障碍物扰动对半开口管道中火焰传播特性的影响

自从1926年Chanman和Wheeler率先开创有障碍物管道中的火焰传播研究工作以来，管道中障碍物扰动引起的火焰加速现象引起了广泛的关注。由于这类现象在燃烧科学上的学术意义及其在生产中诸如安全问题等方面的实际意义，人们相继进行了一系列的研究工作。归纳起来，可以分为两大类：1）封闭管道的火焰传播。人们在不同形状的管道或容器中研究了障碍物对火焰加速的影响，在理论分析和数值计算方面也作了一些有益的工作；2）开口管道的火焰传播。相对于闭口管道，开口管道中的火焰传播研究则逊色得多。这方面尚缺乏系统的实验数据，理论方面的分析也欠缺得多。但当前在实际中，并不乏开口体系的应用，如，现已广泛应用于电力系统的一种燃气除灰装置，是一燃烧气体燃料的半开口系统。因此，研究半开口管道中非稳态燃烧的加速机制具有重要意义。在本论文工作中，通过大量的实验研究，比较系统地研究了障碍物的扰动对预混火焰传播特性的影响。实验在一长L=5m、内径D＝80mm的一端封闭、一端开口的火焰传播管内进行，管内均匀布置障碍物，通过改变障碍物的形状、间距、阻塞比大小，同时选用五种不同的可燃气体，探索了障碍物结构对预混湍流火焰加速和管内压力上升的影响。实验表明，对于敏感气体如氢气和乙炔，由于障碍物扰动产生的影响，火焰不断加速，并最终达到一准稳定状态；在适当的条件下，火焰传播状态可由爆燃向爆轰转变，此时火焰速度发生跃变；而对干不敏感气体如甲烷，则爆燃转爆轰现象不容易发生。在不同的火焰传播状态，障碍物结构特性对火焰速度和压力产生的影响各不相同。在缓燃态，随着阻塞比的变化，最大火焰速度先上升后下降，在BR=0.3～0.4之间存在一最大值；在銮塞态，最大火焰速度受阻塞比变化的影响不明显，略低于燃烧产物的声速；在阻塞比BR＝0.5附近，压力达到最大值。而在爆轰态，随着阻塞比的增加，最大火焰速度和压力逐渐降低，爆燃转爆轰的浓度范围变小。由于在有障碍物的管道中，火焰速度很容易达到声速（变塞态）或超声速（爆轰态），必须考虑流体的马赫数效应。本文在前人研究成果的基础上，给出了湍流马赫数修正的可压缩性两方程湍流模型，模拟了半开口狭长管道中重复布置的障碍物引起的湍流火焰加速现象。最大火焰速度和管内压力的计算结果与实验测量值吻合良好，这表明用修正后的湍流模型能够比较真实地模拟障碍物管内预混火焰的发展过程。通过对管道内障碍物扰动引起的燃烧波加速的机理和技术研究，对流场扰动对燃烧波产生和发展的影响规律有了比较全面的了解，研究结果对气脉冲除灰技术的完善具有直接的指导意义。

Numerical Investigation On The Flowfield Of "Swallowtail" Cavity For Supersonic Mixing Enhancement

A "swallowtail" cavity for the supersonic combustor was proposed to serve as an efficient flame holder for scramjets by enhancing the mass exchange between the cavity and the main flow. A numerical study on the "swallowtail" cavity was conducted by solving the three-dimensional Reynolds-averaged Navier-Stokes equations implemented with a k-epsilon turbulence model in a multi-block mesh. Turbulence model and numerical algorithms were validated first, and then test cases were calculated to investigate into the mechanism of cavity flows. Numerical results demonstrated that the certain mass in the supersonic main flow was sucked into the cavity and moved spirally toward the combustor walls. After that, the flow went out of the cavity at its lateral end, and finally was efficiently mixed with the main flow. The comparison between the "swallowtail" cavity and the conventional one showed that the mass exchanged between the cavity and the main flow was enhanced by the lateral flow that was induced due to the pressure gradient inside the cavity and was driven by the three-dimensional vortex ring generated from the "swallowtail" cavity structure.

Self-organized generation of transverse waves in diverging cylindrical detonations

Self-organized generation of transverse waves associated with the transverse wave instabilities at a diverging cylindrical detonation front was numerically studied by solving two-dimensional Euler equations implemented with an improved two-step chemical kinetic model. After solution validation, four mechanisms of the transverse wave generation were identified from numerical simulations, and referred to as the concave front focusing, the kinked front evolution, the wrinkled front evolution and the transverse wave merging, respectively. The propagation of the cylindrical detonation is maintained by the growth of the transverse waves that match the rate of increase in surface area of the detonation front to asymptotically approach a constant average number of transverse waves per unit length along the circumference of the detonation front. This cell bifurcation phenomenon of cellular detonations is discussed in detail to gain better understanding on detonation physics.

