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- Sol-gel (7)
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- SPME-GC-MS (3)
- Voltammetric electronic tongue (3)
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Improved Durability of Wood Treated with Nano Metal Fluorides against Brown-Rot and White-Rot Fungi
(2022)
Low-water soluble metal fluorides such as magnesium fluoride (MgF2) and calcium Fluoride (CaF2) were evaluated for decay protection of wood. Initially, the biocidal efficacy of nano metal fluorides (NMFs) against wood destroying fungi was assessed with an in-vitro agar test. The results from the test showed that agar medium containing MgF2 and CaF2 was more efficient in preventing fungal decay than stand-alone MgF2 or CaF2. These metal fluorides, in their nanoscopic form synthesized using fluorolytic sol-gel synthesis, were introduced into the sapwood of Scots pine and beech wood and then subjected to accelerated ageing by leaching (EN 84). MAS 19F NMR and X-ray micro CT images showed that metal fluorides were present in treated wood, unleached and leached. Decay resistance of Scots pine and beech wood treated with NMFs was tested against Wood destroying fungi Rhodonia placenta and Trametes versicolor in accordance with EN 113. Results revealed that mass losses were reduced to below 3% in wood treated with the combination of MgF2 and CaF2.
It is concluded that NMFs provide full protection to wood even after it has been leached and can be used as wood preservatives in outdoor environments.
Fluorides are well-known as wood preservatives. One of the limitations of fluoride-based wood preservatives is their high leachability. Alternative to current fluoride salts such as NaF used in wood protection are low water-soluble fluorides. However, impregnation of low water-soluble fluorides into wood poses a challenge. To address this challenge, low water-soluble fluorides like calcium fluoride (CaF2) and magnesium fluoride (MgF2) were synthesized as nanoparticles via the fluorolytic sol−gel synthesis and then impregnated into wood specimens. In this study, the toxicity of nano metal fluorides was assessed by termite mortality, mass loss and visual analysis of treated specimens after eight weeks of exposure to termites, Coptotermes formosanus. Nano metal fluorides with sol concentrations of 0.5 M and higher were found to be effective against termites resulting in 100% termite mortality and significantly inhibited termite feeding. Among the formulations tested, the least damage was found for specimens treated with combinations of CaF2 and MgF2 with an average mass loss less than 1% and visual rating of “1”. These results demonstrate the efficacy of low water-soluble nano metal fluorides to protect Wood from termite attack.
Especially trace amounts of water vapour in gases can be reliably determined by coulometric trace humidity sensors. The principle of these sensors is based on water vapour absorption in a hygroscopic layer and its subsequent electrolytic decomposition. The calibration of sensors was performed in the humidity range, expressed as frost point temperature, from −30°C to −80°C . This range is equivalent to volume fractions smaller than 376 µL·L−1. Generated humidity was measured with coulometric sensors and a chilled dew point hygrometer that was used as reference. An empirical non-linear function was found between sensor signal and measured reference humidity. This function consists of two parameters with a measurement uncertainty. Both calibration parameters were checked by means of one-way analysis of variance. It showed that gas specific function can be used for humidity measurement in nitrogen, hydrogen, dinitrogen monoxide, compressed and synthetic air. It is possible to determine trace humidity in all tested gases with an expanded uncertainty less than 2.1 K (coverage factor k=2 ) regarding frost point temperature.
