Effect of high-temperature shock-wave compression on few-layer MoS2, WS2 and MoSe2

Exposure of few-layer MoS2, WS2 and MoSe2 to high-temperature shock waves causes morphological changes and a significant decrease in the interlayer separation between the (002) planes, the decrease being greatest in MoSe2. Raman spectra show softening of both the A(1g) and the E-2g(1) modes initially, followed by a slightly stiffening. Using first-principles density functional theoretical analysis of the response of few-layer MoS2 to shock waves, we propose that a combination of shear and uniaxial compressive deformation leads to flattening of MoS2 sheets which is responsible for the changes in the vibrational spectra. (C) 2013 Elsevier B.V. All rights reserved.

Electron temperature distribution across a shock wave in a partially ionized gas

The electron temperature structure in a weakly ionized plasma is studied allowing the degree of ionization to vary across the shock wave. The values of the electron temperature and the downstream equilibrium temperature obtained with variable ionization are less than those for frozen ionization. The electron temperature rises sharply behind the shock for variable ionization while a gradual increase is predicted by frozen ionization.

Structure of shock waves at re-entry speeds

The unified structure of steady, one-dimensional shock waves in argon, in the absence of an external electric or magnetic field, is investigated. The analysis is based on a two-temperature, three-fluid continuum approach, using the Navier—Stokes equations as a model and including non-equilibrium collisional as well as radiative ionization phenomena. Quasi charge neutrality and zero velocity slip are assumed. The integral nature of the radiative terms is reduced to analytical forms through suitable spectral and directional approximations. The analysis is based on the method of matched asymptotic expansions. With respect to a suitably chosen small parameter, which is the ratio of atom-atom elastic collisional mean free-path to photon mean free-path, the following shock morphology emerges: within the radiation and electron thermal conduction dominated outer layer occurs an optically transparent discontinuity which consists of a chemically frozen heavy particle (atoms and ions) shock and a collisional ionization relaxation layer. Solutions are obtained for the first order with respect to the small parameter of the problem for two cases: (i) including electron thermal conduction and (ii) neglecting it in the analysis of the outer layer. It has been found that the influence of electron thermal conduction on the shock structure is substantial. Results for various free-stream conditions are presented in the form of tables and figures.

Investigations of separated flow over backward facing steps in IISc hypersonic shock tunnel

Two backward facing step (2 mm and 3 mm step height) models are selected for surface heat transfer measurements. The platinum thin film gauges are deposited on the Macor inserts using both hand paint and vacuum sputtering technique. Using the Eckert reference temperature method the heating rates has been theoretically calculated along the flat plate portion of the model and the theoretical estimates are compared with experimentally determined surface heat transfer rate. Theoretical analysis of heat flux distribution down stream of the backward facing step model has been carried out using Gai’s non-dimensional analysis. Based on the measured surface heating rates on the backward facing step, the reattachment distance is estimated for 2 and 3 mm step height at nominal Mach number of 7.6. It has been found from the present study that for 2 and 3 mm step height, it approximately takes about 10 and 8 step heights downstream of the model respectively for the flow to re-attach.

Structure of shock waves in partially ionized argon

The paper presents a unified picture of the structure of steady one-dimensional shock waves in partially ionized argon in the absence of external electric and magnetic fields. The study is based on a two-temperature three-fluid continuum approach using the Navier-Stokes equations as a model and taking account of nonequilibrium ionization. The analysis of the governing equations is based on the method of matched asymptotic expansions and leads to three layers: (1) a broad thermal layer dominated by electron thermal conduction; (2) an atom-ion shock structured by heavy-particle collisional dissipative mechanisms; and (3) an ionization relaxation layer in which electron-atom inelastic collisions dominate.

Propagation of an isothermal shock in stellar envelopes

We have studied in this paper the propagation of an isothermal shock in the radiative envelopes of the Bosman-Crespin model for a hot star and Boury’s model for a giant star. A spherically symmetric disturbance is supposed to be originated at or outside the surface of the convective core. We have used Whitham’s rule to study the variation in the shock strength and the shock velocity after modifying it for inclusion of pressure, energy and flux of radiation. We find the shock increases in strength as it propagates through the envelopes of decreasing density, pressure and temperature. The velocity of the shock decreases for very weak initial shock strengths, for intermediate initial shock strength it first decreases and then increases, while for large initial shock strength, it always increases. This aspect of the problem throws some light on the stability of the models under consideration.

