Determination of the total acid number (TAN) of used gas engine oils by IR and chemometrics applying a combined strategy for variable selection

The most common analyses carried out to assess gas engine oil quality include determination of viscosity, total base number (TBN), and total acid number (TAN). TAN has been considered to be an important indicator of oil quality, specifically in terms of defining oxidation and the extent of acidic contamination of used oils. TAN can be determined by potentiometric titration, and typical values for used oils can reach up to 4 mg KOH/g. A more convenient approach for the determination of TAN is based on infrared (IR) spectral data and multivariate regression models.We developed partial least-squares (PLS) models for the determination of TAN using IR data measured from monograde mineral gas engine oils (SAE 40, medium ash) that have been used in sewer and wood gas engines run with gaseous fuels from a sewage plant and a wood gasification plant, respectively. The final model performance was 0.07 mg KOH/g for the standard error of prediction (SEP). Essential for the development of powerful empirical models was an appropriate variable selection by combining expert knowledge, biPLS or dyn-biPLS, and a genetic algorithm. The optimum complexities of the models (the number of PLS components) and their prediction performances have been estimated by repeated double cross validation (rdCV).     

Further exploring rm metrics for validation of QSPR models

Quantitative structure-property relationship (QSPR) models are widely used for prediction of properties, activities and/or toxicities of new chemicals. Validation strategies check the reliability of predictions of QSPR models. The classical metrics like Q² and R²_pred (Q²_ext) are commonly used, besides other techniques, for internal validation (mostly leave-one-out) and external validation (test set validation) respectively. Recently, we have proposed a set of novel r_m² metrics which has been extensively used by us and other research groups for validation of QSPR models. In the present attempt, some additional variants of r_m² metrics have been proposed and their applications in judging the quality of predictions of QSPR models have been shown by analyzing results of the QSPR models obtained from three different data sets (n = 119, 90, and 384). In each case, 50 combinations of training and test sets have been generated, and models have been developed based on the training set compounds and subsequently applied for prediction of responses of the test set compounds. Finally, models for a particular data set have been ranked according to the quality of predictions. The role of different validation metrics (including classical metrics and different variants of r_m² metrics) in differentiating the “good” (predictive) models from the “bad” (low predictive) models has been studied. Finally, a set of guidelines has been proposed for checking the predictive quality of QSPR models.     

Low permittivity SrCuSi4O10-LMZBS glass composite for LTCC applications

The tetragonal gillespite type SrCuSi₄O₁₀ (SCS) was prepared by the conventional solid-state ceramic route. The SCS sintered at 1100 °C/6 h showed ε_r = 4.0 and tan δ = 1.1 × 10⁻³ at 5 GHz. The SCS has poor sinterability and the addition of lithium magnesium zinc borosilicate glass (20: Li₂O, 20: MgO, 20: ZnO, 20: B₂O₃, 20: SiO₂) lowered the sintering temperature and improved densification. The SCS ceramic with 5 wt.% LMZBS glass sintered at 900 °C has ε_r = 5.0 and tan δ = 1.9 × 10⁻³ at 5 GHz. The composite is chemically compatible with the common electrode material silver.     

Acoustic chemometric prediction of total solids in bioslurry: A full-scale feasibility study for on-line biogas process monitoring

Dry matter is an important process control parameter in the bioconversion application field. Acoustic chemometrics, as a Process Analytical Technology (PAT) modality for quantitative characterisation of dry matter in complex bioslurry systems (biogas fermentation), has not been successful despite several earlier dedicated attempts. A full-scale feasibility study based on standard addition experiments involving natural plant biomass was conducted using multivariate calibration (Partial Least Squares Regression, PLS-R) of acoustic signatures against dry matter content (total solids, TS). Prediction performance of the optimised process implementation was evaluated using independent test set validation, with estimates of accuracy (slope of predicted vs. reference values) and precision (squared correlation coefficient, r²) of 0.94 and 0.97 respectively, with RMSEP of 0.32% w/w (RMSEP_rel = 3.86%) in the range of 5.8-10.8% w/w dry matter. Based on these excellent prediction performance measures, it is concluded that acoustic chemometrics has come of age as a full grown PAT approach for on-line monitoring of dry matter (TS) in complex bioslurry, with a promising application potential in other biomass processing industries as well.     

