New Raman spectrometer using a digital micromirror device and a photomultiplier tube detector for rapid on-line industrial analysis. Part II: Choice of analytical methods

In this paper, the performances of four improved analytical methods (backward stepwise selection of peak intensities, sum of characteristic peaks of a component, moving window partial least squares, and genetic algorithms) using wavelength selection for the analysis of xylene mixtures by Raman spectroscopy are tested for further use on the new "digital micromirror device associated with a photomultiplier tube" Raman spectrometer. It is shown that the errors of prediction using only a few selected points (from 4 to 49 depending on the method) are almost the same as when using the whole spectral range (1050 points). Compared to the last two methods, the "backward stepwise selection of peak intensities" and "sum of characteristic peaks of a component" methods are robust under industrial conditions and appear to be well suited for chemical quantitative analysis with the new Raman spectrometer, which allows the measurements of the total intensity to be made simultaneously for a number of pre-selected frequencies. Results show that the errors of prediction can be near to or even lower than 2%.     

A positively charged silver nanowire membrane for rapid on-site swabbing extraction and detection of trace inorganic explosives using a portable Raman spectrometer

The sensitive and on-site detection of inorganic explosives has raised serious concerns regarding public safety.However,high stability and non-volatility features currently limit their rapid on-site detection.Surface-enhanced Raman spectroscopy (SERS) is emerging as a powerful technique for the trace-level detection of different molecules.Plasmonic Ag nanowires were produced by a hydrothermal synthesis method using polyvinylpyrrolidone (PVP) as a negatively charged stabilizer.Here,we report a rapid detection method for inorganic explosives based on a simple surface swab with a positively charged diethyldithiocarbamate-modified Ag nanowire membrane coupled with SERS.This membrane,serving as an excellent SERS substrate with high uniformity,stability,and reusability,can capture both typical oxidizers in inorganic explosives and organic nitro-explosives,via electrostatic interaction.The detection level of perchlorates (ClO4-),chlorates (ClO3-),nitrates (NO3-),picric acid,and 2,4-dinitrophenol is as high as 2.0,1.7,0.1,45.8,and 36.6 ng,respectively.In addition,simulated typical inorganic explosives such as black powders,firecrackers,and match heads could also be detected.We believe that this membrane represents an attractive alternative for rapid on-site detection of inorganic explosives with high efficiency.     

A novel sensor for monitoring acoustic cavitation. Part I: Concept, theory, and prototype development

This paper describes a new concept for an ultrasonic cavitation sensor designed specifically for monitoring acoustic emissions generated by small microbubbles when driven by an applied acoustic field. Its novel features include a hollow, open-ended, cylindrical shape, with the sensor being a right circular cylinder of height 32 mm and external diameter 38 mm. The internal diameter of the sensor is 30 mm; its inner surface is fabricated from a 110 /spl mu/m layer of piezoelectrically active film whose measurement bandwidth is sufficient to enable acoustic emissions up to and beyond 10 MHz to be monitored. When in use, the sensor is immersed within the liquid test medium and high frequency (megahertz) acoustic emissions occurring within the hollow body of the sensor are monitored. In order to shield the sensor response from events occurring outside the cylinder, the outer surface of the sensor cylinder is encapsulated within a special 4 mm thick polyurethane-based cavitation shield with acoustic properties specifically developed to be minimally perturbing to the 40 kHz applied acoustic field but attenuating to ultrasound generated at megahertz frequencies (plane-wave transmission loss >30 dB at 1 MHz). This paper introduces the rationale behind the new sensor, describing details of its construction and the materials formulation program undertaken to develop the cavitation shield.     

