This paper reviews the phase structures and oxidation kinetics of complex Ti-Al alloys at oxidation temperatures in the range of 600-1000 °C. The mass gain and parabolic rate constants of the alloys under isothermal exposure at 100 h (or equivalent to cyclic exposure for 300 cycles) is compared. Of the alloying elements investigated, Si appeared to be the most effective in improving the oxidation resistance of Ti-Al alloys at high temperatures. The effect of alloying elements on the mechanical properties of Ti-Al alloys is also discussed. Significant improvement of the mechanical properties of Ti-Al alloys by element additions has been observed through the formation of new phases, grain refinement, and solid solution strengthening.
In order to meet the growing demand for adsorbents to treat wastewater effectively, there has been increased interest in using sustainable biomass feedstocks. In this present study, the dermal tissue of oil palm frond was pyrolyzed with superheated steam at 500 °C to produce nanoporous biochar as bioadsorbent. The effect of operating conditions was investigated to understand the adsorption mechanism and to enhance the adsorption of phenol and tannic acid. The biochar had a microporous structure with a Brunauer-Emmett-Teller surface area of 422 m2/g containing low polar groups. The adsorption capacity of 62.89 mg/g for phenol and 67.41 mg/g for tannic acid were obtained using 3 g/L biochar dosage after 8 h of treatment at solution pH of 6.5 and temperature of 45 °C. The Freundlich model had the best fit to the isotherm data of phenol (R2 of 0.9863), while the Langmuir model best elucidated the isotherm data of tannic acid (R2 of 0.9632). These indicated that the biochar-phenol interface was associated with a heterogeneous multilayer sorption mechanism, while the biochar-tannic acid interface had a nonspecific monolayer sorption mechanism. The residual concentration of 26.3 mg/L phenol and 23.1 mg/L tannic acid was achieved when treated from 260 mg/L three times consecutively with 1 g/L biochar dosage, compared to a reduction to 72.3 mg/L phenol and 69.9 mg/L tannic acid using 3 g/L biochar dosage in a single treatment. The biochar exhibited effective adsorption of phenol and tannic acid, making it possible to treat effluents that contain varieties of phenolic compounds.
The migration process of magnetic nanoparticles and colloids in solution under the influence of magnetic field gradients, which is also known as magnetophoresis, is an essential step in the separation technology used in various biomedical and engineering applications. Many works have demonstrated that in specific situations, separation can be performed easily with the weak magnetic field gradients created by permanent magnets, a process known as low-gradient magnetic separation (LGMS). Due to the level of complexity involved, it is not possible to understand the observed kinetics of LGMS within the classical view of magnetophoresis. Our experimental and theoretical investigations in the last years unravelled the existence of two novel physical effects that speed up the magnetophoresis kinetics and explain the observed feasibility of LGMS. Those two effects are (i) cooperative magnetophoresis (due to the cooperative motion of strongly interacting particles) and (ii) magnetophoresis-induced convection (fluid dynamics instability originating from inhomogeneous magnetic gradients). In this feature article, we present a unified view of magnetophoresis based on the extensive research done on these effects. We present the physical basis of each effect and also propose a classification of magnetophoresis into four distinct regimes. This classification is based on the range of values of two dimensionless quantities, namely, aggregation parameter N* and magnetic Grashof number Grm, which include all of the dependency of LGMS on various physical parameters (such as particle properties, thermodynamic parameters, fluid properties, and magnetic field properties). This analysis provides a holistic view of the classification of transport mechanisms in LGMS, which could be particularly useful in the design of magnetic separators for engineering applications.
Monodispersed iron oxide nanoparticles (IONPs) coated with polystyrenesulfonate (PSS) and cetrimonium bromide (CTAB) have been used to stabilize magnetic Pickering emulsions (MPEs). Magnetophoresis of MPEs under the influence of a low gradient magnetic field (∇B < 100 T/m) was investigated at the macroscopic and microscopic scale. At the macroscopic scale, for the case of pH 7, the MPE achieved a magnetophoretic velocity of 70.9 μm/s under the influence of ∇B at 93.8 T/m. The magnetic separation efficiency of the MPE at 90% was achieved within 30 min for pH 3, 7, and 10. At pH 10, the colloidal stability of the MPE was the lowest compared to that for pH 3 and 7. Thus, MPE at pH 10 required the shortest time for achieving the highest separation efficiency, as the MPE experienced cooperative magnetophoresis at alkaline pH. The creaming rate of the MPE at all conditions was still lower compared to magnetophoresis and was negligible in influencing its separation kinetics profiles. At the microscopic scale, the migration pathways of the MPEs (with diameters between 2.5 and 7.5 μm) undergoing magnetophoresis at ∇B ∼ 13.0 T/m were recorded by an optical microscope. From these experiments, and taking into consideration the MPE size distribution from the dynamic light scattering (DLS) measurement, we determined the averaged microscopic magnetophoretic velocity to be 7.8 ± 5.5 μm/s. By making noncooperative magnetophoresis assumptions (with negligible interactions between the MPEs along their migration pathways), the calculated velocity of individual MPEs was 9.8 μm/s. Such a value was within the percentage error of the experimental result of 7.8 ± 5.5 μm/s. This finding allows for an easy and quick estimation of the magnetophoretic velocity of MPEs at the microscale by using macroscopic separation kinetics data.
