Mathematical modelling of Aspergillus ochraceus inactivation with supercritical carbon dioxide – A kinetic study

The aim of this research was to analyze and model the combined effect of pressure and temperature upon Aspergillus ochraceus spores exposed to high pressure carbon dioxide (HPCD) treatment and to estimate the kinetic parameters. Lately, many empirical or semi-empirical mathematical models were presented and discussed for different microorganisms, mainly bacteria, demonstrating an increased need for tools able to quantify the parameters of the microbial inactivation. A. ocharaceus HPCD inactivation was adequately described by first order reaction kinetics and a synergic effect of pressure and temperature was noticed for the experimental range where pressure varied from 5.4 to 7.0 MPa and temperature varied from 30 to 50 °C. The decimal reduction time (D) ranged from 47.07 min at 5.4 MPa and 30 °C to 5.04 min at 7.0 MPa and 50 °C. In this study three mathematical models were evaluated in order to find the best one that describes accurately the influence of pressure and temperature on the studied microbial response. An empirical exponential equation, that described pressure and temperature influence in the form of a polynomial equation, was found to best describe the dependence of A. ochraceus HPCD inactivation in the range 5.4–7.0 MPa and 30–50 °C.This work adds insight to moulds inactivation at the already existing body of knowledge on bacteria inactivation with HPCD and provides support to potential industrial applications of the minimal–thermal methods that combine high pressure and mild temperature with carbon dioxide for different food matrixes.     

Validation of a mathematical model for predicting high pressure carbon dioxide inactivation kinetics of Escherichia coli spiked on fresh cut carrot

Inactivation kinetics of Escherichia coli spiked on fresh cut carrot and exposed to high pressure carbon dioxide (HPCD) treatment at several conditions of pressure (6, 8, 10, and 12 MPa) and two conditions of temperature (26 and 35 °C) were obtained as a function of the treatment time (up to 30 min).The Weibull model was applied to fit the inactivation kinetics and calculate δ and n model parameters for each pressure and temperature. The results demonstrated that the model was able to fit with good agreement the inactivation curves (high R² and low RMSE values). In a second attempt, the model parameters were correlated with CO₂ density resulting in a linear relationship. Validation of the proposed model was also performed at 6.6 and 10 MPa, 26 °C and at 8 MPa, 35 °C providing log reduction residual values (observed value–predicted value) lower than 0.50 and showing a good agreement between the experimental and the predicted inactivation data.The model proved to be a powerful tool to fit and predict, in the proposed operative range, the inactivation kinetics of E. coli spiked on fresh cut carrot treated by HPCD. The results demonstrated the potential of a relative simple correlative model for the interpretation of the inactivation data and for HPCD process design and optimization.     

Effect of spinel content on hot strength of alumina-spinel castables in the temperature range 1000–1500°C

Hot modulus of rupture of Al₂O₃-spinel castables containing 5–15 wt% alumina-rich magnesia alumina spinel and 1·7 wt% CaO generally increases with increase in spinel content and temperature from 1000 to 1500°C. The magnitudes of hot modulus of rupture of castables containing 15 wt% spinel and 1·7 wt% CaO are 14·3 MPa at 1400°C and 15·6 MPa at 1500°C, while those of castables containing 20 wt% spinel and 1·7 wt% CaO are 12·5 MPa at 1400°C and 14·7 MPa at 1500°C. The former castables contained 15 wt% spinel of −75 μm size, while the latter contained 10 wt% spinel of +75 μm size and another 10 wt% spinel of −75 μm size. The bond linkage between the CA₆ and spinel grains in the matrix is believed to cause both the spinel content and temperature dependence of hot strength of Al₂O₃-spinel castables, as well as fine grain spinel even in amount less than coarser grain spinel to be more effective for enhancing hot strength. The trend of the magnitude of thermal expansion under load (0·2 MPa) above 1500°C of the castables is not necessarily indicative of the magnitude of hot modulus of rupture at 1400 or 1500°C. ©     

Thermal inactivation of airborne viable Bacillus subtilis spores by short-term exposure in axially heated air flow

