We present an incorporation of the kinetic Monte Carlo(kMC)simulation with the adjacency matrix(AM)method to investigate structural parameters of randomly branched polymers.The AMs of branched polymers are obtained by...We present an incorporation of the kinetic Monte Carlo(kMC)simulation with the adjacency matrix(AM)method to investigate structural parameters of randomly branched polymers.The AMs of branched polymers are obtained by the growth generation model,which is employed in the kMC simulation based on Gillespie’s algorithm.Of particular interest is the effect of the branched units on the relevant structural parameters.As an application in randomly hyperbranched polymers formed by AB_(2)type of monomers,average maximum span length,average length of sub-chains,number distribution of branched units,and meansquare radius of gyration are calculated.It is shown that the branched units can give rise to a significant effect on these physical quantities,whereby such a structure-property relationship can be employed to optimize reaction conditions and implement material designs.展开更多
The sulfation and decomposition process has proven effective in selectively extracting lithium from lepidolite.It is essential to clarify the thermochemical behavior and kinetic parameters of decomposition reactions.A...The sulfation and decomposition process has proven effective in selectively extracting lithium from lepidolite.It is essential to clarify the thermochemical behavior and kinetic parameters of decomposition reactions.Accordingly,comprehensive kinetic study by employing thermalgravimetric analysis at various heating rates was presented in this paper.Two main weight loss regions were observed during heating.The initial region corresponded to the dehydration of crystal water,whereas the subsequent region with overlapping peaks involved complex decomposition reactions.The overlapping peaks were separated into two individual reaction peaks and the activation energy of each peak was calculated using isoconversional kinetics methods.The activation energy of peak 1 exhibited a continual increase as the reaction conversion progressed,while that of peak 2 steadily decreased.The optimal kinetic models,identified as belonging to the random nucleation and subsequent growth category,provided valuable insights into the mechanism of the decomposition reactions.Furthermore,the adjustment factor was introduced to reconstruct the kinetic mechanism models,and the reconstructed models described the kinetic mechanism model more accurately for the decomposition reactions.This study enhanced the understanding of the thermochemical behavior and kinetic parameters of the lepidolite sulfation product decomposition reactions,further providing theoretical basis for promoting the selective extraction of lithium.展开更多
Hepatocellular carcinoma presents with three distinct immune phenotypes,including immune-desert,immune-excluded,and immune-inflamed,indicating various treatment responses and prognostic outcomes.The clinical applicati...Hepatocellular carcinoma presents with three distinct immune phenotypes,including immune-desert,immune-excluded,and immune-inflamed,indicating various treatment responses and prognostic outcomes.The clinical application of multi-omics parameters is still restricted by the expensive and less accessible assays,although they accurately reflect immune status.A comprehensive evaluation framework based on“easy-to-obtain”multi-model clinical parameters is urgently required,incorporating clinical features to establish baseline patient profiles and disease staging;routine blood tests assessing systemic metabolic and functional status;immune cell subsets quantifying subcluster dynamics;imaging features delineating tumor morphology,spatial configuration,and perilesional anatomical relationships;immunohistochemical markers positioning qualitative and quantitative detection of tumor antigens from the cellular and molecular level.This integrated phenomic approach aims to improve prognostic stratification and clinical decision-making in hepatocellular carcinoma management conveniently and practically.展开更多