The purpose of this study was to simultaneously predict the drug release and skin permeation of Piroxicam (PX) topical films based on Chitosan (CTS), Xanthan gum (XG) and its Carboxymethyl derivatives (CMXs) as matrix systems. These films were prepared by the solvent casting method, using Tween 80 (T80) as a permeation enhancer. All of the prepared films were assessed for their physicochemical parameters, their in vitro drug release and ex vivo skin permeation studies. Moreover, deep learning models and machine learning models were applied to predict the drug release and permeation rates. The results indicated that all of the films exhibited good consistency and physicochemical properties. Furthermore, it was noticed that when T80 was used in the optimal formulation (F8) based on CTS-CMX3, a satisfactory drug release pattern was found where 99.97% of PX was released and an amount of 1.18 mg/cm2 was permeated after 48 h. Moreover, Generative Adversarial Network (GAN) efficiently enhanced the performance of deep learning models and DNN was chosen as the best predictive approach with MSE values equal to 0.00098 and 0.00182 for the drug release and permeation kinetics, respectively. DNN precisely predicted PX dissolution profiles with f2 values equal to 99.99 for all the formulations.
In this study, a response surface methodology (RSM) approach using central composite design (CCD) was investigated to develop a mathematical model and to optimize the effects of pH, adsorbent amount and temperature related to the hexavalent chromium removal by biosorption on peanut shells (PSh). The highest removal percentage of 30.28% was found by the predicted model under the optimum conditions (pH of 2.11, 0.73 g of PSh and 37.2 °C) for a 100 mg/L initial Cr(VI) concentration, which was very near to the experimental value (29.92%). The PSh was characterized by SEM, EDX, FTIR, BET, XRD analyses. Moreover, a Langmuir isotherm fitted well (R2 = 0.992) with the experimental data, and the maximum adsorption capacity was discovered to be 2.48 and 3.49 mg/g respectively at 25 and 45 °C. Kinetic data were well foreseen by pseudo second order. Thermodynamic study depicted that biosorption of Cr(VI) onto PSh was spontaneous and endothermic. Regeneration of the PSh using NaOH showed a loss <5% in the Cr(VI) removal efficiency up to three recycle runs. In summary, the Cr(VI) removal onto economic, sensitive and selective biosorbent (PSh) was optimized using CCD to study biosorption behaviors.
The fundamental mechanism of biochemistry lies on the reaction kinetics, which is determined by the reaction pathways. Interestingly, the reaction pathway is a challenging concept for undergraduate students. Experimentally, it is difficult to observe, and theoretically, it requires some degree of physics knowledge, namely statistical and quantum mechanics. However, students can utilize computational methods to study the reaction kinetics without paying too much attention but not wholly neglecting the comprehension of physics. We hereby provided an approach to study the reaction kinetics based on density-functional calculations. We particularized the study of the isomerization case involving five molecules at three different temperatures and emphasized the importance of the transition state in the study of reaction kinetics. The results we presented were in good agreement with the experiments and provided useful insights to assist students in the application of their knowledge into their research.
The current novel work presents the optimization of factors affecting defluoridation by Al doped ZnO nanoparticles using response surface methodology (RSM). Al doped ZnO nanoparticles were synthesized by the sol-gel method and validated by FTIR, XRD, TEM/EDS, TGA, BET, and particle size analysis. Moreover, a central composite design (CCD) was developed for the experimental study to know the interaction between Al doped ZnO adsorbent dosage, initial concentration of fluoride, and contact time on fluoride removal efficiency (response) and optimization of the process. Analysis of variance (ANOVA) was achieved to discover the importance of the individual and the effect of variables on the response. The model predicted that the response significantly correlated with the experimental response (R2 = 0.97). Among the factors, the effect of adsorbent dose and contact time was considered to have more influence on the response than the concentration. The optimized process parameters by RSM presented the adsorbent dosage: 0.005 g, initial concentration of fluoride: 1.5 g/L, and contact time: 5 min, respectively. Kinetic, isotherm, and thermodynamic studies were also investigated. The co-existing ions were also studied. These results demonstrated that Al doped ZnO could be a promising adsorbent for effective defluoridation for water.