In this investigation, an experimental facility was developed for quantifying the inactivation of viable bioaerosol particles in a controlled axially heated air flow. The tests were conducted with Bacillus subtilis var. niger endospores. The thermal inactivation of aerosolized spores was measured based on the loss of their culturability that resulted from a short-term exposure to air temperatures ranging from ～150 to >1000 °C. The cross-sectional and longitudinal temperature profiles in the test chamber were determined for different heating and flow conditions. The characteristic exposure temperature (T_e) was defined using a conservative approach to assessing the spore inactivation. Experimentally determined inactivation factors (IF) were corrected to account for the temperature profiles in the axially heated air flow. The reported IF-values serve as the lower approximation of the actual inactivation. Two data sets obtained at different flow rates, Q=18 and 36 L min^?1, represent different exposure conditions. In both cases, the thermal exposure of aerosolized spores produced no effect or only a moderate inactivation when the T_e remained below ～200 °C for 18 L min^?1 and ～250^oC for 36 L min^?1. The IF-values increased exponentially by about four orders of magnitude as the temperature rose by 150 °C. Depending on the flow rate, IF exceeded ～10⁴ at T_e>320 °C (Q=18 L min^?1) or >360 °C (Q=36 L min^?1). At T_e≈375–400 °C, the spore inactivation obtained at both flow rates reached the limit of quantification established in this study protocol, which translates to approximately 99.999% viability loss. The findings were attributed primarily to the heat-induced damage of DNA and denaturation of essential proteins. Up to a certain level of the thermal exposure, these damages are repairable; however, the self-repair capability diminishes as the heat rises and then the damage becomes totally irreversible. The data generated in this study provide an important reference point for thermal inactivation of stress-resistant spores in various biodefense/counterterrorism and air quality control applications.     

Al2O3–SiC composites prepared by warm pressing and sintering of an organosilicon polymer-coated alumina powder

Al₂O₃/SiC micro/nano composites were prepared by axial pressing of poly(allyl)carbosilane-coated submicrometre alumina powder at elevated temperature (called also warm pressing, or plastic forming) with subsequent pressureless sintering in the temperature interval between 1700 and 1850 °C. Warm pressing at 350 °C and 50 MPa resulted in green bodies with high mechanical strength and with markedly higher density than in green bodies prepared by cold isostatic pressing of the same powder at 1000 MPa. The sintering of warm pressed specimens moreover yielded the composites with higher final density (less than 4% of residual porosity) with the microstructure composed of micrometer-sized alumina grains (D₅₀ < 2 μm) with inter- and intragranular SiC precipitates. High sintering temperatures (>1800 °C) promoted the formation of intergranular platelets identified by TEM as 6H polytype of α-SiC. The maximum hardness (19.4 ± 0.5 GPa) and fracture toughness (4.8 ± 0.1 MPa m^1/2) were achieved in the composites containing 8 vol.% of SiC, and sintered for 3 h at 1850 °C. These values are within the limits reported for nanocomposites Al₂O₃/SiC by other authors and do not represent any significant improvement in comparison to monolithic alumina.     

High optical quality Y2O3 transparent ceramics with fine grain size fabricated by low temperature air pre-sintering and post-HIP treatment

High optical quality Y₂O₃ transparent ceramics with fine grain size were successfully fabricated by air pre-sintering at various temperature ranging from 1500 to 1600 °C combined with a post-hot-isostatic pressing (HIP) treatment using co-precipitated powders as the starting material. The fully dense Y₂O₃ transparent ceramic with highest transparency was obtained by pre-sintered at 1550 °C for 4 h in air and post-HIPed at 1600 °C for 3 h (the pressure of HIP 200 MPa), and it had fine microstructure and the average grain size was 0.96 μm. In addition, the in-line transmittance of the ceramic reached 81.7% at 1064 nm (1 mm thickness). By this approach, the transparent Y₂O₃ ceramics with fine grain size (<1.6 μm) were elaborated without any sintering aid.     