Microwave assisted fast fabrication of Fe3O4-MWCNTs nanocomposites and their application as MRI contrast agents

Uniform Fe₃O₄ nanoparticles with diameters of 3-5 nm are successfully decorated onto the external walls of multiwall carbon nanotubes (MWCNTs) by in situ high-temperature decomposition of Fe(acac)₃ in polyol solution under the irradiation of microwave. With this method, reaction time of forming Fe₃O₄-MWCNTs nanocomposites has been significantly shortened to 15 min. The resulting Fe₃O₄-MWCNTs nanocomposites show superparamagnetic property at room temperature and can be remained as stable aqueous dispersion for 2 months. Longitudinal relaxivity (r₁) and transverse relaxivity (r₂) of the magnetic MWCNTs are 8.34 Fe mM⁻¹ S⁻¹ and 146 Fe mM⁻¹ S⁻¹ respectively. The much higher r₂ value and the obvious change in the gray scale of MR images confer the Fe₃O₄-MWCNTs nanocomposites as potential candidates for T₂-weighted MRI contrast agents.     

A kinetic spectrophotometric method for simultaneous determination of phenol and its three derivatives with the aid of artificial neural network

A novel kinetic spectrophotometric method was developed for determination of pyrocatechol, resorcin, hydroquinone and phenol based on their inhibitory effect on the oxidation of Rhodamine B (RhB) in acid medium at pH = 3.0. A linear relationship was observed between the inhibitory effect and the concentrations of the compounds. The absorbance associated with the kinetic reactions was monitored at the maximum wavelength of 557 nm. The effects of different parameters such as pH, concentration of RhB and KBrO₃, and temperature of the reaction were investigated and optimum conditions were established. The linear ranges were 0.22-3.30, 0.108-0.828, 0.36-3.96 and 1.52-19.76 μg mL⁻¹ for pyrocatechol, resorcin, hydroquinone and phenol, respectively, and their corresponding detection limits were 0.15, 0.044, 0.16 and 0.60 μg mL⁻¹. The measured data were processed by several chemometrics methods, such as principal component regression (PCR), partial least squares (PLS) and artificial neural network (ANN), and a set of synthetic mixtures of these compounds was used to verify the established models. It was found that the prediction ability of PLS, PCR and RBF-ANN was similar, however, the RBF-ANN model did perform somewhat better than the other methods. The proposed method was also applied satisfactorily for the simultaneous determination of pyrocatechol, resorcin, hydroquinone and phenol in real water samples.     

Manganese dioxide structural effects on its thermal decomposition

In this work, the influence of the structure, composition and morphology on the amount of mass lost from γ-MnO₂ during heat treatment, and the activation energy for this process (from iso-conversional kinetic analysis), was determined using a statistical approach. It was found that the differential thermogravimetric (DTG) data for electrolytic manganese dioxide (EMD) samples typically show two regions of mass loss; water bound to surface sites and structural water at or near the surface removed between ∼120 and 200 °C, and bulk hydroxyl groups lost in the range ∼200-400 °C. The composition and morphology had the greatest effect on the amount of mass lost; namely, BET surface area and percentage Mn(III) for the first process (r² = 0.92) and percentage Mn(IV), percentage Mn(III) and cation vacancy fraction for the second (r² = 0.89). The activation energy for the first processes was most affected by BET surface area, c₀ and crystallite size in the (2 2 1) direction (r² = 0.89). Relatively poor correlations were found between the amount of water lost and the activation energy for the second process and the material properties measured in this work. This likely relates to the slow kinetics of the first mass loss which complicates the relationships existing for the second.     