This study explores the thin-layer convective solar drying of Marrubium vulgare L.leaves under conditions typical of sun-rich semi-arid climates.Drying experiments were conducted at three inlet-air temperatures(40℃,5...This study explores the thin-layer convective solar drying of Marrubium vulgare L.leaves under conditions typical of sun-rich semi-arid climates.Drying experiments were conducted at three inlet-air temperatures(40℃,50℃,60℃)and two air velocities(1.5 and 2.5 m·s^(-1))using an indirect solar dryer with auxiliary temperature control.Moisture-ratio data were fitted with eight widely used thin-layer models and evaluated using correlation coefficient(r),root-mean-square error(RMSE),and Akaike information criterion(AIC).A complementary heattransfer analysis based on Reynolds and Prandtl numbers with appropriate Nusselt correlations was used to relate flow regime to drying performance,and an energy balance quantified the relative contributions of solar and auxiliary heat.The logarithmic model consistently achieved the lowest RMSE/AIC with r>0.99 across all conditions.Higher temperature and air velocity significantly reduced drying time during the decreasing-rate period,with no constantrate stage observed.On average,solar input supplied the large majority of the thermal demand,while the auxiliary heater compensated short irradiance drops to maintain setpoints.These findings provide a reproducible dataset and a modelling benchmark for M.vulgare leaves,and they support energy-aware design of hybrid solar dryers formedicinal plants in sun-rich regions.展开更多
The increasing production and release of synthetic organic chemicals,including pharmaceuticals,into our envi-ronment has allowed these substances to accumulate in our surface water systems.Current purification technol...The increasing production and release of synthetic organic chemicals,including pharmaceuticals,into our envi-ronment has allowed these substances to accumulate in our surface water systems.Current purification technolo-gies have been unable to eliminate these pollutants,resulting in their ongoing release into aquatic ecosystems.This study focuses on cloperastine(CPS),a cough suppressant and antihistamine medication.The environmental impact of CPS usage has become a concern,mainly due to its increased detection during the COVID-19 pandemic.CPS has been found in wastewater treatment facilities,effluents from senior living residences,river waters,and sewage sludge.However,the photosensitivity of CPS and its photodegradation profile remain largely unknown.This study investigates the photodegradation process of CPS under simulated tertiary treatment conditions using UV photolysis,a method commonly applied in some wastewater treatment plants.Several transformation prod-ucts were identified,evaluating their kinetic profiles using chemometric approaches(i.e.,curve fitting and the hard-soft multivariate curve resolution-alternating least squares(HS-MCR-ALS)algorithm)and calculating the reaction quantum yield.As a result,three different transformation products have been detected and correctly identified.In addition,a comprehensive description of the kinetic pathway involved in the photodegradation process of the CPS drug has been provided,including observed kinetic rate constants.展开更多
The effects of acid surface dissolution on the flotation kinetics of ilmenite(IL)and its common accompanied gangue minerals including olivine-pyroxene(Ol-Px),tremolite-clinochlore(Tr-Cch)and quartz were investigated.T...The effects of acid surface dissolution on the flotation kinetics of ilmenite(IL)and its common accompanied gangue minerals including olivine-pyroxene(Ol-Px),tremolite-clinochlore(Tr-Cch)and quartz were investigated.The results show that through the surface dissolution the adsorption rate constant for ilmenite increases from 5.272 to 8.441 mol/(g·min)while it decreases for Ol-Px,Tr-Cch and quartz from 6.332,7.309 and 7.774 mol/(g·min)to 5.034,6.223 and 7.371 mol/(g·min),respectively.Also,the flotation experiments on a binary mixture of minerals indicate that after surface dissolution the values of modified rate constant for ilmenite flotation from Ol-Px,Tr-Cch and quartz are enhanced from 36.15,36.52 and 47.86 min-1 to 41.72,45.78 and 56.24 min-1,respectively.This results in the improvement of kinetic selectivity index(SI)in the separation of treated ilmenite from gangue minerals.As evidenced by ICP-MS analysis,the decrease of kinetic parameters for gangue minerals can be due to the removal of Fe^2+,Ca^2+and Mg^2+ions from their surfaces,which results in the lack of enough active sites to interact with collector species.As confirmed by contact angle measurements,this prevents the formation of a stable hydrophobic layer on the minerals surfaces for creating stable attachments between minerals and bubbles.Generally,the improvement of ilmenite flotation kinetics has a negative correlation with the iron content in its accompanied gangue minerals.展开更多