Qualitative analysis using Raman spectroscopy and chemometrics: a comprehensive model system for narcotics analysis

The rapid, on-site identification of illicit narcotics, such as cocaine, is hindered by the diverse nature of the samples, which can contain a large variety of materials in a wide concentration range. This sample variance has a very strong influence on the analytical methodologies that can be utilized and in general prevents the widespread use of quantitative analysis of illicit narcotics on a routine basis. Raman spectroscopy, coupled with chemometric methods, can be used for in situ qualitative and quantitative analysis of illicit narcotics; however, careful consideration must be given to dealing with the extensive variety of sample types. To assess the efficacy of combining Raman spectroscopy and chemometrics for the identification of a target analyte under real-world conditions, a large-scale model sample system (633 samples) using a target (acetaminophen) mixed with a wide variety of excipients was created. Materials that exhibit problematic factors such as fluorescence, variable Raman scattering intensities, and extensive peak overlap were included to challenge the efficacy of chemometric data preprocessing and classification methods. In contrast to spectral matching analyte identification approaches, we have taken a chemometric classification model-based approach to account for the wide variances in spectral data. The first derivative of the Raman spectra from the fingerprint region (750-1900 cm(-1)) yielded the best classifications. Using a robust segmented cross-validation method, correct classification rates of better than ～90% could be attained with regression-based classification, compared to ～35% for SIMCA. This study demonstrates that even with very high degrees of sample variance, as evidenced by dramatic changes in Raman spectra, it is possible to obtain reasonably reliable identification using a combination of Raman spectroscopy and chemometrics. The model sample set can now be used to validate more advanced chemometric or machine learning algorithms being developed for the identification of analytes such as illicit narcotics.     

Characterisation and optimisation of flexible transfer lines for liquid helium. Part I: Experimental results

The transfer of liquid helium (LHe) into mobile dewars or transport vessels is a common and unavoidable process at LHe decant stations. During this transfer reasonable amounts of LHe evaporate due to heat leak and pressure drop. Thus generated helium gas needs to be collected and reliquefied which requires a huge amount of electrical energy. Therefore, the design of transfer lines used at LHe decant stations has been optimised to establish a LHe transfer with minor evaporation losses which increases the overall efficiency and capacity of LHe decant stations. This paper presents the experimental results achieved during the thermohydraulic optimisation of a flexible LHe transfer line. An extensive measurement campaign with a set of dedicated transfer lines equipped with pressure and temperature sensors led to unique experimental data of this specific transfer process. The experimental results cover the heat leak, the pressure drop, the transfer rate, the outlet quality, and the cool-down and warm-up behaviour of the examined transfer lines. Based on the obtained results the design of the considered flexible transfer line has been optimised, featuring reduced heat leak and pressure drop.     

An energetic formulation for the linear viscoelastic problem. Part I: Theoretical results and first calculations

An extremal principle is formulated for the linear viscoelastic problem with general viscous kernel. This is an extension of the classical total potential energy principle of the linear elasticity. Then a discretized formulation in space and time is shown for frame structures, using finite element technique. Several numerical examples, for two different kinds of viscoelastic materials, testify the accuracy and reliability of the proposed method. The matrix conditioning indexes obtained are compared with those achieved by applying the least square method.     

Similitude study for a laminated cylindrical tube under tensile, torsion, bending, internal and external pressure. Part I: governing equations

A general analytical model is developed for the stresses and displacements of an assembly of several coaxial laminated hollow circular cylinders made of orthotropic layers, and subjected to internal and external pressure, tensile, torsion and bending loads. Slip and friction conditions at the interfaces are not considered in lieu of perfect bonding. The model results are compared to the experimental tensile test of a composite tube. Displacements and stresses are evaluated for different angle-ply layers and radius-tothickness ratios.     

A total lagrangian formulation for the geometrically nonlinear analysis of structures using finite elements. Part I. Two-dimensional problems: Shell and plate structures

A total Lagrangian finite element formulation for the geometrically nonlinear analysis (large displacement/large rotations) of shells is presented. Explicit expressions of all relevant finite element matrices are obtained by means of the definition of a local co-ordinate system, based on the shell principal curvature directions, for the evaluation of strains and stresses. A series of examples of nonlinear analysis of shell and plate structures is given.     