On-line predictions of the aspen fibre and birch bark content in unbleached hardwood pulp, using NIR spectroscopy and multivariate data analysis

An on-line fibre-based near-infrared (NIR) spectrometric analyser was adapted for on-site process analysis at an integrated paperboard mill. The analyser uses multivariate techniques for the quantitative predication of the aspen fibre (aspen) and the birch bark contents of sheets of unbleached hardwood pulp. The NIR analyser is a prototype constructed from standard NIR components. The spectroscopic data was processed by using principal component analysis (PCA) and partial least square (PLS) regression. Three sample sets were collected from three experimental designs, each composed of known pulp contents of birch, aspen and birch bark. Sets 1 and 2 were used for model calibration and set 3 was used to validate the models. The PLS model that produced the best predictions gave an error of prediction (RMSEP) of 13% for aspen and less than 2% for birch bark. Eight components resulted in an R²X of 99.3%, R²Y of 99.6%, and Q² of 95.3%. For additional validation of aspen, three unbleached hardwood samples from the mill's production were calculated to lie between − 7% and + 6%, regarding to the PLS model. When vessel cells were counted under a light microscope a value for the aspen content of 4.7% was obtained. The predictive models evaluated were suitable for quality assessments rather than quantitative determination.     

Improved dielectric and ferroelectric properties in Ti-doped BiFeO3-PbTiO3 thin films prepared by pulsed laser deposition

Ti-modified thin films of multiferroic 0.72Bi(Fe_1 − xTi_x)O₃-0.28PbTiO₃ (BFPT, x = 0 and 0.02) solid solution were prepared by pulsed laser deposition. The BFPT (x = 0 and 0.02) films possess a tetragonal structure with highly preferential (001) orientation. The effects of the ionic substitution on the properties of BFPT (x = 0 and 0.02) films have been investigated. The leakage current of the BFPT (x = 0.02) thin film is significantly reduced, and the dielectric and ferroelectric properties greatly improved by the aliovalent ionic substitution of Ti⁴⁺ for Fe³⁺. The BFPT (x = 0.02) thin film exhibits a reasonably high remnant polarization P_r with 2P_r up to 90 μC/cm² at 312 kV/cm and a switchable polarization up to 92 μC/cm² at 417 kV/cm.     

Enhanced ferroelectric properties of Mg doped (Ba,Sr)TiO3 thick films grown on (001) SrTiO3 substrates

Highly (001)-oriented 1 mol% Mg doped (Ba_0.67,Sr_0.33)TiO₃ (BST) films with a thickness of 1.25 μm were grown on (110) SrRuO₃/(001) SrTiO₃ substrates by pulsed laser deposition. X-ray diffraction measurements reveal that the BST thick films have very high crystalline quality, and have a distorted lattice with a large tetragonality a/c = 1.012. The BST thick films have a remanent polarization (P_r) value as large as 10.1 μC/cm² and a coercive electric field (E_c) value of 65.0 kV/cm. The films possess dielectric constant and loss values of ε_r = 385.36 and tgδ = 0.038 at 1 kHz and room temperature. The leakage currents of the films are on the order of 10^− 5 A/cm² at ± 150 kV/cm. The mechanism for enhancing electric properties of the Mg doped BST films was also discussed.     

Enhanced ferroelectric properties of Pb(Zr0.80Ti0.20)O3/PbO thin films prepared by radio frequency magnetron sputtering

The Pb(Zr_0.80Ti_0.20)O₃ (PZT) thin films with and without a PbO buffer layer were deposited on the Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by radio frequency (rf) magnetron sputtering method. The PbO buffer layer improves the microstructure and electrical properties of the PZT thin films. High phase purity and good microstructure of the PZT thin films with a PbO buffer layer were obtained. The effect of the PbO buffer layer on the ferroelectric properties of the PZT thin films was also investigated. The PZT thin films with a PbO buffer layer possess better ferroelectric properties with higher remnant polarization (P_r = 25.6 μC/cm²), and lower coercive field (E_c = 60.5 kV/cm) than that of the films without a PbO buffer layer (P_r = 9.4 μC/cm², E_c = 101.3 kV/cm). Enhanced ferroelectric properties of the PZT thin films with a PbO buffer layer is attributed to high phase purity and good microstructure.     

