Nitromethane pyrolysis in shock tubes and a micro flow reactor with a controlled temperature profile

Nitromethane has many applications, such as in racing, as a gasoline fuel additive, and as a monopropellant. Despite a large number of studies and the small size of the molecule, the combustion chemistry of nitromethane is still not well understood. To improve models, the pyrolysis of nitromethane (CH₃NO₂) was investigated experimentally in shock tubes and in a micro flow reactor with a controlled temperature profile (MFR), under dilute conditions. Several spectroscopic diagnostics were used in the shock tubes to follow the concentration time histories of CO, H₂O (both using IR laser absorption), and CH₃NO₂ (UV light absorption). A quadrupole mass spectrometer was used to measure CH₃NO₂, NO₂, CH₄, C₂H₄, and C₂H₂ at various temperatures with the MFR. These unique experimental results were compared to modern, detailed kinetics models from the literature, and no mechanism was able to reproduce these data over the wide range of conditions investigated. Predictions for the CO and H₂O levels were generally inaccurate, and the CH₄, C₂H₄, and C₂H₂ predictions were poor in most cases for the MFR data. Importantly, all models largely differ in their predictions. A numerical analysis was performed to identify ways to improve the next generation of nitromethane models. Results indicate that nitromethane decomposition needs to be improved below 1050 K, and that hydrocarbon-NOx interactions still need to be further investigated.     

Scattering by small defects in the neighbourhood of a fluid-solid interface

The scattering of incident plane elastic waves by a varietyof different defects that lie upon a fluid-solid interface isconsidered here using matched asymptotic expansions. The expansionscheme is developed in terms of a parameter , the ratio of typicaldefect length scale to a typical wavelength of the incidentfield, taken to be small. Three different canonical situations occur and these are illustratedvia three specific examples treated here: a rigid strut, anedge crack, and a rigid strip. In each case the leading-ordermatching is performed to identify the leading-order contributionof the defect to the acoustic field in the far field. In particular,each defect is identified with a source of dipole response ininterfacial stress of displacement. It is shown in the limit as s<<s1 that in the inner problemsthe fluid and solid pieces uncouple in a particularly convenientmanner allowing analytical solutions to be deduced. These arethen matched with appropriate outer solutions.     

Ein Beitrag zum Einfluß des Stoffüberganges auf eine erzwungene Konvektion an einer fluiden Phasengrenze

The interfacial-dynamic behaviour of a fluid two-phase-system with mass transfer was investigated under influence of forced convection in the manner of flat jets directed to the interface. The tangential velocities were measured at a characteristic point near to the interface air/water or in the interface itself using a Laser-Doppler-Velocimeter in dependence on the velocities of jets into two phases in both cases with and without transfer of acetone. The variations of velocities due to the interfacial effects are only detectable at small velocities of the jets. They are discussed by model conceptions and compared with the results of a theoretical research of heat transfer in a fluid two-phase-system (Interfacial-dynamic surface renewal model).     

A Comparison of Contact Stiffness Measurements Obtained by the Digital Image Correlation and Ultrasound Techniques

The digital image correlation (DIC) and ultrasound techniques have both previously been employed to measure the contact stiffness of real engineering interfaces, but a comprehensive comparison of these techniques has not previously been carried out. Such a comparison is addressed in the present paper. The principal novelty in this work is that DIC and ultrasound are used to simultaneously measure contact stiffness in the same tests and on the same contact interface. The results show that ultrasound measures somewhat higher contact stiffness magnitudes than DIC: at an average normal contact pressure of 70 MPa, ultrasound was around three times stiffer. Given that the techniques are vastly different in their measurement approach (DIC measures micron-scale relative displacements from external side-on images of the interface, while ultrasound uses the reflection of an Ångstrom scale ultrasonic perturbation from the interior of the interface itself), this level of agreement is thought to be encouraging. The difference in results can partly be explained by consideration of inherent physical differences between the techniques which have previously received little attention. Ultrasound measurement will always give the local elastic ‘unloading stiffness’ (even at a plastically deforming contact); whereas, a load-deflection technique like DIC, will give the ‘loading stiffness’. The reason for this difference is discussed in the paper and tests carried out under increasing tangential load in the pre-sliding regime illustrate this difference experimentally. Under normal loading, the increase in real contact area obscures the effect to some extent as both DIC and ultrasound stiffnesses increase with normal load. The results suggest that rough interfaces may be satisfactorily modelled as a variable stiffness spring whose stiffness increases with contact pressure as the smooth contact case is approached.     

Determination of the Frictional Properties of Titanium and Nickel Alloys Using the Digital Image Correlation Method

The paper describes experiments to investigate the frictional properties of a Titanium alloy (Ti-6Al-4V) and a Nickel alloy (Udimet 720) under representative engineering conditions. Flat fretting pads with rounded corners were clamped against a flat specimen and a servo-hydraulic tensile testing machine was used to apply cyclic displacement to the specimen. Slip displacement between the specimen and pad was measured remotely using an LVDT and locally using digital image correlation. The latter approach allowed accurate determination of the tangential contact stiffness from frictional hysteresis loops. The results obtained show that the contacts are significantly less stiff than would be predicted by a smooth elastic contact analysis. A finite element model of the experimental contact geometry was constructed and it was shown that good agreement with the experimental measurements of contact stiffness can be obtained with a suitable choice of elastic modulus for a compliant surface layer.     