Transesterified milkweed (Asclepias) seed oil as a biodiesel fuel

The methyl and ethyl esters of milkweed (Asclepias) seed oil were prepared and compared to soybean esters in laboratory tests to determine biodiesel fuel performance properties. The pour points of the methyl and ethyl milkweed esters measured −6 °C and −10 °C, respectively, which is consistent with the high levels of unsaturation characteristic of milkweed seed oil. The oxidative stabilities measured by OSI at 100 °C were between 0.8 and 4.1 h for all samples tested. The kinematic viscosities determined at 40 °C by ASTM D 445 averaged 4.9 mm²/s for milkweed methyl esters and 4.2 mm²/s for soybean methyl esters. Lubricity values determined by ASTM D 6079 at 60 °C were comparable to the corresponding soybean esters with average ball wear scar values of 118 μm for milkweed methyl esters and 200 μm for milkweed ethyl esters.     

Modelling of the inactivation kinetics of Escherichia coli,Saccharomyces cerevisiae and pectin methylesterase in orange juice treated with ultrasonic-assisted supercritical carbon dioxide

The combined effect of supercritical carbon dioxide (SC-CO₂) and high power ultrasound (HPU) on the inactivation kinetics of Escherichia coli, Saccharomyces cerevisiae and pectin-methyl esterase (PME) in orange juice was studied in order to select models that can predict their inactivation behaviour based on process parameters. Experiments were performed at different temperatures (31–41 °C, 225 bar) and pressures (100–350 bar, 36 °C). The inactivation rate of E. coli, S. cerevisiae and PME increased with pressure and temperature during SC-CO₂ + HPU treatments. The SC-CO₂ + HPU inactivation kinetics of E. coli, S. cerevisiae and PME were represented by models that included temperature, pressure and treatment time as variables, based on the Biphasic, the Peleg Type B, and the fractional models, respectively. The HPU-assisted SC-CO₂ batch system permits the use of mild process conditions and treatment times that can be even shorter than those of continuous SC-CO₂ systems.     

Ball milling assisted hydrothermal synthesis of ZrO2 nanopowders

The formation of ZrO₂ nanopowders under various hydrothermal conditions such as temperature, time, autoclave rotation speed, heating rate and particularly assistance of ball milling during reaction was investigated. Full ZrO₂ formation (with monoclinic phase) from zirconium solution was completed at shorter times with increasing temperature such as after 4 h at 150 °C, 2 h at 175 °C and less than 2 h at 200 °C. Crystallite size increased from 2.9 to 4 nm with increasing reaction temperature from 125 °C to 200 °C, respectively. Ball milling assisted hydrothermal runs were performed to understand the effect of mechanical force on phase formation, crystallinity and particle size distribution. Monoclinic ZrO₂ was formed in both milled and non-milled runs when zirconium solution was used. Mean particle size for the 2 M solution was measured to be 94 nm for the milled and 117 nm for the non-milled powders. However, when amorphous aqueous zirconia gels (precipitated at pH 5.8) were used, tetragonal phase was also formed in addition to monoclinic phase. Mean particle size was measured to be 0.7 μm (d₉₀≅1.3 μm) for the milled and 7.9 μm (d₉₀≅13 μm) for the non-milled powders. Ball milling during hydrothermal reactions of both zirconium solution and aqueous zirconium gel resulted in smaller crystallite size and mean particle size and, at the same time, effectively controlled particle size distribution (or agglomeration) of nanopowders.     

Fabrication of porous SiO2/C composite from rice husks

Porous SiO₂/carbon composites were fabricated by heating pellets composed of rice husk (RH) powders in small (<74 μm), medium(74–175 μm) and large(150–300 μm) sizes. The contents of the small RH were fixed at 30 mass% and the RH pellets molded at 10, 15, and 30 MPa were heated at 800–1150 °C in an inert atmosphere. The weight loss due to the thermal decomposition of the organic materials in the pellet peaked at 1000 °C, whereas the specimen heated at 1000 °C showed the lowest carbon content and density, 29 mass% and 0.40 g cm⁻³, respectively. The SiO₂ phase of the specimens were amorphous at 800 and 1150 °C, but a cristobalite phase was visible at 1000 °C. The specimen fire at 1000 °C showed a higher compressive strength than the others, and the large RH particles were seen to increase the strength of the product while an increase in molding pressure decreased the medium pore size, from 17 to 7 μm, and increased the strength, from 0.25 to 3.52 MPa. The specific surface area (SSA) of the specimen peaked at 450 m² g⁻¹, at 1000 °C and finally, the mesopore size of the specimens was similar throughout, at ∼2 nm.     