Notch stress concepts for the fatigue assessment of welded joints - Background and applications

Among modern fatigue design concepts for welded structures, the linear-elastic notch stress concept gains increasing industrial acceptance. There are two variants of this concept, one for thick walled (t ? 5 mm) welded joints with the reference radius r_ref = 1.00 mm, which is already included in the fatigue design recommendations of the IIW and applied for the assessment of big welded structures, and one for thin walled (t < 5 mm) welded joints with the reference radius r_ref = 0.05 mm, which is more and more used in the automotive industry.The concept with r_ref = 1.00 mm is based on the micro-support theory of Neuber with the fictitious radius r_ref = 1.00 mm, derived by Radaj. The background of the concept with r_ref = 0.05 mm is the relationship between the stress-intensity factor and the notch stress according to Creager and Paris as well as Irvin’s theory of crack blunting. Besides these two theories, the definition of both of these radii has also an experimental background; they are observed in many welded joints.In the present paper, first the background and then different applications of both concept variants are described: the application of the reference radius of r_ref = 1.00 mm for MAG-welded offshore K-nodes (t = 30 mm) and sandwich panels for ship decks (t = 5 mm), and the application of r_ref = 0.05 mm for spot-welded automotive doors (t = 1 mm) and MAG-welded automotive trailing links (t = 3-4 mm). The sandwich panels were evaluated additionally with r_ref = 0.05 mm. Calculations and experimental results are compared and the reliability of the notch stress concept variants underlined. Additionally, recommendations for the slope of design lines distinguishing between thin and thick dimensions are given, i.e. k = 3.0 and 5.0 (normal stress, shear stress) for thick and stiff structures, k = 5.0 and 7.0 for thin and flexible structures.     

Enhanced performance of sandwich structure Pb0.8La0.1Ca0.1Ti0.975O3 thin film for pyroelectric applications

Using the advantages of low-temperature crystallization and high orientation in Pb_0.8La_0.1Ca_0.1Ti_0.975O₃ (PLCT) film, a dense PLCT/porous PLCT/dense PLCT sandwich structure was obtained in the present study. It is found that dense PLCT layer can both sustain the porous density in the core layer and also lead to better preferential orientation of the sandwich structure. In the sandwich structure, low dielectric constant (ε_r = 43) and leakage current density (J < 9 × 10^− 5A/cm²) are simultaneously achieved. Because of high orientation in sandwich structure, the pyrocoefficient (p > 185 µC/m² K) is still keeping a relatively large value. The resulting high figure of merit (F_V′ = 4.5 µC/m² K, F_d′ = 228 µC/m² K) make the sandwich structure films good candidate for pyroelectric thin-film devices.     

A promising red phosphor MgMoO4:Eu for white light emitting diodes

Motivated by the need for new red phosphors for solid-state lighting applications Eu³⁺-doped MgMoO₄ was prepared by solid-state reaction and its excitation and emission spectra were measured at room temperature. In addition, the effects of firing temperature and Eu³⁺ doping concentration on the PL intensities were also investigated. Compared with Y₂O₂S:0.05Eu³⁺, the obtained Mg_0.80MoO₄:Eu³⁺_0.20 phosphor shows a stronger excitation band near 400 nm and intensely red-emission lines at 616 nm correspond to the forced electric dipole ⁵D₀ → ⁷F₂ transitions on Eu³⁺ under 394 nm light excitation. The CIE chromaticity coordinates (x = 0.651, y = 0.348) of Mg_0.80MoO₄:Eu³⁺_0.20 close to the NTSC (National Television Standard Committee) standard values, and therefore may find application on near UV InGaN chip-based white light emitting diodes.     