The aim of this review was to systematically explore the underlying musculoskeletal biomechanical mechanisms of carrying and to describe its potential relationship with low back pain. This literature review was carried out using AMED, CINAHL, Compendex and MEDLINE electronic databases. Articles published from 2004 to 2012 were selected for consideration. Articles were considered if at least one measurement of kinetics, kinematics or other related musculoskeletal parameters related to biomechanics were included within the study. After combining the main keywords, 677 papers were identified. However, only 10 studies met all the inclusion criteria. Age, body mass index, gender and level of physical activity were identified as the factors that may influence the biomechanics of carrying activity. Carrying a loaded backpack was reported leading to posterior pelvic tilt, reduced lumbar lordosis, but increased cervical lordosis, thoracic kyphosis and trunk forward lean. Furthermore, while carrying bilaterally, lumbo-pelvic coordination was also reported to be more in-phase, as well as reduced coordination variability in transverse plane. Future studies investigating the biomechanics of a standardized carrying activity for clinical test are recommended.
The purpose of this study was to determine the relationship between supporting leg strength and supporting leg balance; and their correlation with kicking performance. Thirty four recreational male futsal players with a mean age 23.2±1.5 years old voluntarily participated in this study. Physical characteristics of participants (age, weight, height and body mass index) were recorded prior to test. Force platform was used to record kinetics variables during maximal instep kick (with and without target) and during the Balance Stork Test. Ball flight after impact with the kicking foot was recorded using high speed video camera set at 120 frame per second, with 500 hertz shutter speed. Ball velocity was then calculated using motion analysis software. Pearson correlation was used to determine the relationship between variables. Results indicated no significant correlation between maximal vertical force (max-vGRF) with the ball velocity for both condition of kicks; between strength (max-vGRF) and balance (at 95% ellipse area) of supporting leg; between supporting leg balance and ball velocity; between supporting leg balance and ball accuracy. However, negative significant correlations exist between max-vGRF and ball accuracy. Max-vGRF and ball velocity for both kicking without target and kicking with target was found highly correlated. As a conclusion, kicking performance was not primarily influenced by either the supporting leg strength (MVF) or supporting leg balance (95% ellipse area).
This study is an attempt to investigate the adsorption of petroleum hydrocarbon (toluene) from aqueous solutions using granular activated carbon (GAC) synthesized from oil palm shell (OPS) (referred as OPSbased GAC). This study involved a series of batch experiments to determine the adsorption equilibrium and kinetics. The batch experiments were conducted by shaking 200 mL toluene solution containing 0.4 g GAC (initial concentrations of 5, 15, 25 and 30 mg/L) at 180 rpm at 30°C. The OPS-based GAC achieved more than 80% toluene removal in all the experiments. The adsorption capacity of the OPSbased GAC estimated using Freundlich isotherm was 6.039 mg/g (L/mg)1/n. The adsorption kinetic study showed that the adsorption of toluene was of chemisorption as the experimental data fitted better to the pseudo-second-order kinetic model than the pseudo-first-order kinetic model.
Many studies have been done on various species of insects to investigate their potential use in industries. This is because insects have high protein content which could be further manipulated. Due to its eating habit, Zophobas morio larvae, also known as super mealworm has been shown to have high amylase activity. In this study, amylase from super mealworm has been immobilized via Cross-Linked Enzyme Aggregates (CLEA) technique and its kinetic performance, evaluated. CLEA is one of the best immobilization method with respect to enzyme stability and reusability. Kinetic performance of both free and CLEA-amylase were evaluated based on the Michaelis-Menten model. Results obtained based on Hanes-Woolf, LineweaverBurk, Eadie-Hofstee and Hyperbolic Regression plots showed that the kinetic parameters, Vmax and KM, changed upon immobilization. For CLEA-amylase, Hanes-Woolf plot showed the bestfitted model based on R2 with Vmax= 1.068 mM/min and KM= 0.182 mM, however, LineweaverBurk plot was used to obtain the kinetic parameters for free amylase, with Vmax and KM of 17.230 mM/min and 2.470 mM, respectively. Thus it is observed that upon immobilization, Vmax for amylase dropped appreciably, however, much lower substrate concentration is needed to saturate the enzymatic sites to reach its maximum catalytic efficiency. The result from this study might open the new path in discovering the potential use of insects in industrial applications, for example, making use of the recovered enzymes in the detergent industry.
