The “Chunnel” Fire. I: Chemoplastic Softening in Rapidly Heated Concrete

This paper and its companion paper present the main results of an assessment of the fire in the Channel Tunnel (the “Chunnel”), which destroyed a part of the concrete tunnel rings by thermal spalling. The study seeks (1) to evaluate the effect of thermal damage (loss of elastic stiffness) and thermal decohesion (loss of material strength) upon the stress state and cracking at a structural level; and (2) to check whether restrained thermal dilatation can explain the thermal spalling observed during the fire. In the present paper, a macroscopic material model for rapidly heated concrete is developed. It accounts explicitly for the dehydration of concrete and its cross-effects with deformation (chemomechanical couplings) and temperature (chemothermal couplings). The thermal decohesion is considered as chemoplastic softening within the theoretical framework of chemoplasticity. Furthermore, kinetics of dehydration, dimensional analysis, and thermodynamic equilibrium considerations show that a unique thermal dehydration function exists that relates the hydration degree to the temperature rise, provided that the characteristic time of dehydration is much inferior to the characteristic time of structural heat conduction. The experimental determination of the thermal dehydration function from in-situ measurements of the elastic modulus versus furnace temperature rise is shown from experimental data available from the chunnel concrete. Finally, by way of an example, the proposed constitutive model for rapidly heated concrete is combined with the three-parameter William-Warnke criterion extended to isotropic chemoplastic softening.     

Effects of Size and Slenderness on Ductility of Fracturing Structures

The ductility of an elastic structure with a growing crack may be defined as the ratio of the additional load-point displacement that is caused by the crack at the moment of loss of stability under displacement control to the elastic displacement at no crack at the moment of peak load. The stability loss at displacement control is known to occur when the load-deflection curve of the whole structural system with the loading device (characterized by a spring) reaches a snapback point. Based on the known stress intensity factor as a function of crack length, the well-known method of linear elastic fracture mechanics is used to calculate the load-deflection curve and determine the states of snapback and maximum loads. An example of a notched three-point bend beam with a growing crack is analyzed numerically. The ductility is determined and its dependence of the structure size, slenderness, and stiffness of the loading device is clarified. The family of the curves of ductility versus structure size at various loading device stiffnesses is found to exhibit at a certain critical stiffness a transition from bounded single-valued functions of D to unbounded two-valued functions of D. The method of solution is general and is applicable to cracked structures of any shape. The flexibility (force) method can be adapted to extend the ductility analysis to structural assemblages provided that the stress intensity factor of the cracked structural part considered alone is known. This study leads to an improved understanding of ductility, which should be useful mainly for design against dynamic loads.     

Non-diffractive Vector Bessel Beams

Abstract

The non-diffractive vector Bessel beams of an arbitrary order are examined as both the solution to the vector Helmholtz wave equation and the superposition of vector components of the angular spectrum. The transverse and longitudinal intensity components of the vector Bessel beams are analysed for the radial, azimuthal, circular and linear polarizations. The radially and azimuthally polarized beams are assumed to be formed by the axicon polarizers used with the initially unpolarized or linearly polarized light. Conditions in which the linearly polarized Bessel beams can be approximated by the scalar solutions to the wave equation are also discussed.     

Metal-Coated Fullerenes C60Mn: Calculations for M = Be,Mg, Al AND n = 12, 20, 32

Abstract

Semiempirical quantum-chemical PM3 calculations are reported for a relatively new class of exohedral metallo-fullerenes - metal-coated or metal-covered fullerenes: C₆₀M_n. The exohedral species were recently observed, however, their geometrical and electronic structure is not known yet. In this paper, relatively-even metal-atom distributions over the fullerene rings are considered - such regular forms are computed for M= Be, Mg, Al. Three selected stoichiometrics are treated: C₆₀M₁₂, C₆₀M₂₀, and C₆₀M₃₂. The stoichiometrics correspond to the location of the metal atoms above the twelve pentagons, above the twenty hexagons, and above each of the thirty two rings of C₆₀ This interesting arrangement over the rings is possible only for some types of atoms, while other elements are localized above bonds or atoms, or inside the cage, or even react and destroy the cage. Other limitation comes from the parametrization of the computational methods - the computations are performed with the PM3 semiempirical method and metal-layer atomization heats are used as a stability measure. Structural characteristics are presented, too. Considerable reductions of the cage symmetry are reported and their relationships to Jahn-Teller effect are discussed, too (no case of the icosahedral symmetry is found).     

