Fault diagnosis in chemical processes using Fisher discriminant analysis, discriminant partial least squares, and principal component analysis

Principal component analysis (PCA) is the most commonly used dimensionality reduction technique for detecting and diagnosing faults in chemical processes. Although PCA contains certain optimality properties in terms of fault detection, and has been widely applied for fault diagnosis, it is not best suited for fault diagnosis. Discriminant partial least squares (DPLS) has been shown to improve fault diagnosis for small-scale classification problems as compared with PCA. Fisher's discriminant analysis (FDA) has advantages from a theoretical point of view. In this paper, we develop an information criterion that automatically determines the order of the dimensionality reduction for FDA and DPLS, and show that FDA and DPLS are more proficient than PCA for diagnosing faults, both theoretically and by applying these techniques to simulated data collected from the Tennessee Eastman chemical plant simulator.     

Characterization of sprayed CuInS2 films by XRD and Raman spectroscopy measurements

We studied CuInS₂ (CIS) film growth using two deposition methods, which were high electrostatic field assisted ultrasonic spray (HEFAUS) deposition and sulfurization of Cu-In metallic film. The sprayed-films were grown with chalcopyrite ordering and Cu-Au ordering mixed. In order to obtain higher quality CIS films, post-sulfurization was carried out for sprayed-films. The post-sulfurization induced improvement of crystallinity and enhancement of chalcopyrite ordering. However, it was observed that Cu-Au ordering still coexisted in the CIS film after post-sulfurization. With the same sulfurization condition, sulfurization was done to transform Cu-In metallic film into CIS film. The sulfurized metallic film was turned out to be formed as CIS film with higher crystallinity and better chalcopyrite ordering than sulfurized sprayed-films. All fabricated films were characterized by X-ray diffraction, Raman scattering, scanning electron microscope and energy dispersive X-ray analysis measurements.     

Wavelet neural networks for modelling high pressure inactivation kinetics of Listeria monocytogenes in UHT whole milk

The aim of the present work was to investigate the applicability of a Wavelet Neural Network to describe the inactivation pattern of Listeria monocytogenes by high hydrostatic pressure in ultra high temperature (UHT) whole milk, and evaluate its performance against models used in predictive microbiology such as the re-parameterized Gompertz and modified Weibull equations. A comparative study with linear partial least squares regression (PLS-R) as well as neural network (NN) models demonstrated on the same dataset has been also considered. Milk was artificially inoculated with an initial population of the pathogen of ca. 10⁷ CFU/ml and exposed to a range of high pressures (350, 450, 550, 600 MPa) for up to 40 min at ambient temperature (ca. 25 °C). Typical survival curves were obtained including a shoulder, a log-linear and a tailing phase. Increasing the magnitude of the applied pressure resulted in increasing levels of inactivation. Modelling approaches provided good fit to experimental training data as inferred by the low values of the root mean squared error (RMSE) and the high values of regression coefficient (R²). Models were validated at 400 and 500 MPa with independent experimental data. First or second order polynomial models were employed to relate the inactivation parameters to pressure, whereas the wavelet network as well as the PLS and NN models were utilised as a one-step modelling approach. The prediction performance of the proposed learning-based network was better at both validation pressures. The development of accurate models to describe the survival curves of micro-organisms in high pressure treatment would be very important to the food industry for process optimisation, food safety and would eventually expand the applicability of this non-thermal process.     

Influence of the deposition conditions on the crystallographic structure and the GaAs refraction index

An experimental study of the influence of deposition conditions of GaAs thin films growth, by radio frequency sputtering method, on the structure and the refraction index has been performed. The X-ray diffraction and spectrophotometer results, with different deposition conditions, are reported.The refraction index depends on the structure, which also depends on four deposition parameters, namely, the self-bias voltage, V_p, the argon pressure, P_Ar, the target-to-substrate distance, d, and the substrate temperature, T_s. Hence, it has been observed that, the index refraction of the films decreases with V_p and T_s and increases essentially with P_Ar.     

Ultra-high g deceleration–time measurement for the penetration into steel target

This paper presented an ultra-high g deceleration measurement device for studies of the penetration into steel target. More than 145,000g deceleration value was measured by this device during a penetration experiment where the steel target was 50 mm thick. Both the design of the device and the experiment of penetration into steel target were described in detail. Numerical simulation utilizing ANSYS/LS_DYNA was carried out with the same penetration condition. The numerical simulation analysis results were consistent with the experimental result. However, compared with theoretical analysis result of a previously published penetration model, the experiment one showed some disparities.     