Generalization of robustness test procedure for error estimators. Part II: test results for error estimators using SPR and REP

In this part of the paper we shall use the formulation given in the first part to assess the quality of recovery‐based error estimators using two recovery methods, i.e. superconvergent patch recovery (SPR) and recovery by equilibrium in patches (REP). The recovery methods have been shown to be asymptotically robust and superconvergent when applied to two‐dimensional problems. In this study we shall examine the behaviour of the recovery methods on several three‐dimensional mesh patterns for patches located either inside or at boundaries. This is performed by first finding an asymptotic finite element solution, irrespective of boundary conditions at far ends of the domain, and then applying the recovery methods. The test procedure near kinked boundaries is explained in a step‐by‐step manner. The results are given in a series of tables and figures for various cases of three‐dimensional mesh patterns. It has been experienced that the full superconvergent property is generally lost due to presence of boundary layer solution and the definition of the recoveries near boundaries though the results of the robustness test is still within an acceptable range. Copyright © 2005 John Wiley & Sons, Ltd.     

Process zone analysis for the single-edge notched specimen: Part I. Process zone size and crack profile

A systematic analysis of the process zone is presented. Relations among the process zone size, load and crack opening displacement (COD) are derived using the weight function method and a power function closing pressure distribution in the process zone. These relations are specialized and used to study the behaviour of the single-edge notched (SEN) specimen loaded in tension and in bending. This study shows that the method presented here may be successfully used to analyze the fracture of finite-size specimens.     

Determination of pre-impact occupant postures and analysis of consequences on injury outcome. Part I: a driving simulator study

This paper considers pre-impact vehicle maneuvers and analyzes the resulting driver motion from their comfort seating position. Part I of this work consists of analyzing the driver behavior during a crash. The study is conducted using the LAMIH driving simulator and involves 76 participants. The emergency situation is created by a truck emerging from behind a tractor on the opposite side of the road and tearing along the participant. The driver positioning throughout the simulation is recorded via five video cameras allowing view of the front scene, the driver face, feet and pedals, hands on the steering wheel and global lateral view. Data related to braking force, seat pressure, muscular activity for major groups of muscles and actions on the steering wheel are also collected.The typical response to this type of emergency event is to brace rearward into the seat and to straighten the arms against the steering wheel, or, to swerve to attempt to avoid the impacting vehicle. While turning the steering wheel, the forearm can be directly positioned on the airbag module at time of crash which represents a potential injurious situation.These positions are used in Part II to determine scenario of positions for numerical simulation of a frontal collision.     

Determination of lamb wave dispersion data in lossy anisotropic plates using time domain finite element analysis. Part I: theory and experimental verification

A theoretical and experimental approach for extraction of guided wave dispersion data in plate structures is described. Finite element modeling is used to calculate the surface displacement data (in-plane and out-of-plane) when the plate is subject to either symmetrical or antisymmetrical impulsive force stimulation at one or both of the parallel faces. Fourier transformation of the resultant space-time displacement histories is then employed to obtain phase velocity as a function of frequency. Experimental verification in the case of antisymmetrical stimulation is provided by means of a high-power Q-switched laser source that is used to excite guided waves in the plate. The subsequent out-of-plane displacement data were then obtained by means of a scanning laser vibrometer, and good agreement between theory and experiment is demonstrated. Examples of dispersion data are provided for aluminum, and excellent correlation between the data sets and conventional Rayleigh-Lamb theory for plate structures was obtained. This was then extended to lossy polymeric plates, in addition to both unpolarized and polarized piezoelectric ceramic plates, again with good agreement between the finite element modeling and optical experiments. The last set of results prepares the way for a detailed investigation of the nonhomogeneous piezoelectric composite waveguides described in a companion paper (Part II).     

Methodological approaches for histamine quantification using derivatization by chloroethylnitrosourea and ELISA measurement: Part I. Optimization of derivated histamine detection with coated-plates using optimal design

Using derivatization by chloroethylnitrosourea (CENU) a new strategy was used for raising antibodies directed against hapten (< 300 Da) and the quantification of these haptens by ELISA. After raising antibodies directed against histamine, they were characterized and used for ELISA measurements. The development of a quantitative method needs an optimization of both detection and derivatization step. Experimental design methodology has been applied to optimize the conditions of the detection of the derivatized histamine. Methods and results were closely related.     