Trace humidity was measured by using miniaturized planar coulometric sensors in technical gases such as hydrogen, nitrogen, helium, nitrous oxide, and synthetic air. Frost point temperatures tf in the gases ranged from −60 °C to −30 °C, which is equivalent to a vapour mole fraction xv from 10 μmol mol−1 to 376 μmol mol−1. In addition, the generated humidity was determined by using a precision dew point hygrometer as reference. Nonlinear calibration functions were calculated that correlated electric current (sensor signal) and reference humidity. Parameters of functions were tested with one-way analysis of variances (ANOVA) to prove if all used sensors had a similar behavior in the same gas during experiments. Results of ANOVA confirmed that averaged functions can be applied for trace humidity measurement in nitrogen, helium, nitrous oxide, and synthetic air. The calculated functions were negligibly different for nitrogen, helium, and synthetic air. In humidified nitrous oxide, a minor change of parameters was observed due to lower electrical currents. In total contrast to that, the measured sensor signals were significantly higher in humidified hydrogen and each sensor required its own calibration function. The reason was a recombination effect that favoured multiple measurements of water molecules. Nevertheless, it was possible to measure continuously trace humidity in all tested gases by using coulometric sensors with an expanded uncertainty below 2 K (k = 2).
This work reported the investigation on the effect of relaxation to the permittivity (epsilon' r ) characteristic of Mg1-x Zn x TiO3 ceramics for x = 0 – 0.5 (MZT0 – MZT0.5) measured from 1 Hz to 330 MHz. Within that frequency range, the relaxation effect that consists of the space charge (SC) and the dipolar (D) polarization mechanisms were identified. The contribution of the D relaxation in MZT0 – MZT0.2 systems extents overall from about 100 Hz to 330 MHz, while that in MZT0.3 – MZT0.5 systems is from 50 kHz to 330 MHz. The remaining frequencies, i.e. from 1 to 90 Hz for MZT0 – MZT0.2 and from 1 Hz to 50 kHz for MZT0.3 – MZT0.5, are attributed to the SC relaxation. The D polarization mechanism provides constant epsilon' r values which vary from (15.4 – 17.0) ± 0.3 throughout the samples. Contribution of the SC polarization mechanism to the characteristic is supported by the simultaneous presence of different content and level of resistivity of the secondary phase of (Mg1-αZnα)2TiO4 in MZT0 – MZT0.2 systems and of (Zn1-αMgα)2TiO4 in MZT0.3 – MZT0.5, along with the presence of the main Mg1-x Zn x TiO3 phase, as a result of the variation of zinc content in the systems.
Planar coulometric sensors were tested in humidified synthetic air at various gas temperatures. Generated frost point temperature in the gas ranged from -30 °C to -60 °C and were measured by coulometric sensors and in addition by a calibrated dew point hygrometer. The gas temperatures, which were measured by a calibrated Pt100 sensor, were set to -20 °C, 0 °C, 23 °C, 40 °C, 50 °C, and 60 °C during the experiments. Empiric nonlinear functions were calculated between the generated humidity and the sensor signals. In comparison to the measured signals at 23 °C, the sensor signals were lower at the other gas temperatures. The measurements at 60 °C showed indistinct results due to a great signal noise. The response behavior of the sensors was similar at 23 °C, 40 °C and 50 °C. In contrast to that, the sensors reacted slowly at a gas temperature of -20 °C and 0 °C. In summary, with coulometric sensors it was possible to measure continuously trace humidity with an expanded uncertainty below 2 K.
The objective of this work is to report the improvement obtained in the discrimination of complex aroma and taste with subtle differences in odor and flavor, by the use of fast suitable procedures for the cases of measurements in the field demanding decision-making in real time. The proposed electronic sensing systems, formed by an E-nose and VE-tongue, were used to discriminate cumin cultivars from different geographical origins, as well as to quantify the cumin adulteration percentages by using unsupervised and supervised chemometric tools. Thus, the results obtained are sufficiently encouraging as a starting point for the development of new electronic sensing systems with more improvement such the reliability of the sensors’ performance as well as the chemometric tools in order to deal with a complex dataset.
The detection of the aroma and flavour volatile compounds of spices is key in product quality control. Accordingly, it is necessary to develop new electronic sensing systems for food adulteration control and authenticity assessment for protecting customer's health.