Computations of Low-Energy Non-Icosahedral Structures of C6− 60

Abstract

Owing to the three-fold degeneracy of the LUMO in C₆₀, its hexa-anion is not subjected to Jahn-Teller distortions. In contrast to the accepted presumptions, however, computations at the MNDO, AMI, PM3, SAM1, HF/STO-3G, HF/3-21G, and HF/4-31G levels show that the completely relaxed, non-icosahedral cage of C^6? ₆₀is lower in energy. The computed energy gain varies between 60 and 150 kJ/mol and thus, it is consistently significant (the most sophisticated approach, HF/4-31G, yields 93 kJ/mol). The longest C-C bond in the relaxed structures is at most computed 0.05 Å longer compared to the 5/6 bond in the icosahedral C^6? ₆₀The symmetry of C^6? ₆₀is relaxed to D₂ A C_2v, isomer is discussed, too.     

The Conceptual Design of a Radiant Chamber and Preliminary Optimization of a Process Tubular Furnace

The design procedure of a process tubular furnace (or fired heater) can generally be divided into three design stages: the preliminary design of furnace, a detailed thermal and hydraulic simulation of the furnace, and final design solution, and the mechanical solution of the furnace (stress analysis, drawings preparation, etc.). The first design stage (the preliminary design of the furnace and cost prediction) is usually connected with a proposal for the customer when only the basic process and furnace design data are usually known. In this design stage, it is appropriate for the furnace designer to not have much detail for a reliable design method. The procedure for the preliminary design of a radiant chamber is usually a main part of such a design method because the radiant chamber represents a basic and dominant part of the modern process tubular furnace. The conceptual (or preliminary) design of the radiant chamber makes up the main part of this process. The presented method is based on standard, time-tested design methods (e.g., the Lobo-Evans method and Belokon's method). It is shown how these standard global design methods can be (for common operating conditions) suitable, generalized, and simplified. It allows for the purpose of the conceptual radiant chamber design the arrangement of the basic heat transfer equation for the radiant chamber. The derived form of the heat transfer equation then allows one to obtain basic process and geometrical radiant chamber characteristics of the given furnace type (cylindrical, box, etc.) iteratively. A developed radiant chamber calculation connected with standard procedures for the design of the furnace convection parts and stack (together with cost predictions) is used, and the method for a quick preliminary evaluation of the influence of the main design and process furnace parameters (dimensions of radiant chamber and convection parts, average heat flux to radiant tubes, absorbed heat in radiant chamber and convection part of furnace, stack size, and fuel consumption) for the total costs was developed. It allows the optimization of the furnace from an investment, operating, or total cost point-of-view in the preliminary design stage of the furnace. The developed method can also be used for the effective solution of the furnace integration into the process. The application of the developed method is demonstrated through a case study—the optimum design of a furnace for a crude atmospheric distillation unit.     

Zirconocene silanolate complexes and their heterogeneous siliceous analogues as catalysts for phenylsilane dehydropolymerization