Effects of Y2O3 addition on microwave dielectric characteristics of Al2O3 ceramics

Microwave dielectric characteristics of alumina ceramics with yttria addition were investigated. The sintering temperature was lowered, and the dielectric constant (ε_r) did not remarkably change by adding yttria. The microwave dielectric loss (tan δ) increased from 8.4 × 10^− 5 to 2.2 × 10^− 4, due to the presence of Al₅Y₃O₁₂ secondary phase. The grain size had significant effects on the dielectric loss, and there was an optimum grain size where the dielectric loss reached the minimum.     

Electromagnetic wave absorption properties of multi-walled carbon nanotubes decorated with La-doped BaTiO3 nanocrystals synthesized by a solvothermal method

Ba_1−xLa_xTiO₃/multi-walled carbon nanotube (MWCNT) nanocomposites with different concentrations of La³⁺ doping, were synthesized by a solvothermal process. The prepared nanocomposites had a hybrid microstructure in which Ba_1−xLa_xTiO₃ nanocrystals with diameter of 10–30 nm were firmly immobilized on the MWCNTs sidewalls. Electromagnetic (EM) wave absorption properties of La-doped BaTiO₃/MWCNT nanocomposites were investigated in the 7.5–18 GHz frequency range for an absorber thickness of 1 mm. The reflection loss (RL) calculated from the EM parameters of the samples, moved to low frequencies with increasing La³⁺ doping. The widest absorption bandwidth, with the lowest frequency range, was observed in a nanocomposite doped with 1.5 at% La³⁺. An RL exceeding −5 dB for this sample was obtained in the frequencies ranging from 9.6 to 16.3 GHz, with the optimal RL of −17.4 dB at 10.9 GHz, due to enhanced interfacial polarization resulting in developed ε^″r${{\epsilon }^{″}}_{\text{r}}$. In addition, the RL for the sample shifted to the low frequency region and the peaks became sharper in the 2–18 GHz frequency range with increasing absorber thickness. For BaTiO₃/MWCNT nanocomposites, La³⁺ doping can greatly improve the EM wave absorbing ability in a thin absorber thickness and the donor-doped nanocomposites show promise for application in EM wave shielding materials with broad absorption bandwidths.     

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.     

Structural and electrical properties of BiFeO3 thin films by solution deposition and microwave annealing

Lead-free polycrystalline BiFeO₃ (BFO) thin films were developed using a chemical solution deposition method to deposit the films and the multi-mode 2.45 GHz microwave furnace to optimize the annealing condition of the films. Phase-pure BFO films were obtained at 500 °C-600 °C for 1-5 min with a heating rate of 10 °C/min. The film by microwave annealing (MW) at 550 °C for 5 min exhibited a (012)-preferred orientation with a dense morphology of grain size ~ 294 nm. Its dielectric constant of 96.2, low leakage current density of 2.466 × 10^− 6 A/cm², polarization (2P_r) and coercive field (2E_c) of 0.931 μC/cm² and 57.37 kV/cm, respectively, were improved compared to those by conventional annealing (CA) at the same annealing conditions.     

Synthesis of (1 − x)Ca2/5Sm2/5TiO3-xLi1/2Nd1/2TiO3 ceramic powder via ethylenediaminetetraacetic acid precursor

(1 − x)Ca_2/5Sm_2/5TiO₃-xLi_1/2Nd_1/2TiO₃ (CSLNT) ceramic powder was prepared by a liquid mixing method using ethylenediaminetetraacetic acid (EDTA) as the chelating agent. TG, DTA, XRD and TEM characterized the precursors and derived oxide powders. When x = 0.3, perovskite CSLNT was synthesized at 1000 °C for 3 h in air. The CSLNT (x = 0.3) ceramics sintered at 1200 °C for 3 h show excellent microwave dielectric properties of ?_r = 99, Q_f = 6200 GHz and τ_f = 9 × 10⁻⁶ °C⁻¹.