Biological synthesis of silver nanoparticles using the fungus Aspergillus flavus

The fungus, Aspergillus flavus when challenged with silver nitrate solution accumulated silver nanoparticles on the surface of its cell wall in 72 h. These nanoparticles dislodged by ultrasonication showed an absorption peak at 420 nm in UV-visible spectrum corresponding to the plasmon resonance of silver nanoparticles. The transmission electron micrographs of dislodged nanoparticles in aqueous solution showed the production of reasonably monodisperse silver nanoparticles (average particle size: 8.92 ± 1.61 nm) by the fungus. X-ray diffraction spectrum of the nanoparticles confirmed the formation of metallic silver. The Fourier transform infrared spectroscopy confirmed the presence of protein as the stabilizing agent surrounding the silver nanoparticles. These protein-stabilized silver nanoparticles produced a characteristic emission peak at 553 nm when excited at 420 nm in photoluminescence spectrum. The use of fungus for silver nanoparticles synthesis offers the benefits of eco-friendliness and amenability for large-scale production.     

Structural and photocatalytic properties of TiO2/SiOx/TiOx multi-layer prepared by electron-beam evaporation method

TiO₂/SiO_x/TiO_x multi-layers on quartz glass were prepared by electron-beam evaporation method and their structural and photocatalytic properties were investigated. The photocatalytic activity of the TiO₂/SiO_x/TiO_x multi-layer was evaluated by the photodecomposition of methylene blue in aqueous solution. As the thickness of the SiO_x inter-layer increased, the surface roughness of the TiO₂/SiO_x/TiO_x multi-layer increased but the anatase crystallite size decreased. The TiO₂/SiO_x(80 nm)/TiO_x multi-layer exhibited excellent photocatalytic activity resulting from higher surface roughness and more trap levels in the SiO_x(80 nm) inter-layer.     

Effect of thermal treatments on the structure of MoNxOy thin films

MoN_xO_y films were deposited on steel substrates by dc reactive magnetron sputtering. The depositions were carried out from a pure molybdenum target, varying the flow rate of reactive gases. X-ray diffraction (XRD) results revealed the occurrence of cubic MoN_x and hexagonal (δ-MoN) phases for the films with high nitrogen flow rates. The increase of oxygen content induces the decrease of the grain size of the molybdenum nitride crystallites. The thermal stability of a set of samples was studied in vacuum, for an annealing time of 1 h, for temperatures ranging from 500 to 800 °C in 100 °C steps. The results showed that pure molybdenum nitride films changed their structure from a meta-stable cubic MoN to hexagonal δ-MoN and cubic γ-Mo₂N-type structures with increasing annealing temperatures. The samples with molybdenum nitride films evidenced a good thermal stability, but those with molybdenum oxynitride coatings showed a tendency to detach with the increase of the annealing temperature.     

Characterization of sol-gel derived TiO2/ZrO2 films and powders by Raman spectroscopy

The effect of zirconium dioxide addition on crystal structure of sol-gel TiO₂ mesoporous films and powders has been investigated by means of Raman spectroscopy, X-Ray diffraction, and Atomic force microscopy. Zirconium incorporation (up to 30 mol%) into TiO₂ lattice resulted in the formation of Ti_1 − xZr_xO₂ solid solution with anatase structure for the binary powders has been proved. Appearance of tetragonal ZrO₂ phase was observed for the samples with high zirconium content.     

Green synthesis of gold nanoparticles using ethanolic leaf extract of Centella asiatica

Here, we report a novel use of the ethanolic leaf extract of Centella asiatica to produce gold nanoparticles by reduction of AuCl₄⁻ ions. The phytochemicals present in the leaf extract served as effective reducing and capping agent. The gold nanoparticles obtained were characterized by UV-visible spectra, transmission electron microscopy (TEM) and X-ray diffraction (XRD). TEM studies showed the particles to be of various shapes and sizes. Selected-area electron diffraction (SAED) pattern and high-resolution TEM image confirmed a fcc phase and high crystallinity of the particles. The XRD patterns showed a (1 1 1) preferential orientation of the gold nanoparticles. Fourier transform infra-red spectroscopy (FTIR) measurements showed the GNPs having a coating of phenolic compounds indicating a possible role of biomolecules responsible for capping and efficient stabilization of the gold nanoparticles. As no synthetic reagents were used in this method, the synthesized gold nanoparticles have potential for application in bio-molecular imaging and therapy.     