Microwave dielectric properties of the (BaxSr1−x)TiO3 thin films on alumina substrate

Barium strontium titanate, (Ba_xSr_1?x)TiO₃ (BST) thin films have been prepared on alumina substrate by sol–gel technique. The X-ray patterns analysis indicated that the thin films are perovskite and polycrystalline structure. The interdigital electrode with 140 nm thickness Au/Ti was fabricated on the film with the finger length of 80 μm, width of 10 μm and gaps of 5 μm. The temperature dependence of dielectric constant of the BST thin films in the range from ?50 °C to 50 °C was measured at 1 MHz. The dielectric properties of the BST thin films were measured by HP 8510C vector network analyzer from 50 MHz to 20 GHz.     

ZnO thin film nanostructures for hydrogen gas sensing applications

A ZnO thin film-based gas sensor was fabricated using a SiO₂/Si substrate with a platinum comb-like integrated electrode and heating element. The structural characteristics, morphology, and surface roughness of the as-grown ZnO nanostructure were investigated. The film revealed the presence of a c-axis oriented (002) phase with a grain size of 20.8 nm. The sensor response was tested for hydrogen concentrations of 50, 70, 100, 200, 400, and 500 ppm at the optimum operating temperature of 350 °C. The sensitivities towards 50 and 200 ppm of hydrogen gas at 350 °C were approximately 78% and 98%, respectively. A linear response was observed for hydrogen concentrations within the range of 50 ppm–200 ppm. These results demonstrated the potential application of the ZnO nanostructure for the fabrication of cost-effective and high-performance gas sensors.     

Ultradrawing above the static melting temperature of ultra-high molecular weight isotactic poly(1-butene) having low ductility in the crystalline state

Ultra-high molecular weight isotactic poly(1-butene) (UHMW-PB1) melt-grown crystal (MGC) films were drawn using the PIN drawing technique. Although the UHMW-PB1 MGC films had poor ductility in the crystalline state, they were ultradrawable in the molten state above the static melting temperature (T_m). The drawability of the MGC films was strongly influenced by the draw temperature, the sample thickness, and the contact time between the metal heater and sample, and it increased with decreasing sample thickness. The maximum draw ratio (DR_max) was nearly constant when the sample thickness was less than 100 μm at a given draw temperature. The contact time between the metal heater and sample needed to draw continuously in the molten state was at least 0.1 s. The ductility increased rapidly above 130 °C, reaching a maximum at 200 °C, and decreased at higher temperatures. A DR_max of 170 was achieved at 200 °C under optimum conditions. The efficiency of the drawing, based on the Herman crystalline orientation function (f_c) and tensile properties versus DR, was lower for films drawn at higher temperatures. The highest f_c of 0.996, tensile modulus of 14 GPa, and strength of 900 MPa were obtained by ultradrawing with DR = 50 at 155 °C. This modulus corresponded to 58% of the X-ray crystal modulus (24 GPa), whereas the modulus of PB1 films drawn in the crystalline state corresponded to only 12–13% (3 GPa) of the theoretical crystal modulus.     