In this work, the capability of the E-nose and VE-tongue in combination with SPME-GC-MS to correctly discriminate between several cumin samples of different geographical origins and to detect their adulteration, by using unsupervised and supervised chemometric tools, was evaluated. Regarding the aroma profile, eleven volatile compounds were characterized by SPME-GC-MS; all of them were found in cumin powder while only eight are found in cumin seeds. The main volatile compounds detected were b-pinene, m-cymene, g-terpinene, cuminaldehyde and cuminic alcohol, in different proportions depending on the cumin sample form (seed or powder). In summary, the results obtained are sufficiently encouraging as a starting point for the development of new electronic sensing systems with more improvement in the reliability of the sensor's performance as well as chemometric tools in order to deal with a complex dataset.
A portable device for calibration of trace humidity sensors and an adopted calibration procedure have been developed. The calibration device is based on humidity generation by permeating water through polymeric membrane tubes. Water vapour transmission rates for various polymers were experimentally determined in order to select the most suitable polymeric material. The developed trace humidity generator consists of a gas-flow polymeric hose immersed in a water reservoir thermostated by a sensorcontrolled heater. Mole fractions of water vapour between 1 µmol/ molˉ¹ and 350 µmol/molˉ¹ (equivalent to frost-point temperatures from -76 °C to -31 °C) were generated by varying either the operating temperature or gas flow. The operating temperature can be varied from 20 °C to 60 °C and kept stable within 0.1 K. Uncertainty analysis indicated that the trace humidity generator produces gas flows of constant humidity amounts with a relative expanded uncertainty less than 3.4% (k = 2) of the generated value.
An experimental investigation has been carried out to characterize and discriminate seven saffron samples and to verify their declared geographical origin using a voltammetric electronic tongue (VE-tongue). The ability of multivariable analysis methods such as Principal Component Analysis (PCA), Hierarchical Cluster Analysis (HCA) to classify the saffron samples according to their geographical origin have been investigated. A good discrimination has reached using PCA and HCA in the VE-tongue characterization case. Furthermore, cross validation and Partial Least Square (PLS) techniques were applied in order to build suitable management and prediction models for the determination of safranal concentration in saffron samples based on SPME-GC-MS and UV-Vis Spectrophotometry. The obtained results reveals that some relationships were established between the VE-tongue signal, SPMEGC-MS and UV-Vis spectrophotometry methods to predict safranal concentration levels in saffron samples by using the PLS model. In the light of these results, we can say that the proposed electronic system offer a fast, simple and efficient tool to recognize the declared geographical origin of the saffron samples.
A series of Mg₁₋ₓZnₓTiO₃, x = 0–0.5 (MZT0–MZT0.5) ceramics was synthesised and characterised. The dielectric properties of the samples in the frequency range of
1 Hz – 7.7 GHz were explored using three different methods:
a contacting electrode method, a parallel-plate method and a perturbed resonator method. The electrical properties in the space charge and dipolar polarisation frequency ranges are discussed in relation to the phase composition and microstructure data. Differences in the zinc Substitution divided the dielectrics into two groups, namely MZT0-MZT0.2 and MZT0.3–MZT0.5, each with different amount of a main Mg₁₋ₓZnₓTiO₃ solid solution phase and a secondary solid solution phase. Zinc substitution promoted the density of the ceramics, improved the purity of the main phase and increased the permittivity for frequencies up to 10⁸ Hz, but reduced the permittivity in the microwave range. In the MZT0.3–MZT0.5 samples, for frequencies less than 1 MHz the quality (Q x ƒ) factors were lower and log σ ₐ.c, the AC conductivity, was higher than for the MZT0–MZT0.2 samples. Above 10 MHz, the (Q x ƒ) factors and log σ ₐ.c of the two groups were similar.