High performance nano-titania photocatalytic paper composite. Part I: Experimental design study for TiO2 composite sheet using a natural zeolite microparticle system and its photocatalytic property

Nanosized titanium dioxide (TiO₂) photocatalytic papers were successfully prepared using a natural zeolite microparticle retention aid in papermaking. Applying a factorial experimental design, natural zeolite has been demonstrated to be the most significant and interactive factor for increasing the TiO₂ retention rate in paper stock. The photocatalysis of as-prepared sheets was evaluated with toluene as one of the representative volatile organic compounds (VOCs). Under UV irradiation, it was shown to be effective in removing gaseous toluene by photodecomposition, assisted by adsorption. It was revealed that natural zeolite plays an important role in both increasing retention rate of TiO₂ nanoparticles and enhancing photocatalytic efficiency of the paper. The photocatalytic paper can be potentially applied for environmental purification.     

Single photon ionization time-of-flight mass spectrometry with a pulsed electron beam pumped excimer VUV lamp for on-line gas analysis: setup and first results on cigarette smoke and human breath

Single-photon ionization (SPI) using vacuum ultraviolet (VUV) light produced by an electron beam pumped rare gas excimer source has been coupled to a compact and mobile time-of-flight mass spectrometer (TOFMS). The novel device enables real-time on-line monitoring of organic trace substances in complex gaseous matrixes down to the ppb range. The pulsed VUV radiation of the light source is employed for SPI in the ion source of the TOFMS. Ion extraction is also carried out in a pulsed mode with a short time delay with respect to ionization. The experimental setup of the interface VUV light source/time-of-flight mass spectrometer is described, and the novel SPI-TOFMS system is characterized by means of standard calibration gases. Limits of detection down to 50 ppb for aliphatic and aromatic hydrocarbons were achieved. First on-line applications comprised real-time measurements of aromatic and aliphatic trace compounds in mainstream cigarette smoke, which represents a highly dynamic fluctuating gaseous matrix. Time resolution was sufficient to monitor the smoking process on a puff-by-puff resolved basis. Furthermore, human breath analysis has been carried out to detect differences in the breath of a smoker and a nonsmoker, respectively. Several well-known biomarkers for smoke could be identified in the smoker's breath. The possibility for even shorter measurement times while maintaining the achieved sensitivity makes this new device a promising tool for on-line analysis of organic trace compounds in process gases or biological systems.     

Failure analysis of a martensitic stainless steel (CA-15M) roll manufactured by centrifugal casting. Part I: Material and fractographic characterization

The failure analysis of a martensitic stainless steel (CA-15M) roll manufactured by centrifugal casting and used in cast glass rolling was carried out by means of traditional characterization techniques (optical metallography, SEM, EDX microanalysis, tensile testing and XRD). The roll was in the as-cast condition and its microstructure featured large proportion of δ ferrite (between 20% and 27%) in a martensitic (α′) matrix, with the δ/α′ interfaces presenting an intergranular network of M₂₃C₆ carbides. The crack propagation began in the internal surface of the roll, with δ/α′ intergranular and transgranular cleavage in the “equiaxed region” of the casting, progressing to δ/α′ intergranular ductile fracture in the “columnar” and “chilled regions”. Tensile thermal stresses in the internal surface of the roll associated with microstructural embrittlement (network of interfacial carbide and microporosities) are thought to be the main causes for the premature failure of the roll. Finally, materials selection was performed to replace the CA-15M stainless steel with another class of stainless steel for centrifugal casting.     

An automatic adaptive refinement procedure for the reproducing kernel particle method. Part I: Stress recovery and a posteriori error estimation

In this study, an adaptive refinement procedure using the reproducing kernel particle method (RKPM) for the solution of 2D elastostatic problems is suggested. This adaptive refinement procedure is based on the Zienkiewicz and Zhu (ZZ) error estimator for the a posteriori error estimation and an adaptive finite point mesh generator for new point mesh generation. The presentation of the work is divided into two parts. In Part I, concentration will be paid on the stress recovery and the a posteriori error estimation processes for the RKPM. The proposed error estimator is different from most recovery type error estimators suggested previously in such a way that, rather than using the least-squares fitting approach, the recovery stress field is constructed by an extraction function approach. Numerical studies using 2D benchmark boundary value problems indicated that the recovered stress field obtained is more accurate and converges at a higher rate than the RKPM stress field. In Part II of the study, concentration will be shifted to the development of an adaptive refinement algorithm for the RKPM.