Phthalocyanine 4 (Pc 4) photodynamic therapy of human OVCAR-3 tumor xenografts

Photodynamic therapy (PDT) is a cancer treatment modality utilizing a photosensitizer, light and oxygen. Photodynamic therapy with Photofrin has been approved by the U.S. Food and Drug Administration for treatment of advanced esophageal and early lung cancer. Because of certain drawbacks associated with the use of Photofrin, there is a need to identify new photosensitizers for human use. The photosensitizer Pc 4 (HOSiPc-OSi[CH3]2[CH2]3N[CH3]2) has yielded promising PDT effects in many in vitro and in vivo systems. The aim of this study was to assess the usefulness of Pc 4 as a PDT photosensitizer for a human tumor grown as a xenograft in athymic nude mice. The ovarian epithelial carcinoma (OVCAR-3) was heterotransplanted subcutaneously in athymic nude mice. Sixty mice bearing OVCAR-3 tumors (approximately 80-130 mm3) were divided into six groups of 10 animals each, three for controls and three for treatment. The Pc 4 was given by tail vein injection, and 48 h later a 1 cm area encompassing the tumor was irradiated with light from a diode laser coupled to a fiberoptic terminating in a microlens (lambda = 672 nm, 150 J/cm2, 150 mW/cm2). Tumors of control animals receiving no treatment, light alone or Pc 4 alone continued to grow. Of animals receiving 0.4 mg/kg Pc 4 and light, one (10%) had a complete response and was cured (no regrowth up to 90 days post-PDT), while all others (90%) had a partial response and were delayed in regrowth. Of animals receiving 0.6 mg/kg Pc 4 and light, eight (80%) had a complete response, and two of these were cured. Of animals receiving 1.0 mg/kg Pc 4 and light, six (60%) had a complete response, and two of these were cured. In additional experiments, tumors from animals treated with Pc 4 (1 mg/kg) and light were removed 15, 30, 60 and 180 min post-PDT, and from these tumors DNA and protein were extracted. Agarose gel electrophoresis revealed the presence of apoptotic DNA fragmentation as early as 15 min post-PDT. Western blotting showed the cleavage of the 116 kDa native poly(ADP-ribose) polymerase (PARP) into fragments of approximately 90 kDa, another indication of apoptosis, and the presence of p21/WAF1/CIP1 (p21) in all PDT-treated tumors. These changes did not occur in control tumors. Pc 4 appears to be an effective photosensitizer for PDT of human tumors grown as xenografts in nude mice. Early apoptosis, as revealed by PARP cleavage, DNA fragmentation and p21 overexpression, may be responsible for the excellent Pc 4-PDT response. Clinical trials of Pc 4-PDT are warranted.     

H2O time histories in the H2-NO2 system for validation of NOx hydrocarbon kinetics mechanisms

The development and refinement of NOx chemical kinetic mechanisms have been instrumental in understanding and reducing NOx formation. However, relatively little work has been performed with NOx species as the oxidizer, and such experiments can provide unique insights into NOx kinetics. Furthermore, speciation data can often provide useful information that complements global measurements such as ignition delay times in facilitating mechanism refinement. To provide such speciation data in the H₂-NO₂ system, H₂O measurements were performed using a fixed-wavelength, direct absorption laser diagnostic near 1.39 µm behind reflected shock waves in fuel-lean, near-stoichiometric, and fuel-rich mixtures of H₂ and NO₂ highly diluted in argon. Experiments were performed between 917 and 1782 K near atmospheric pressure. The H₂O profiles obtained herein are markedly different from those using O₂ as the oxidizer obtained in a previous study. The GRI 3.0 mechanism was found to greatly underestimate the H₂O formation, whereas two modern mechanisms were found to predict the H₂O formation quite accurately except at colder temperatures for fuel-rich conditions. Explanations for the differences between these mechanisms are given and discussed, with the conclusion that older mechanisms such as GRI 3.0 should not be used to model hydrocarbon/NOx combustion chemistry as they are lacking several key reactions and species, namely NO₃ and HONO. The discrepancy between models and data at lower temperatures could not be reconciled even when modifying two of the most-sensitive reaction rates. To the best of the authors’ knowledge, this study presents the first shock-tube speciation study in the H₂-NO₂ system.     

Polymethylhydrosiloxane (PMHS)/trifluoroacetic acid (TFA): a novel system for reductive amination reactions

Polymethylhydrosiloxane (PMHS)/trifluoroacetic acid (TFA) was discovered as a novel metal-free system for reductive amination reactions. A variety of (het)aryl amines as well as a representative carbamate and urea were successfully alkylated by benzaldehyde in the presence of PMHS and TFA in dichloromethane at room temperature in moderate to excellent yields (28-87%). Furthermore, this reaction protocol was successfully applied to the alkylation of p-nitroaniline with a wide range of aldehydes, ketones, and a representative acetal to obtain the alkylated products in yields ranging from 40% to 92%. The current work represents one of the very few examples of PMHS being activated by a Brønsted acid.