Even purified enzyme preparations are often heterogeneous. For example, preparations of aspartate aminotransferase or cytochrome oxidase can consist of several different forms of the enzyme. For this reason we consider how different the kinetics of the reactions catalysed by a mixture of forms of an enzyme must be to provide some indication of the characteristics of the species present. Based on the standard Michaelis-Menten model, we show that if the Michaelis constants (Km) of two isoforms differ by a factor of at least 20 the steady-state kinetics can be used to characterise the mixture. However, even if heterogeneity is reflected in the kinetic data, the proportions of the different forms of the enzyme cannot be estimated from the kinetic data alone. Consequently, the heterogeneity of enzyme preparations is rarely reflected in measurements of their steady-state kinetics unless the species present have significantly different kinetic properties. This has two implications: (1) it is difficult, but not impossible, to detect molecular heterogeneity using kinetic data and (2) even when it is possible, a considerable quantity of high quality data is required.
In this study, the photocatalytic degradation of batik wastewater in the presence of zinc oxide (ZnO) as photocatalyst was
investigated. The effect of various operating parameters, such as pH of batik wastewater, catalyst dosage and aeration
on the photocatalytic degradation process, was examined. The mineralization of batik wastewater was also evaluated
through chemical oxygen demand analysis. The decolorization of batik wastewater was enhanced at acidic conditions
(pH3) which was 88.2% after 10 h irradiated under solar light, meanwhile its mineralization was 286 mg/L after 12 h
irradiation time. The data obtained for photocatalytic degradation of batik wastewater was well fitted with the LangmuirHinshelwood
kinetic model. It can be concluded that batik wastewater could be decolorized and mineralized under solar
light irradiation with presence of ZnO.
This study was conducted to investigate the batch and fixed-bed adsorption properties of boron on curcumin-impregnated activated carbon (Cur-AC). The maximum boron removal was obtained at pH5.5 and 120 min of contact time. Langmuir and Freundlich isotherm models were applied and it was determined that the experimental data conformed to both models. The Langmuir maximum adsorption capacities for Cur-AC (5.00 mg/g) and regenerated Cur-AC (3.61 mg/g) were obviously higher than the capacity for bare activated carbon (0.59 mg/g). Kinetic studies indicated the adsorption of boron conformed to the intra-particle model. The highest boron removal in fixed-bed column adsorption was achieved up to 99% for the first 5 min at an inlet concentration of 890 mg/L and a flow rate of 8.0 mL/min. Thomas and the Yoon-Nelson models gave better fit to the experimental data. Cur-AC can be reused after elution processes with slightly lower adsorption capacity.
Microscopic models of reaction-diffusion processes on the cell membrane can link local spatiotemporal effects to macroscopic self-organized patterns often observed on the membrane. Simulation schemes based on the microscopic lattice method (MLM) can model these processes at the microscopic scale by tracking individual molecules, represented as hard spheres, on fine lattice voxels. Although MLM is simple to implement and is generally less computationally demanding than off-lattice approaches, its accuracy and consistency in modeling surface reactions have not been fully verified. Using the Spatiocyte scheme, we study the accuracy of MLM in diffusion-influenced surface reactions. We derive the lattice-based bimolecular association rates for two-dimensional (2D) surface-surface reaction and one-dimensional (1D) volume-surface adsorption according to the Smoluchowski-Collins-Kimball model and random walk theory. We match the time-dependent rates on lattice with off-lattice counterparts to obtain the correct expressions for MLM parameters in terms of physical constants. The expressions indicate that the voxel size needs to be at least 0.6% larger than the molecule to accurately simulate surface reactions on triangular lattice. On square lattice, the minimum voxel size should be even larger, at 5%. We also demonstrate the ability of MLM-based schemes such as Spatiocyte to simulate a reaction-diffusion model that involves all dimensions: three-dimensional (3D) diffusion in the cytoplasm, 2D diffusion on the cell membrane, and 1D cytoplasm-membrane adsorption. With the model, we examine the contribution of the 2D reaction pathway to the overall reaction rate at different reactant diffusivity, reactivity, and concentrations.
