signals were recorded in a two-dimensional, time-integrated fashion to give information on the location and distribution of the radical farms in the combustors. High signal levels were detected in localised regions immediately downstream of shock reflections, an indication of localised hydroxyl formation supporting the concept of radical farming. Results are presented for a symmetric as well as an asymmetric scramjet geometry. These data represent the first successful visualisation of radical farms in the hot pockets of a supersonic combustor. Spectrally resolved measurements have been obtained in the ultraviolet wavelength range between 300 and 400 nm. This data shows that the OH! chemiluminescence signal around 306nm is not the most dominant source of radiation observed in the radical farms.