Different electronic sensor systems coupled with multivariate data analysis were applied to characterize and classify seven saffron samples and to verify their declared geographical origin. The proposed electronic sensing consists of a low-cost electronic nose (E-nose) based on metal oxide semiconductor sensors and a voltammetric electronic tongue (VE-tongue) based on voltammetric sensors. The ability of multivariable analysis methods such as Principal Component Analysis (PCA), Hierarchical Cluster Analysis (HCA) and Support Vector Machines (SVMs) to classify the saffron samples according to their geographical origin have been investigated. Both PCA and HCA have shown an overlapping of E-nose responses. Moreover, the SVM analysis of the E-nose database reached a 66.07% success rate in the recognition of the saffron sample odour. On the other hand, good discrimination has been reached using PCA and HCA in the VE-tongue characterization case, besides a 100% accuracy in the saffron flavour recognition was attained. To validate the proposed electronic sensing systems, analytical chemical methods such as SPME-GC-MS and UV-Vis spectrophotometry were used. These analytical methods could be helpful tools to identify the composition of volatile compounds of the analysed saffron samples. Moreover, UV-Vis spectrophotometry was also used to determine the non-volatile profile of the samples from different geographic origins. It is demonstrated that the electronic sensing systems' findings are in a satisfactory correlation with the analytical methods. In the light of these results, we might say that the electronic systems offer a fast, simple and efficient tool to recognize the declared geographical origin of the saffron samples.
Gas sensors are applied for facilitating the safe use of hydrogen in, for example, fuel cell and hydrogen fuelled vehicles. New sensor developments, aimed at meeting the increasingly stringent performance requirements in emerging applications, are reviewed. The strategy of combining different detection principles, i.e. sensors based on electrochemical cells, semiconductors or field effects in combination with thermal conductivity sensing or catalytic combustion elements, in one new measuring system is reported. This extends the dynamic measuring range of the sensor while improving sensor reliability to achieve higher safety integrity through diverse redundancy. The application of new nanoscaled materials, nanowires, carbon tubes and graphene as well as the improvements in electronic components and optical elements are evaluated in view of key operating parameters such as measuring range, sensor response time and low working temperature.
The efficiency of gas sensor application for facilitating the safe use of hydrogen depends to a considerable extent on the response time of the sensor to change in hydrogen concentration. The response and recovery times have been measured for five different hydrogen sensors, three commercially available and two promising prototypes which operate at room temperature.
Experiments according to ISO 26142 show that most of the sensors surpass much for a concentration change from clean to hydrogen containing air the demands of the Standard for the response times t(90) and values of 2 to lös were estimated. For an opposite shift to clean air, the recovery times t(10) are from 7 to 70 s. Results of transient behaviour can be fitted with an exponential approach. It can be demonstrated that results on transient behaviour depend not only from investigation method, and the experimental conditions, like gas changing rate and concentration jump, as well as from operating
Parameters of sensors. In comparison to commercial MOS and MIS-FET hydrogen sensors new sensor prototypes operating at room temperature possesses in particular longer recovery times.
Gas sensors are applied for facilitating the safe use of hydrogen in, for example, fuel cell and hydrogen fuelled vehicles. New sensor developments, aimed at meeting the increasingly stringent performance requirements in emerging applications are presented based on in-house technical developments and a literature study. The strategy of combining different detection principles, i.e. sensors based on electrochemical cells, semiconductors or field effects in combination with thermal conductivity sensor or catalytic combustion elements, in one new measuring system is reported. This extends the dynamic measuring range of the sensor while improving sensor reliability to achieve higher safety integrity through diverse redundancy. The application of new nanoscaled materials, nano wires, carbon tubes and graphene as well as the improvements in electronic components of fieldeffect, resistive-type and optical systems are evaluated in view of key operating parameters such as sensor response time, low energy consumption and low working temperature.
A hydrogen sensor based on a silicon Metal/Solid Electrolyte/Insulator/Semiconductor (MEIS) structure with thin layers of the super-ionic conductor LaF3 and Pd gate metal was investigated in a hybrid structure on a resistance heater mounted on a ceramic substrate. The sensor was operated at room temperature, however, a short heating impulse once a day ensures a fast and reproducible dynamic behavior. The sensor was characterized in the concentration range typical for alarm levels up to 40% of the lower flammability limit and shows a logarithmic dependency of the sensor signal from the hydrogen concentration and a mean sensitivity of about 140 mV/decade. The response time (t90) is about 8 s. In a long term test for a period of three month, the sensor was exposed to hydrogen every two weeks. The sensor signal was shown to be stable in dynamic behavior, sensitivity and signal difference.