Diaphragmless shock wave generators for industrial applications of shock waves

The prime focus of this study is to design a 50 mm internal diameter diaphragmless shock tube that can be used in an industrial facility for repeated loading of shock waves. The instantaneous rise in pressure and temperature of a medium can be used in a variety of industrial applications. We designed, fabricated and tested three different shock wave generators of which one system employs a highly elastic rubber membrane and the other systems use a fast acting pneumatic valve instead of conventional metal diaphragms. The valve opening speed is obtained with the help of a high speed camera. For shock generation systems with a pneumatic cylinder, it ranges from 0.325 to 1.15 m/s while it is around 8.3 m/s for the rubber membrane. Experiments are conducted using the three diaphragmless systems and the results obtained are analyzed carefully to obtain a relation between the opening speed of the valve and the amount of gas that is actually utilized in the generation of the shock wave for each system. The rubber membrane is not suitable for industrial applications because it needs to be replaced regularly and cannot withstand high driver pressures. The maximum shock Mach number obtained using the new diaphragmless system that uses the pneumatic valve is 2.125 +/- 0.2%. This system shows much promise for automation in an industrial environment.

Unimolecular HCl elimination from 1,2-dichloroethane: A single pulse shock tube and ab initio study

Thermal decomposition of 1,2-dichloroethane (1,2-DCE) has been studied in the temperature range of 10501175 K behind reflected shock waves in a single pulse shock tube. The unimolecular elimination of HCl is found to be the major channel through which 1,2-DCE decomposes under these conditions. The rate constant for the unimolecular elimination of HCl from 1,2-dichloroethane is found to be 10(13.98+/-0.80) exp(-57.8+/-2.0/RT) s(-1), where the activation energy is given in kcal mol(-1) and is very close to that value for CH3CH2Cl (EC). Ab initio (HF and MP2) and DFT calculations have been carried out to find the activation barrier and the structure of the transition state for this reaction channel from both EC and 1,2-DCE. The preexponential factors calculated at various levels of theory (BF/6-311++G**, MP2/6-311++G**, and B3LYP/6-311++G**) are (approximate to10(15) s(-1)) significantly larger than the experimental results. If the torsional mode in the ground state is treated as free internal rotation the preexponential factors reduce significantly, giving excellent agreement with experimental values. The DFT results are in excellent (fortuitous?) agreement with the experimental value for activation energy for 1,2-DCE while the MP2 and HF results seem to overestimate the barrier. However, DFT results for EC is 4.5 kcal mol(-1) less than the previously reported experimental values. At all levels, theory predicts an increase in HCI elimination barrier on beta-Cl substitution on EC.

Heat shock protein 70 as a biomarker of heat stress in a simulated hot cockpit

Background: Fighter pilots are frequently exposed to high temperatures during high-speed low-level flight. Heat strain can result in temporary impairment of cognitive functions and when severe, loss of consciousness and consequent loss of life and equipment. Induction of stress proteins is a highly conserved stress response mechanism from bacteria to humans. induced stress protein levels are known to be cytoprotective and have been correlated with stress tolerance. Although many studies on the heat shock response mechanisms have been performed in cell culture and animal model systems, there is very limited information on stress protein induction in human subjects. Hypothesis: Heat shock proteins (Hsp), especially Hsp70, may be induced in human subjects exposed to high temperatures in a hot cockpit designed to simulate heat stress experienced in low flying sorties. Methods: Six healthy volunteers were subjected to heat stress at 55degreesC in a high temperature cockpit simulator for a period of 1 h at 30% humidity. Physiological parameters such as oral and skin temperatures, heart rate, and sweat rate were monitored regularly during this time. The level of Hsp70 in leukocytes was examined before and after the heat exposure in each subject. Conclusions: Hsp70 was found to be significantly induced in all the six subjects exposed to heat stress. The level of induced Hsp70 appears to correlate with other strain indicators such as accumulative circulatory strain and Craig's modified index. The usefulness of Hsp70 as a molecular marker of heat stress in humans is discussed.

Structure and morphology studies of chromium film at elevated temperature in hypersonic environment

This paper presents the after shock heated structural and morphological studies of chromium film coated on hypersonic test model as a passive drag reduction element. The structural changes and the composition of phases of chromium due to shock heating (2850 K) are characterized using X-ray diffraction studies. Surface morphology changes of chromium coating have been studied using scanning electron microscopy (SEM) before and after shock heating. Significant amount of chromium ablation and sublimation from the model surface is noticed from SEM micrographs. Traces of randomly oriented chromium oxides formed along the coated surface confirm surface reaction of chromium with oxygen present behind the shock. Large traces of amorphous chromium oxide phases are also observed.