Extraction of bioactive components from Centella asiatica using subcritical water

Bioactive components, asiatic acid and asiaticoside, were extracted from Centella asiatica using subcritical water as an extraction solvent. Extraction yields of asiatic acid and asiaticoside were measured using high-performance liquid chromatography (HPLC) at temperatures from 100 to 250 °C and pressures from 10 to 40 MPa. As temperature or pressure increased, the extraction yield of asiatic acid and asiaticoside increased. At the optimal extraction conditions of 40 MPa and 250 °C, the extraction yield of asiatic acid was 7.8 mg/g and the extraction yield of asiaticoside was 10.0 mg/g. Extracted asiatic acid and asiaticoside could be collected from water as particles with a simple filtering process. Dynamic light scattering (DLS) was used to characterize particle size. Particles containing asiatic acid were larger (1.21 μm) than particles containing asiaticoside (0.76 μm). The extraction yields of asiatic acid and asiaticoside using subcritical water at 40 MPa and 250 °C were higher than extraction yields using conventional liquid solvent extraction with methanol or ethanol at room temperature while the subcritical water extraction yields were lower than extraction yields with methanol or ethanol at its boiling point temperature.     

Fabrication and properties of ultra highly porous silicon carbide by the gelation–freezing method

Silicon carbide (SiC) with ultra high porosity and unidirectionally oriented micrometer-sized cylindrical pores was prepared using a novel gelation–freezing (GF) method. Gelatin, water and silicon carbide powder were mixed and cooled at 7 °C. The obtained gels were frozen from ?10 to ?70 °C, dried using a vacuum freeze drier, degreased at 600 °C and then sintered at 1800 °C for 2 h. The gels could be easily formed into various shapes, such as cylinders, large pipes and honeycombs using molds. Scanning electron microscopy (SEM) observations of the sintered bodies showed a microstructure composed of ordered micrometer-sized cylindrical cells with unidirectional orientation. The cell size ranging from 34 to 147 μm could be modulated by changing the freezing temperatures. The numbers of cells for the samples frozen at ?10 and ?70 °C were 47 and 900 cells/mm², respectively, as determined from cross-sections of the sintered bodies. The resulting porous SiC with a total porosity of 86%, exhibited air permeability from 2.3 × 10^?11 to 1.0 × 10^?10 m², which was the same as the calculated ideal permeability, and high compressive strength of 16.6 MPa. The porosity, number of cells, air permeability and strength of the present porous SiC were significantly higher than that reported for other porous SiC ceramics.     

Mechanical behavior of zirconium diboride–silicon carbide ceramics at elevated temperature in air

The mechanical properties of zirconium diboride–silicon carbide (ZrB₂–SiC) ceramics were characterized from room temperature up to 1600 °C in air. ZrB₂ containing nominally 30 vol% SiC was hot pressed to full density at 1950 °C using B₄C as a sintering aid. After hot pressing, the composition was determined to be 68.5 vol% ZrB₂, 29.5 vol% SiC, and 2.0 vol% B₄C using image analysis. The average ZrB₂ grain size was 1.9 μm. The average SiC particles size was 1.2 μm, but the SiC particles formed larger clusters. The room temperature flexural strength was 680 MPa and strength increased to 750 MPa at 800 °C. Strength decreased to ～360 MPa at 1500 °C and 1600 °C. The elastic modulus at room temperature was 510 GPa. Modulus decreased nearly linearly with temperature to 210 GPa at 1500 °C, with a more rapid decrease to 110 GPa at 1600 °C. The fracture toughness was 3.6 MPa·m^½ at room temperature, increased to 4.8 MPa·m^½ at 800 °C, and then decreased linearly to 3.3 MPa·m^½ at 1600 °C. The strength was controlled by the SiC cluster size up to 1000 °C, and oxidation damage above 1200 °C.     

Supercritical carbon dioxide extraction of Capsicum peppers: Global yield and capsaicinoid content

The objective of this study was to select a variety of pepper with high concentration of capsaicin and subject it to supercritical fluid extraction (SFE), in order to determine the best conditions of temperature (40, 50 and 60 °C) and pressure (15, 25 and 35 MPa) in terms of global yield (X₀) and capsaicinoids content of the extracts. The influence of drying process (freeze and oven drying) on X₀, capsaicin (C) and dihydrocapsaicin (DHC) contents and total phenolics was also analyzed. Capsicum frutescens showed the highest levels of capsaicinoids (1516 μg/g fresh fruit). For the responses C and DHC, the extraction conditions of 15 MPa and 40 °C provided the highest concentrations (C ⿿ 42 mg/g extract and DHC ⿿ 18.5 mg/g extract). The freeze drying process resulted in extracts with the highest concentration of capsaicinoids (61 mg/g extract), but in contrast, the phenolics were less susceptible to different drying processes, with a mean concentration of 35 mg GAE/g extract. The kinetics experiments indicated that the extraction rate of oleoresin was slightly slower than that of capsaicinoids at the operation conditions (40 °C and 15 MPa).     