Determination of probable mechanism function and kinetic parameters is important to hydrometallurgical kinetics.In this work,the most probable mechanism function and kinetic parameters of gibbsite dissolution in NaOH ...Determination of probable mechanism function and kinetic parameters is important to hydrometallurgical kinetics.In this work,the most probable mechanism function and kinetic parameters of gibbsite dissolution in NaOH solution are studied.The sample,the mixture of synthetic gibbsite and sodium hydroxide solution,was scanned in high-pressure differential scanning calorimetry(DSC) equipment with the heating rate of 10 K·min-1. Integral equation and differential equation of non-isothermal kinetics were solved to fit the data related to DSC curve.According to the calculation results,the most probable mechanism function for pure synthetic gibbsite dissolution in sodium hydroxide solution is presented based on the optimum procedure in the database of the mechanism function.The apparent activation energy obtained is(75±1) kJ·mol-1,the frequency factor is 10 8±1mol·s-1,and the reaction is a second order reaction.展开更多
The thermal behavior,non-isothermal thermal decomposition reaction kinetics and specific heat capacity of hexanitro-hexaazaisowurtzitane(HNIW)were studied by differential scanning calorimeter(DSC)and Micro-DSCIapparat...The thermal behavior,non-isothermal thermal decomposition reaction kinetics and specific heat capacity of hexanitro-hexaazaisowurtzitane(HNIW)were studied by differential scanning calorimeter(DSC)and Micro-DSCIapparatus,The kinetic parameters of the thermal decomposition reaction(the apparent activation energy(E,)and pre-exponential factor(A))were calcu-lated by non-isothermal DSC curves.The results show that the differential mlechanism function and values of E,and A of the ther-mal decomposition reaction of HNIW are 3(1-a)[-ln(1-a)]"·,155.04 kJ·mol^(-1)and 10""s^(-1),respectively.The critical tem-perature of thermal explosion of the title compound is 226.60℃.The entropy of activation(AS·),enthalpy of activation(AH·)and free energy of activation(AG·)of this reaction are 11.60J·mol·K^(-1),152.04 kJ·mol^(-1)and 146.29 kJ·mol^(-1),respec-tively.The equation of specific heat capacity of HNIW with temperature is C,=0.2472+0.002705992Tin the temperature range of 283 K to 343K.The values of self-accelerating decomposition temperature,adiabatic time-to-maximum decomposition rate and adiabatic time-to-explosion are 486.5K,54.81s and 54.31s,respectively.Thermal sensitivity probability density distribution curve of HNIW is constructed.展开更多
In this paper,Dy^(3+)incorporated BaSi_(2)O_(5)phosphors were synthesized by gel co mbustion method and characterized by X-ray diffraction(XRD).The effects of various heating rate s on thermoluminescence(TL)kinetics a...In this paper,Dy^(3+)incorporated BaSi_(2)O_(5)phosphors were synthesized by gel co mbustion method and characterized by X-ray diffraction(XRD).The effects of various heating rate s on thermoluminescence(TL)kinetics and glow peak temperatures of Dy^(3+)incorporated BaSi_(2)O_(5)phosphors exposed toβirradiation at room temperature were investigated.The glow curves of the phosphor exposed toβ-irradiation(0.1-100 Gy)consist of four main peaks located at 87,130,271,and 327℃and exhibit a good linearity between 0.1 and100 Gy.Three experimental techniques including variable heating rate(VHR),repeated initial rise(RIR),peak shape(PS)and computerized glow curve deconvolution(CGCD)were employed to determine TL kinetic parameters.Our findings indicate that the TL glow peaks of the phosphor obey first-order kinetics.Analysis of the main dosimetric peaks through the techniques mentio ned above indicates that activation energies(E)and pre-exponential factor(s)are in the range of 0.80-1.50 eV and 1.15×10^(8)-3.28×10^(13)s^(-1).Additionally,it is found that the temperature of the glow peaks shifts toward the higher temperatures and the TL intensity smoothly decreases as the heating rate increases.The effect on the TL intensities and glow peak temperatu res of the heating rate is discussed in terms of thermal quenching.展开更多