Intensified biosynthesis of silver nanoparticles using a native extremophilic Ureibacillus thermosphaericus strain

The microflora of Ramsar geothermal hot springs located in Mazandaran province, Iran was screened for native thermophilic bacteria that are capable of biosynthesis of silver nanoparticles. One isolate identified as “Ureibacillus thermosphaericus” showed high potential for silver nanoparticle biosynthesis with extracellular mechanism and selected for the biosynthesis optimization. Biosynthesis reactions were conducted using the culture supernatant at different temperatures (60-80 °C) and silver ion concentrations (0.001-0.1 M). The results obtained showed that pure spherical nanoparticles in the range of 10-100 nm were produced, and the maximum nanoparticle production was achieved using 0.01 M Ag-NO₃ at 80 °C. In conclusion, the findings of this study confirmed the great biocatalyzing potential of the extremophilic U. thermosphaericus supernatant for intensified biosynthesis of silver nanoparticle at elevated temperatures and high silver ion concentrations.     

Characterization of N-doped TiO2 films prepared by reactive sputtering using air/Ar mixtures

Nitrogen-doped titanium dioxide (TiO_2 − xN_x) thin films desirable for visible light photocatalysts were prepared by reactive sputtering using air/Ar mixtures. Using air as the reactive gas allows the process to conduct at high base pressures (low vacuum), which reduces substantially the processing time. The obtained films transformed from mixed phases to anatase phase as the air/Ar flow ratio increased. Substitutional doping of nitrogen verified by X-ray photoelectron spectroscopy accounts for the red-shift of absorption edge in the absorption spectra. Anatase TiO_2 − xN_x films could incorporate up to about 7.5 at.% substitutional nitrogen and a maximum of 23 at.% nitrogen was determined in the films with mixed phases. The optical band gaps of the TiO_2 − xN_x films calculated from Tauc plots varied from 3.05 to 3.11 eV and those of the mixed phase ranged from 2.77 to 3.00 eV, which are all lower than that for pure anatase TiO₂ and fall into the visible light regime.     

Biosynthesis of silver nanoparticles using leaves of Stevia rebaudiana

The synthesis of silver nanoparticles employing a shadow-dried Stevia rebaudiana leaf extract in AgNO₃ solution is reported. Transmission electron microscopy and X-ray diffraction inspections indicate that nanoparticles are spherical and polydispersed with diameters ranging between 2 and 50 nm with a maximum at 15 nm. Ultraviolet–visible spectra recorded against the reaction time confirms the reduction of silver nanoparticles indicating that the formation and the aggregation of nanoparticles take place shortly after the mixing, as they persist concurrently with characteristic times of 48.5 min and 454.5 min, respectively. Aggregation is found to be the dominant mechanism after the first 73 min. Proton nuclear magnetic resonance spectrum of the silver nanoparticles reveals the existence of aliphatic, alcoholic and olefinic CH₂ and CH₃ groups, as well as some aromatic compounds but no sign of aldehydes or carboxylic acids. Infrared absorption of the silver nanoparticles suggests that the capping reagents of silver and gold nanoparticles reduced in plant extracts/broths are of the same chemical composition of different ratios. Ketones are shown to play a somehow active role for the formation of nanoparticles in plant extracts/broths.     

Optimal exponential feeding strategy for dual-substrate biostimulation of phenol degradation using Cupriavidus taiwanensis

The exponential feeding strategy (EFS) of dual substrates (i.e., phenol and glycerol) was applied to optimize the overall performance of phenol degradation by Cupriavidus taiwanensis R186. Addition of a second substrate (e.g., glycerol) could stimulate the phenol biodegradation efficiency of strain R186. Hence, a feasible EFS was developed for fed-batch phenol biodegradation using the dual-substrate biostimulation technique. The phenol degradation kinetics was well characterized with proposed model and response surface analysis. Our findings quantitatively revealed that glycerol could effectively enhance the phenol degradation performance, as the highest phenol degradation efficiency occurred with the supplementation of 0.8–1.2 g L⁻¹ of glycerol. The optimal dual-substrate EFS was identified via contour analysis and kinetic modeling. With the optimal dual-substrate EFS (i.e., a feeding rate constant (α₁ and α₂) of 0.5 and 0.3, respectively), the shortest time (ca. 13.80 h) for phenol degradation was achieved with a specific growth rate of ca. 0.281 h⁻¹.     