Laminar Burning Velocities and Markstein Lengths of Premixed Methane/Air Flames near the Lean Flammability Limit in Microgravity

Effects of flame stretch on the laminar burning velocities of near-limit fuel-lean methane/air flames have been studied experimentally using a microgravity environment to minimize the complications of buoyancy. Outwardly propagating spherical flames were employed to assess the sensitivities of the laminar burning velocity to flame stretch, represented by Markstein lengths, and the fundamental laminar burning velocities of unstretched flames. Resulting data were reported for methane/air mixtures at ambient temperature and pressure, over the specific range of equivalence ratio that extended from 0.512 (the microgravity flammability limit found in the combustion chamber) to 0.601. Present measurements of unstretched laminar burning velocities were in good agreement with the unique existing microgravity data set at all measured equivalence ratios. Most of previous 1-g experiments using a variety of experimental techniques, however, appeared to give significantly higher burning velocities than the microgravity results. Furthermore, the burning velocities predicted by three chemical reaction mechanisms, which have been tuned primarily under off-limit conditions, were also considerably higher than the present experimental data. Additional results of the present investigation were derived for the overall activation energy and corresponding Zeldovich numbers, and the variation of the global flame Lewis numbers with equivalence ratio. The implications of these results were discussed. 2010 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Sequence specific recognition and cleavage of DNA by synthetic molecules

DNA recognition is an essential biological process responsible for the regulation of cellular functions including protein synthesis and cell division and is implicated in the mechanism of action of some anticancer drugs. Studies directed towards defining the elements responsible for sequence specific DNA recognition through the study of the interactions of synthetic organic ligands with DNA are described.

DNA recognition by poly-N-methylpyrrolecarboxamides was studied by the synthesis and characterization of a series of molecules where the number of contiguous N-methylpyrrolecarboxamide units was increased from 2 to 9. The effect of this incremental change in structure on DNA recognition has been investigated at base pair resolution using affinity cleaving and MPE•Fe(II) footprinting techniques. These studies led to a quantitative relationship between the number of amides in the molecule and the DNA binding site size. This relationship is called the n + 1 rule and it states that a poly-N methylpyrrolecarboxamide molecule with n amides will bind n + 1 base pairs of DNA. This rule is consistent with a model where the carboxamides of these compounds form three center bridging hydrogen bonds between adjacent base pairs on opposite strands of the helix. The poly-N methylpyrrolecarboxamide recognition element was found to preferentially bind poly dA•poly dT stretches; however, both binding site selection and orientation were found to be affected by flanking sequences. Cleavage of large DNA is also described.

One approach towards the design of molecules that bind large sequences of double helical DNA sequence specifically is to couple DNA binding subunits of similar or diverse base pair specificity. Bis-EDTA-distamycin-fumaramide (BEDF) is an octaamide dimer of two tri-N methylpyrrolecarboxamide subunits linked by fumaramide. DNA recognition by BEDF was compared to P7E, an octaamide molecule containing seven consecutive pyrroles. These two compounds were found to recognize the same sites on pBR322 with approximately the same affinities demonstrating that fumaramide is an effective linking element for Nmethylpyrrolecarboxamide recognition subunits. Further studies involved the synthesis and characterization of a trimer of tetra-N-methylpyrrolecarboxamide subunits linked by β-alanine ((P4)_(3)E). This trimerization produced a molecule which is capable of recognizing 16 base pairs of A•T DNA, more than a turn and a half of the DNA helix.

DNA footprinting is a powerful direct method for determining the binding sites of proteins and small molecules on heterogeneous DNA. It was found that attachment of EDTA•Fe(II) to spermine creates a molecule, SE•Fe(II), which binds and cleaves DNA sequence neutrally. This lack of specificity provides evidence that at the nucleotide level polyamines recognize heterogeneous DNA independent of sequence and allows SE•Fe(II) to be used as a footprinting reagent. SE•Fe(II) was compared with two other small molecule footprinting reagents, EDTA•Fe(II) and MPE•Fe(II).