Corn field experiments with two treatments, NP and NPK, where N in the form of urea, P in the form of calcium phosphate, and K in the form of KCl were applied at rates of 187.5, 33.3, and 125 kg ha^-1, respectively, o...Corn field experiments with two treatments, NP and NPK, where N in the form of urea, P in the form of calcium phosphate, and K in the form of KCl were applied at rates of 187.5, 33.3, and 125 kg ha^-1, respectively, on soils derived from Quaternary red clay were conducted in the hilly red soil region of Zhejiang Province, China. Plant grains and stalks were collected for determination of K content. Seven equations were used to describe the kinetics of K release from surface soil samples taken before the corn experiments under electric field strengths of 44.4 and 88.8 V cm^-1 by means of electro-ultrafiltration （EUF） and to determine if their parameters had a practical application. The second-order and Elovich equations excellently described K release; the first-order, power function, and parabolic diffusion equations also described K release well; but the zero-order and exponential equations were not so good at reflecting K release. Five reference standards from the field experiments, including relative grain yield （yield of the NP treatment/yield of the NPK treatment）, relative dry matter yield （dry matter of the NP treatment/dry matter of the NPK treatment）, quantity of K uptake in the NP treatment （no K application）, soil exchangeable K, and soil HNO3-soluble K, were used to test the effectiveness of equation parameters obtained from the slope or intercept of these equations. Correlations of the ymax （the maximum desorbable quantity of K） in the second-order equation and the constant b in the first-order and Elovich equations to all five reference standards were highly significant （P ≤ 0.01）. The constant a in the power function equation was highly significant （P 〈 0.01） for four of the five reference standards with the fifth being significant （P ≤ 0.05）. The constant b in the parabolic equation was also significantly correlated （P ≤ 0.05） to the relative grain yield and soil HNO3-soluble K. These suggested that all of these parameters could be used to estimate the soil K supplying capacity and the crop response to K fertilizer.展开更多
Combustion kinetic parameters(i.e.,activation energy and frequency factor) of coal have been proven to relate closely to coal properties;however,the quantitative relationship between them still requires further study....Combustion kinetic parameters(i.e.,activation energy and frequency factor) of coal have been proven to relate closely to coal properties;however,the quantitative relationship between them still requires further study.This paper adopts a support vector regression machine(SVR) to generate the models of the non-linear relationship between combustion kinetic parameters and coal quality.Kinetic analyses on the thermo-gravimetry(TG) data of 80 coal samples were performed to prepare training data and testing data for the SVR.The models developed were used in the estimation of the combustion kinetic parameters of ten testing samples.The predicted results showed that the root mean square errors(RMSEs) were 2.571 for the activation energy and 0.565 for the frequency factor in logarithmic form,respectively.TG curves defined by predicted kinetic parameters were fitted to the experimental data with a high degree of precision.展开更多
For processing parts made from medium carbon steel, toughness and flexibility are of importance. There- fore, to achieve these properties, the cementite in the steels is spheroidized through heat treatment. Different ...For processing parts made from medium carbon steel, toughness and flexibility are of importance. There- fore, to achieve these properties, the cementite in the steels is spheroidized through heat treatment. Different parameters such as the time and temperature of spheroidizing and the initial microstructure of the steel affect the amount of spheroidized cementite. In the present work, the percent of contribution of two parameters, i.e. initial microstructure and spheroidizing time, to the percent of spheroidization in CK60 steel was investigated using Taguchi robust design. The initial microstructures consisted of martensite, coarse pearlite, fine pearlite and bainite and the chosen spheroidization times were 4, 8, 12, and 16h. Spheroidizing was done at the constant temperature 700℃. After spheroidizing was completed, the samples were prepared in order to observe their microstructure under an optical microscope and to determine the spheroidized percent using MIPTM （metallographic image processing） software. It was found that the spheroidizing time had the most influence （58.5 ~//0） on spheroidized percent and the initial microstructure only had a 31.1% contribution. Finally, the instantaneous growth rate of the carbide was also deduced.展开更多