The efficient catalytic dehydropolymerization of phenylsilane by homogeneous zirconocene bissilanolates ([{(c-C₅H₉)₇Si₈O₁₂O}₂Zr(η⁵-C₅H₅)₂] (1a); [{(c-C₅H₉)₇Si₈O₁₂O}₂Zr(η⁵-C₅H₄Bu)₂] (1b) [{(c-C₅H₉)₇Si₇O₉(OSiMe₃)O₂}Zr(η⁵-C₅H₅)₂] (4); [{(Me₃CO)₃SiO}₂Zr(η⁵-C₅H₅)₂] (5)) and chlorosilanolates ([{(c-C₅H₉)₇Si₈O₁₂O}ZrCl(η⁵-C₅H₄Bu)₂] (2); ([{(c-C₅H₉)₇Si₇O₉O₃}Zr₂Cl(η⁵-C₅H₅)₄] (3a); [{(c-C₅H₉)₇Si₇O₉O₃}Zr₂Cl(η⁵-C₅H₄Bu)₄] (3b)) has been demonstrated. The presence of at least one silanol ligand in the zirconocene moiety was found essential for high catalytic performance. Solid state structure of complex 1a was determined by single crystal X-ray diffraction analysis. A series of nine zirconocene-siliceous catalysts were prepared by grafting of zirconocene moiety onto silica using three general methods: (a) reaction of [(η⁵-C₅H₅)₂ZrCl₂] with silica in the presence of NEt₃; (b) reaction of [(η⁵-C₅H₅)₂ZrMe₂] with silica; (c) reaction of solely [(η⁵-C₅H₅)₂ZrCl₂] with silica. Supported catalysts were characterized by ICP-MS, FT-IR, TGA and selected examples by XPS analysis. Those catalysts prepared by method (a) and (b) were found efficient in the phenylsilane polymerization although a higher Zr/monomer ratio had to be used in comparison with homogeneous analogues. The low concentration of residual silanol groups in supported catalysts was found essential for their high catalytic performance. Advantageous reusability of supported catalysts was demonstrated using SiO₂₍₅₀₀₎/Cp₂ZrCl₂/NEt₃(5.8). The catalytic performance was retained in three consecutive cycles producing polymers with almost identical properties.     

Influence of a compatibilizer on the morphology development in polymer blends under elongation

Compatibilization is the modification of the interface in immiscible polymer blends in order to refine and stabilize their phase structure. The presence of a compatibilizer at the interface markedly affects the deformation behaviour of the dispersed droplets during and after cessation of flow. In this work the morphology development in blends of polystyrene and linear low-density polyethylene compatibilized with styrene-butadiene-styrene triblock copolymer during and after uniaxial elongation was investigated by means of electron microscopy and small-angle X-ray scattering. The incorporation of only 1 wt.-% of the compatibilizer led to a pronounced increase of the stationary elongational viscosity of the blend. It was found, that at moderate capillary number (Ca ≈ Ca_CR) the compatibilizer stabilises the droplets against break-ups during the flow. When Ca >> Ca_CR no differences in the deformation of uncompatibilized and compatibilized droplets were observed. After cessation of the flow, the presence of the compatibilizer prevented the droplet break-up and supported and accelerated the shape recovery of the elongated particles.     

Influence of different SiC surface treatments performed prior to Ni ohmic contacts formation

This work is dealing with the influence of surface treatment on ohmic contacts to hexagonal N-type SiC with medium doping level. The contact materials were Ni and Ni₂Si. The structures had to be annealed at high temperatures in order to reach ohmic behavior. A number of surface treatment methods were tested: wet cleaning, plasma etching, intentional oxidation with etching, H₂ annealing and their combinations. After some types of cleaning, the SiC surface was immediately analysed using the XPS method. The results of the analyses showed that the composition of the surface was not much influenced by these treatments. At lower annealing temperatures (approx. up to 850 °C) the prepared contacts showed Schottky behavior with large scatter of parameters. After annealing at approx. 960 °C, where the onset of ohmic behavior is expected, the structures were truly ohmic and of good parameters. Cleaning methods had just a negligible influence on the electrical parameters of the ohmic contacts. An explanation for these observed facts is suggested: Although - already on the basis of the XPS results - we could speak about a negligible influence of the cleaning onto the contact parameters, there might come across also other mechanisms coming from interaction of contact materials with SiC, which caused similar behavior of ohmic contacts on differently treated surfaces.     

Experimental Method for Complex Thermo-mechanical Material Analysis

An experimental system for complex thermo-mechanical material analysis is presented in this article. The system provides simultaneous measurements of tensile properties as well as heat generation in the process of tensile deformation. The cooling curve of the sample after its reversible deformation was measured. On the basis of an exponential model of a cooling body with respect to the Biot number Bi, it is possible to calculate the specific heat capacity c _p , the thermal diffusivity α, and the thermal conductivity k. The method had been tested on a variety of materials and the results were compared to those in the technical literature or obtained by reference independent experiments and showed very good agreement.