The antileaching efficacy of sol-gel-derived TiO2- and SiO2-based precursors has been evaluated through laboratory leaching trials with pine sapwood in two different ways. In a one-step process, wood was vacuum impregnated by the precursor solutions containing CuCl2. The copper (Cu) emission rates of the sol-gel-based impregnated woods were up to 70% lower than that of wood treated with pure CuCl2 solution at the same level of concentration. More improvement (80%) could be achieved in a two-step process, in which sol-gel precursors were introduced into an already CuCl2-treated wood. The refinement was attributed to several effects. In the one-step approach, Cu was embedded in the TiO2/SiO2 gels formed in the wood texture. During a two-step impregnation, gel layers that were formed in the wooden interior acted as an effective diffusion barrier. The sol-gel impregnations made wood more hydrophobic; therefore, the low amount of water that penetrated the cell wall was less efficient to leach out Cu.
Decay resistance of pine sapwood treated with titanium alkoxide solutions was tested against the brown-rot fungi Coniophora puteana and Poria placenta for exposure times of 10 and 16 wk. In practice, wood-specimens were vacuum-impregnated by alcoholic solutions of titanium alkoxide with concentrations in the range of 5–16 mass % (solid content in solution) and subsequently cured under different humidity conditions. Results reveal that treated wood degraded up to 5% in comparison to untreated one that deteriorated 38% and 50%, respectively against both wood-decay fungi. Even full protection (mass loss below 3%) was achieved against brown rot with titanium alkoxide solution containing solid content of around 5 mass% with a weight percentage gain (WPG) of 9 mass%. With increased concentration, fungal resistance decreased slightly which was associated with more cracks and imperfections formed in the deposited layers of titanium dioxide in the adjacent wood matrix. Thermal analysis verified that a considerable amount of precursor remained in the wood structure as un-hydrolyzed organic residues. These organics, being bioactive, had the tendency to induce similar fungicidal effects as those of conventional fungicides. The amount of organic residues is correlated with the decay resistance of the tested samples. In a prolonged decay test, mass losses of 16-wk incubated samples do not show behavior different from that of the wood samples incubated for 10 wk. This result implies that the decay protection is permanent and confirms further the fungicidal activity of titanium-alkoxide-treated wood.
Fire retardancy effects in single and double layered sol-gel derived TiO2 and SiO2-wood composites
(2012)
Sol–gel derived TiO2 and SiO2-wood inorganic composites are prepared by direct vacuum infiltration of silicon and titanium alkoxide based precursors in pine sapwood in one or two cycles followed by a controlled thermal curing process. The resulting flame retardancy effect is investigated under two different fire scenarios using cone calorimetry and oxygen index (LOI). Heat release rates (HRR) especially the values for the second peak, are reduced moderately for all single layered composites. This effect is more pronounced for double layered composites where HRR was reduced up to 40 % showing flame retardancy potential in developing fires. Beside this, smoke release was lowered up to 72 % indicating that these systems had less fire hazards compared to untreated wood, whereas no meaningful improvement is realized in terms of fire load (total heat evolved) and initial HRR increase. However impressively, the LOI of the composites were increased up to 41 vol% in comparison to 23 vol% for untreated wood displaying a remarkable flame retardancy against reaction to a small flame. An approximate linear interdependence among the fire properties and the material loading as well as fire residue was observed. A residual protection layer mechanism is proposed improving the residue properties for the investigated composites.
A new planar sensor element for continuous coulometric trace humidity measurements in industrial gases has been developed. In order to ensure precise measurements a calibration facility including a precision dew point hygrometer as a reference device was developed. The sensor can measure the humidity in the frost point temperature range of -20 °C to -80 °C and has an expanded uncertainty of 2 K, a fast reaction time and a settling time of the entire system from 15 to 30 min.