Lack of sufficient nitrogenous substrate and buffering potential have been acknowledged as impediments to the treatment of palm oil mill effluent through co-digestion processes. In this study, ammonium bicarbonate was used to provide the nitrogenous substrate and buffering potential. To regulate the impact of ammonium bicarbonate toxicity on the anaerobic co-digestion system, dosages from 0 to 40 mg/L were supplemented. The biogas yield was used to indicate the effects of NH4+ toxicity. In a solar-assisted bioreactor, solar radiation was first collected by a solar panel and converted into electricity, which was then used to heat a mixture of palm oil mill effluent and cattle manure to maintain the reactor in the mesophilic temperature range. This co-digestion operation was performed semi-continuously and was analyzed at a 50:50 mixing ratio of palm oil mill effluent and cattle manure. The results indicate that the additional dosing of ammonium bicarbonate can significantly enhance biogas production. Maximum cumulative biogas and methane productions of 2034.00 mL and 1430.51 mL, respectively, were obtained with the optimum addition of 10 mg/L ammonium bicarbonate; these values are 29.80% and 42.30% higher, respectively, than that obtained in the control co-digestion operation without addition of ammonium bicarbonate. Utilization of a mathematical equation (G = Gmk/t) to describe a kinetic analysis of the biogas yield also indicated that the optimum ammonium bicarbonate dose was 10 mg/L. The results of this study suggest that supplementation with ammonium bicarbonate doses of up to 40 mg/L can be used to provide nitrogenous substrates and buffering potential in anaerobic co-digestion processes. The determination of the optimal dose provides an alternative and efficient option for enhanced biogas production, which will have obvious economic advantages for feasible industrial applications.
Low temperature thermal pre-treatment is a low-cost method to break down the structure of extracellular polymeric substances in waste activated sludge (WAS) while improving the sludge biodegradability. However, previous models on low temperature thermal pre-treatment did not adequately elucidate the behaviour of sludge hydrolysis process for the duration ranging from 5 to 9 h. Therefore, this work had developed an inclusive functional model to describe the kinetics of sludge hydrolysis for a wide range of treatment conditions (30 °C-90 °C within 0 and 16 h). As compared with treatment duration, the treatment temperature played a greater impact in solubilizing WAS. Accordingly, the 90 °C treatment had consistently produced WAS with the highest degree of solubility. Nonetheless, the mediocre discrepancies between 90 °C and 75 °C may challenge the practicality of increasing the treatment temperatures beyond 75 °C. The effects of treatment duration on soluble chemical oxygen demand, soluble carbohydrate and soluble protein were only significant during the first 4 h, except for humic substances release that continued to increase with treatment duration. Finally, a good fit with R2 > 0.95 was achieved using an inclusive multivariate non-linear model, substantiating the functionality to predict the kinetics of sludge hydrolysis at arbitrary treatment conditions.
In this work, graphene oxide (GO) and its reduced graphene oxide-zinc oxide nanocomposite (rGO-ZnO) was used for the removal of Cr (VI) from aqueous medium. By employing a variety of characterization techniques, morphological and structural properties of the adsorbents were determined. The adsorption study was done by varying concentration, temperature, pH, time, and amount of adsorbent. The results obtained confirmed that rGO-ZnO is a more economical and promising adsorbent for removing Cr (VI) as compared to GO. Kinetic study was also performed, which suggested that sorption of Cr (VI) follows the pseudo-first-order model. For equilibrium study, non-linear Langmuir was found a better fitted model than its linearized form. The maximum adsorption capacity calculated for GO and rGO-ZnO nanocomposite were 19.49 mg/g and 25.45 mg/g, respectively. Endothermic and spontaneous nature of adsorption was detected with positive values of ΔS (change in entropy), which reflects the structural changes happening at the liquid/solid interface.
Concerns have been raised about the safety and tolerability of phytosterol esters due to their vulnerability to oxidation. Herein, oxidation of the unsaturated fatty acid-phytosterol ester, namely β-sitosteryl oleate, was observed in comparison to native β-sitosterol after accelerated storage at 65 °C for 35 days in a bulk oil model system. Depending on the sterol structure, various chemical indices of lipid oxidation, including hydroperoxide value (HPV), thiobarbituric acid reactive substances (TBARS), p-anisidine value (AnV), and 7-keto derivatives, changed at varying rates in both samples. Such indicators for β-sitosteryl oleate appeared to be obtained at higher concentrations than those for β-sitosterol. The first order kinetic was used to describe the losses of β-sitosteryl oleate and β-sitosterol in bulk oil. It was discovered that the β-sitosteryl oleate (k = 0.0202 day-1) underwent oxidative alteration more rapidly than β-sitosterol (k = 0.0099 day-1). Results indicated that physical structure was the principal factor in the determination of storage stability of phytosterol and its ester. Research on antioxidants and storage techniques can be expanded in order to reduce the oxidative loss of phytosterol esters during storage and improve the safety and tolerability of phytosterol esters.