Numerical and Experimental Investigation On The Prevention of Co Deflagration

The exhaust gases from industrial furnaces contain a huge amount of heat and chemical enthalpy. However, it is hard to recover this energy since exhaust gases invariably contain combustible components such as carbon monoxide (CC). If the CO is unexpectedly ignited during the heat recovery process, deflagration or even detonation could occur, with serious consequences such as complete destruction of the equipment. In order to safely utilize the heat energy contained in exhaust gas, danger of its explosion must be fully avoided. The mechanism of gas deflagration and its prevention must therefore be studied. In this paper, we describe a numerical and experimental investigation of the deflagration process in a semi-opened tube. The results show that, upon ignition, a low-pressure wave initially spreads within the tube and then deflagration begins. For the purpose of preventing deflagration, an appropriate amount of nitrogen was injected into the tube at a fixed position. Both simulation and experimental results have shown that the injection of inert gas can successfully interrupt the deflagration process. The peak value of the deflagration pressure can thereby be reduced by around 50%. (C) 2008 Elsevier Ltd. All rights reserved.

Theoretical studies of novel organic systems : biradicals, polyradicals, and conducting polymers

Chapter 1

Cyclobutanediyl has been studied in both its singlet and triplet states by ab initio electronic structure theory. The triplet, which is the ground state of the molecule, exists in both C_(2h) and C_(2v) forms, which interconvert via a C_s transition state. For the singlet, only a C_(2h) form is found. It passes, via a C_s transition state, onto the C_(2v) surface on which bicyclobutane is the only minimum. The ring-flipping (inversion) process in bicyclobutane includes the singlet biradical as an intermediate, and involves a novel, nonleast motion pathway. Semiclassical periodic orbit theory indicates that the various minima on both the singlet and triplet surfaces can interconvert via quantum mechanical tunneling.

Chapter 2

The dimethylenepolycyclobutadienes (n) are the non-Kekulé analogues of the classical acenes. Application of a variety of theoretical methods reveals several novel features of such structures. Most interesting is the emergence of a parity rule. When n is even, n is predicted to be a singlet, with n disjoint NBMOs. When n is odd, theory predicts a triplet ground state with (n+1) NBMOs that are not fully disjoint.

Chapter 3

Bi(cyclobutadienyl) (2), the cyclobutadiene analogue of biphenyl, and its homologues tri- (3) and tetra(cyclobutadienyl) (4) have been studied using electronic structure theory. Ab initio calculations on 2 reveal that the central bond is a true double bond, and that the structure is best thought of as two allyl radicals plus an ethylene. The singlet and triplet states are essentially degenerate. Trimer 3 is two allyls plus a dimethylenecyclobutanediyl, while 4 is two coplanar bi(cyclobutadienyl) units connected by a single bond. For both 3 and 4, the quintet, triplet, and singlet states are essentially degenerate, indicating that they are tetraradicals. The infinite polymer, polycyclobutadiene, has been studied by HMO, EHCO, and VEH methods. Several geometries based on the structures of 3 and 4 have been studied, and the band structures are quite intriguing. A novel crossing between the valence and conduction bands produces a small band gap and a high density of states at the Fermi level.

Chapter 4

At the level of Hückel theory, polyfulvene has a HOCO-LUCO degeneracy much like that seen in polyacetylene. Higher levels of theory remove the degeneracy, but the band gap (E_g) is predicted to be significantly smaller than analogous structures such as polythiophene and polypyrrole at the fulvenoid geometry. An alternative geometry, which we have termed quinoid, is also conceivable for polyfulvene, and it is predicted to have a much larger E_g. The effects of benzannelation to produce analogues of polyisothianaphthene have been evaluated. We propose a new model for such structures based on conventional orbital mixing arguments. Several of the proposed structures have quite interesting properties, which suggest that they are excellent candidates for conducting polymers.

Chapter 5

Theoretical studies of polydimethylenecyclobutene and polydiisopropylidene- cyclobutene reveal that, because of steric crowding, they cannot achieve a planar, fully conjugated structure in either their undoped or doped states. Rather, the structure consists of essentially orthogonal hexatriene units. Such a structure is incompatible with conventional conduction mechanisms involving polarons and bipolarons.

Progress in numerical modeling of non-premixed combustion

Progress is made on the numerical modeling of both laminar and turbulent non-premixed flames. Instead of solving the transport equations for the numerous species involved in the combustion process, the present study proposes reduced-order combustion models based on local flame structures.