High-temperature kinetics of the reaction between CN and hydrocarbons using a novel high-enthalpy flow tube

More than 70 molecules of varied nature have been identified in the envelopes of carbon-rich stars through their spectral fingerprints in the microwave or far infrared regions. Many of them are carbon chain molecules and radicals, and a significant number are unique to the circumstellar medium. The determination of relevant laboratory kinetics data is critical to keep up with the development of the high spectral and spatial resolution observations and of the refinement of chemical models. Neutralneutral reactions of the CN radical with unsaturated hydrocarbons could be a dominant route in the formation of cyanopolyynes, even at low temperatures and deserve a detailed laboratory investigation. The approach we have developed aims to bridge the temperature gap between resistively heated flow tubes and shock tubes. The present kinetic measurements are obtained using a new reactor combining a high-enthalpy source with a flow tube and a pulsed laser photolysislaser-induced fluorescence system to probe the undergoing chemical reactions. The high-enthalpy flow tube has been used to measure the rate constant of the reaction of the CN radical with propane (C3H8), propene (C3H6), allene (C3H4), 1,3-butadiene (1,3-C4H6), and 1-butyne (C4H6) over a temperature range extending from 300 to 1200 K. All studied reactions of CN with unsaturated hydrocarbons are rapid, with rate coefficients greater than 10-10 cm3 center dot molecule-1 center dot s-1 and exhibit slight negative temperature dependence above room temperature. (c) 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 753766, 2012

Manually operated piston-driven shock tube

A simple hand-operated shock tube capable of producing Mach 2 shock waves is described. Performance of this miniature shock tube using compressed high pressure air created by a manually operated piston in the driver section of the shock tube as driver gas with air at 1 atm pressure as the test gas in the driven tube is presented. The performance of the shock tube is found to match well with the theoretically estimated values using normal shock relations. Applications of this shock tube named Reddy tube, include study of blast-induced traumatic brain injuries and high temperature chemical kinetics.

Two-step Synthesis of MoS2 Nanotubes using Shock Waves with Lead as Growth Promoter

A new two-step procedure for the synthesis of MoS2 nanotubes using lead as a growth promoter is reported. In the first step, molybdenum suboxide nanowhiskers containing a small amount of lead atoms were created by exposing a pressed MoS2+Pb mixture to highly compressed shock-heated argon gas, with estimated temperatures exceeding 9900 K. In the second step, these molybdenum suboxide nanowhiskers served as templates for the sulfidization of the oxide into MoS2 nanotubes (by using H2S gas in a reducing atmosphere at 820 degrees C). Unlike the case of WS2 nanotubes, the synthesis of a pure phase of MoS2 nanotubes from molybdenum oxide has proven challenging, due mostly to the volatile nature of the latter at the high requisite reaction temperatures (>800 degrees C). In contrast, the nature and apparent reaction mechanism of the method reported herein are amenable to future scale-up. The high-temperature shockwave system should also facilitate the synthesis of new nanostructures from other layered materials.

Thermal Decomposition of Propargyl Alcohol: Single Pulse Shock Tube Experimental and ab Initio Theoretical Study

Thermal decomposition of propargyl alcohol (C3H3OH), a molecule of interest in interstellar chemistry and combustion, was investigated using a single pulse shock tube in the temperature ranging from 953 to 1262 K. The products identified include acetylene, propyne, vinylacetylene, propynal, propenal, and benzene. The experimentally observed overall rate constant for thermal decomposition of propargyl alcohol was found to be k = 10((10.17 +/- 0.36)) exp(-39.70 +/- 1.83)/RT) s(-1) Ab initio theoretical calculations were carried out to understand the potential energy surfaces involved in the primary and secondary steps of propargyl alcohol thermal decomposition. Transition state theory was used to predict the rate constants, which were then used and refined in a kinetic simulation of the product profile. The first step in the decomposition is C-O bond dissociation, leading to the formation of two important radicals in combustion, OH and propargyl. This has been used to study the reverse OH propargyl radical reaction, about which there appears to be no prior work. Depending on the site of attack, this reaction leads to propargyl alcohol or propenal, one of the major products at temperatures below 1200 K. A detailed mechanism has been derived to explain all the observed products.