Micronization and characterization of squid lecithin/polyethylene glycol composite using particles from gas saturated solutions (PGSS) process

Lecithin was isolated from squid viscera residues after supercritical carbon dioxide (SC-CO₂) extraction at 25 MPa and 45 °C. The particle formation of squid lecithin with biodegradable polymer, polyethylene glycol (PEG) was performed by PGSS using SC-CO₂ in a thermostatted stirred vessel. By applying different temperatures (40 and 50 °C) and pressures (20–30 MPa), conditions were optimized. Two nozzles of different diameters (250 and 300 μm) were used for PGSS and the reaction time was 1 h. The average diameter of the particles obtained by PGSS at different conditions was about 0.74–1.62 μm. The lowest average size of lecithin particle with PEG was found by the highest SC-CO₂ density conditions with the stirring speed of 400 rpm and nozzle size of 250 μm. The inclusion of lecithin in PEG was quantified by HPLC. Acid value and peroxide value was measured after micronization of lecithin.     

Extraction of dietary fiber from Citrus junos peel with subcritical water

The juice processing by-product of Citrus junos is a high potential source of valuable compounds such as essential oils and a high amount of dietary fiber, consisting of pectin, hemicellulose, and cellulose. The residues obtained from supercritical CO₂ extraction of C. junos peel was used as a starting material for hydrothermal treatment to separate pectin and hemicellulose. The experimental apparatus used was a semi-continuous flow extractor. Treatment conditions were in the temperature range of 160–320 °C and water flow rates of 2.1, 3.5, and 7.0 mL/min under a pressure of 20 MPa. Approximately 78% of the pectin was contained in the fraction collected at 160 °C at each flow rate. Most of the hemicellulose was separated from cellulose up until the fraction obtained at 200 °C. The proportion of cellulose in the residue obtained after hydrothermal treatment at 200 °C reached about 80%. Moreover, the characteristics of recovered cellulose were expected to exhibit greater crystallinity and lower impurity than that of the raw material based on the results of scanning electron microscopy (SEM), attenuated total reflectance Fourier transmission infrared (ATR-FTIR), and thermogravimetric-differential thermal analyses (TG-DTA).     

Screening of twelve Clostridium botulinum (group I) spores for high-pressure resistance at elevated-temperatures

Twelve strains of Clostridium botulinum group I spores, suspended in phosphate buffer (0.1 M) at approximately 10⁷ CFU/ml concentration, were subjected to high pressure treatments (800 and 900 MPa; 0.5–15 min) at elevated temperatures (90 and 100 °C). The treatments were chosen to have a range of pressure/temperature severity to be able to discriminate the spore strains for their pressure resistance. An insulated test chamber was used to achieve temperature stability during treatment. Preliminary tests showed the need for an 8 day anaerobic incubation for enumeration. Results showed that strains PA9508B, HO9504A and CK2-A had higher pressure resistance than others among the 12 strains studied. Strain 62A was least resistant and completely inactivated by the treatment. Estimated D values of the more resistant strains were in the 0.66–1.8 min range at 900 MPa at 100 °C treatment. The temperature sensitivity parameter (Z_P value) in the 800–900 MPa pressure range varied between 10 and 16 °C, and pressure sensitivity parameter (Z_T value) in the 90–100 °C temperature range varied between 340 and 760 MPa. The most pressure resistant strain was PA9508B with an estimated Z_P value of 16.0 °C and Z_T value of 470 MPa. Since the pathogenic strains of C. botulinum have different pressure resistance, the most resistance strain should be selected as the basis for process establishment.