Microstructure effect on mechanical properties of in situ synthesized titanium matrix composites reinforced with TiB and La2O3

High temperature titanium matrix composites (TMCs) with different volume fraction of reinforcements were insitu synthesized by casting and hot forging. An effort was made to investigate the mechanical properties as a function of the microstructure of composites. Tensile tests were performed at room temperature, 600 °C, 650 °C and 700 °C respectively. Creep behavior at 650 °C was characterized in the stress range of 200-300 MPa. Results indicated that the composite with 2.11 vol.% reinforcements had the highest tensile strength and lowest steady state creep rate. Morphology of TiB whiskers was critical to mechanical properties of TMCs. TiB whiskers fracture and debonding acted as the dominant failure modes.     

Ferroelectric and fatigue-free properties of Au/(Bi,La)4Ti3O12/ITO thin film capacitors by pulsed laser deposition

Ferroelectric Bi_3.25La_0.75Ti₃O₁₂ (BLT) thin films were deposited on indium-tin-oxide (ITO) coated glass substrates by pulsed-laser-ablation method. Films deposited at 400 °C and annealed at 650 °C resulted in remnant polarization and coercive field values of 14-16 μC/cm² and 90-100 kV/cm, respectively. The fatigue measurements were conducted until 1 × 10¹¹ cycles but the individual switched and unswitched polarizations showed unequal magnitudes. Such an unequal switching polarization proves that an extrinsic effect mainly associated with the electrode exists in this thin film capacitor. The overall switching polarizations showed no polarization degradation, suggesting that BLT films are fatigue resistive even on hybrid-metal-oxide electrodes.     

Raman spectroscopic and X-ray diffraction investigations of epitaxial BiCrO3 thin films

Epitaxial BiCrO₃ thin films were grown onto NdGaO₃ (110)- and (LaAlO₃)_0.3-(Sr₂AlTaO₆)_0.7 (100)-oriented substrates by pulsed laser deposition. High resolution X-ray diffraction and pole figure measurements were performed in order to obtain information about the crystal structure of the films, about their quality and about the mutual crystallographic orientation between the films and the substrates. The monoclinic (111) plane of BiCrO₃ was found out to be parallel to the substrate surface. The epitaxial relation between films and substrates was verified by using polarisation dependent Raman spectroscopic experiments and theoretical calculations based on symmetry.     

Comparison of creep crack growth rate in heat affected zone of welded joint for 9%Cr ferritic heat resistant steel based on C, dδ/dt, K and Q parameters

Creep crack growth behavior is very sensitive to the materials’ micro-structures such as the heat affected zone of a weld joint. This is a main issue to be clarified for 9%Cr ferritic heat resistant steel for their application in structural components. In this paper, high temperature creep crack growth tests were conducted on CT specimens with cracks in the heat affected zone of weld joints of W added 9%Cr ferritic heat resistant steel, ASME grade P92. The creep crack growth behavior in the heat affected zone of welded joint was investigated using the Q^∗ concept following which the algorithm of predicting the life of creep crack growth has been proposed. Furthermore, three-dimensional elastic-plastic creep FEM analyses were conducted and the effect of stress multiaxiality of welded joint on creep crack growth rate was discussed as compared with that of base metal.     

Estimation of the transient creep parameter C(t) under combined mechanical and thermal stresses

This paper reports finite element analyses for an axially loaded cylinder with three different types of thermal stress. The magnitudes of the thermal and mechanical loadings are varied and creep crack tip parameters are evaluated for part-through-wall and fully penetrating defects with a range of sizes. The relaxation rate for the creep crack tip parameter is examined in detail and is found to depend on the magnitudes of the mechanical and thermal loads and on whether or not there is plasticity on initial loading. Simplified formulae are developed for describing the rate of relaxation by a modified redistribution time.     

In-situ analyses on the reactive sputtering process to deposit Al-doped ZnO films using an Al-Zn alloy target

The kinetic energies of generated ions were investigated during the reactive sputtering process to deposit Al-doped ZnO (AZO) films using an Al-Zn alloy target. The sputtering system was equipped with specially designed double feedback system to stabilise the reactive sputtering processes and analysis was performed with a quadrupole mass spectrometer combined with an energy analyser. Negative ions O⁻, O₂⁻, AlO⁻ and AlO₂⁻ with high kinetic energies corresponding to cathode voltage are generated at the partially oxidised target surface, after which some of the ions undergo subsequent charge exchange and/or dissociation. Positive ions O⁺, Ar⁺, Zn⁺ and Al⁺ with lower kinetic energies (around 10 eV) are generated by charge exchange of sputtered neutral O, Ar, Zn and Al atoms, respectively. As the target surface oxidises, cathode voltage decrease, the flux of high-energy negative ions increases and the electrical properties of the AZO degrade by ion bombardment as well as the AZO films that are deposited by conventional magnetron sputtering using an AZO target.