For laminar non-premixed flames, curvature and multi-dimensional diffusion effects are found critical for the accurate prediction of sooting tendencies. A new numerical model based on modified flamelet equations is proposed. Sooting tendencies are calculated numerically using the proposed model for a wide range of species. These first numerically-computed sooting tendencies are in good agreement with experimental data. To further quantify curvature and multi-dimensional effects, a general flamelet formulation is derived mathematically. A budget analysis of the general flamelet equations is performed on an axisymmetric laminar diffusion flame. A new chemistry tabulation method based on the general flamelet formulation is proposed. This new tabulation method is applied to the same flame and demonstrates significant improvement compared to previous techniques.

For turbulent non-premixed flames, a new model to account for chemistry-turbulence interactions is proposed. %It is found that these interactions are not important for radicals and small species, but substantial for aromatic species. The validity of various existing flamelet-based chemistry tabulation methods is examined, and a new linear relaxation model is proposed for aromatic species. The proposed relaxation model is validated against full chemistry calculations. To further quantify the importance of aromatic chemistry-turbulence interactions, Large-Eddy Simulations (LES) have been performed on a turbulent sooting jet flame. %The aforementioned relaxation model is used to provide closure for the chemical source terms of transported aromatic species. The effects of turbulent unsteadiness on soot are highlighted by comparing the LES results with a separate LES using fully-tabulated chemistry. It is shown that turbulent unsteady effects are of critical importance for the accurate prediction of not only the inception locations, but also the magnitude and fluctuations of soot.

Combustion of CS₂/O₂ in a laminar mixing layer and processes in the CO chemical laser

The combustion of CS₂ and O₂ in a free burning laminar mixing layer at low pressure was investigated using emission spectroscopy. The temperature fields, CO vibrational distributions, and CO concentrations were measured. The data indicate that vibration ally excited CO was produced in the mixing layer flames, but that there were no vibrational population inversions. In comparison with the CS₂/O₂ premixed flames, the mixing layer flames favored greater production of COS and CO₂. Computer modeling was used to study the mechanisms responsible for the production of COS and CO₂, and to study how the branching chain mechanism responsible for production of CO affects the behavior of the mixing layer flame. The influences of the gas additives, N₂O, COS, and CNBr, were also investigated.

Characterization and modeling of premixed turbulent n-heptane flames in the thin reaction zone regime

n-heptane/air premixed turbulent flames in the high-Karlovitz portion of the thin reaction zone regime are characterized and modeled in this thesis using Direct Numerical Simulations (DNS) with detailed chemistry. In order to perform these simulations, a time-integration scheme that can efficiently handle the stiffness of the equations solved is developed first. A first simulation with unity Lewis number is considered in order to assess the effect of turbulence on the flame in the absence of differential diffusion. A second simulation with non-unity Lewis numbers is considered to study how turbulence affects differential diffusion. In the absence of differential diffusion, minimal departure from the 1D unstretched flame structure (species vs. temperature profiles) is observed. In the non-unity Lewis number case, the flame structure lies between that of 1D unstretched flames with "laminar" non-unity Lewis numbers and unity Lewis number. This is attributed to effective Lewis numbers resulting from intense turbulent mixing and a first model is proposed. The reaction zone is shown to be thin for both flames, yet large chemical source term fluctuations are observed. The fuel consumption rate is found to be only weakly correlated with stretch, although local extinctions in the non-unity Lewis number case are well correlated with high curvature. These results explain the apparent turbulent flame speeds. Other variables that better correlate with this fuel burning rate are identified through a coordinate transformation. It is shown that the unity Lewis number turbulent flames can be accurately described by a set of 1D (in progress variable space) flamelet equations parameterized by the dissipation rate of the progress variable. In the non-unity Lewis number flames, the flamelet equations suggest a dependence on a second parameter, the diffusion of the progress variable. A new tabulation approach is proposed for the simulation of such flames with these dimensionally-reduced manifolds.

The changes in various iron compounds in culture media for algae. [Translation from: Archiv fur Hydrobiologie Supplemente Band 38(1/2) 151-169, 1970.]

The purpose of this work is a contribution to the quantitative record of the use of iron by planktonic algae. Preliminary experiments with Chlorella to determine the rate of iron intake in the presence of inorganic sources of iron did not produce the desired result. The crucial point of this work is the investigation of the influence of various external factors on the stability of FeEDTA (FeEDTA = Ferric(III)-compound of ethylene-diamine tetra-acetic acid), since this compound appears to be particularly well-suited as a source of iron for planktonic algae (e.g. TAMIYA et al. 1953). Cultures of Chlorella fusca in a light thermostat were used in experimental research. Methods and results are discussed.