One-step crystallization is one of the most energy conserving methods for glass-ceramics preparation.However,only a few kinetics studies focused on the glass-ceramics prepared by the one-step crystallization.The onest...One-step crystallization is one of the most energy conserving methods for glass-ceramics preparation.However,only a few kinetics studies focused on the glass-ceramics prepared by the one-step crystallization.The onestep crystallization kinetic parameters were studied using differential scanning calorimetry.The activation energy（Ea）and the Avrami parameter（n）were calculated as 152.79kJ·mol-1 and 4.39,respectively.These parameters indicate that continuous nucleation and three-dimensional crystal growth are the dominating mechanisms in the one-step crystallization process of the parent glass.The properties of the obtained glass-ceramics can be compared to the glass-ceramics prepared by the two-stage heat treatment and sintering method.This crystallization kinetics research can be used to evaluate the one-step crystallization potential of a parent glass.展开更多
The exact calculation of point kinetic parameters is very important in nuclear reactor safety assessment, and most sophisticated safety codes such as RELAP5, PARCS,DYN3D, and PARET are using these parameters in their ...The exact calculation of point kinetic parameters is very important in nuclear reactor safety assessment, and most sophisticated safety codes such as RELAP5, PARCS,DYN3D, and PARET are using these parameters in their dynamic models. These parameters include effective delayed neutron fractions as well as mean generation time.These parameters are adjoint-weighted, and adjoint flux is employed as a weighting function in their evaluation.Adjoint flux calculation is an easy task for most of deterministic codes, but its evaluation is cumbersome for Monte Carlo codes. However, in recent years, some sophisticated techniques have been proposed for Monte Carlo-based point kinetic parameters calculation without any need of adjoint flux. The most straightforward scheme is known as the ‘‘prompt method'' and has been used widely in literature. The main objective of this article is dedicated to point kinetic parameters calculation in Tehran research reactor(TRR) using deterministic as well as probabilistic techniques. WIMS-D5B and CITATION codes have been used in deterministic calculation of forward and adjoint fluxes in the TRR core. On the other hand, the MCNP Monte Carlo code has been employed in the ‘‘prompt method''scheme for effective delayed neutron fraction evaluation.Deterministic results have been cross-checked with probabilistic ones and validated with SAR and experimental data. In comparison with experimental results, the relativedifferences of deterministic as well as probabilistic methods are 7.6 and 3.2%, respectively. These quantities are10.7 and 6.4%, respectively, in comparison with SAR report.展开更多
A deep understanding of turbulence structure is important for investigating the characteristics of the atmospheric boundary layer,especially over heterogeneous terrain.In the present study,turbulence intensity and tur...A deep understanding of turbulence structure is important for investigating the characteristics of the atmospheric boundary layer,especially over heterogeneous terrain.In the present study,turbulence intensity and turbulent kinetic energy（TKE）parameters are analyzed for different conditions with respect to stability,wind direction and wind speed over a valley region of the Loess Plateau of China during December 2003 and January 2004.The purpose of the study is to examine whether the observed turbulence intensity and TKE parameters satisfy Monin–Obukhov similarity theory（MOST）,and analyze the wind shear effect on,and thermal buoyancy function of,the TKE,despite the terrain heterogeneity.The results demonstrate that the normalized intensity of turbulence follows MOST for all stability in the horizontal and vertical directions,as well as the normalized TKE in the horizontal direction.The shear effect of the wind speed in the Loess Plateau region is strong in winter and could enhance turbulence for all stability conditions.During daytime,the buoyancy and shear effect together constitute the generation of TKE under unstable conditions.At night,the contribution of buoyancy to TKE is relatively small,and mechanical shearing is the main production form of turbulence.展开更多
Kinetics of oxidation of MgO-C refractories was investigated by shrinking core modeling of the gas-solid reactions taking place during heating the porous materials to the high temperatures. Samples containing 4.5-17 w...Kinetics of oxidation of MgO-C refractories was investigated by shrinking core modeling of the gas-solid reactions taking place during heating the porous materials to the high temperatures. Samples containing 4.5-17 wt pct graphite were isothermally oxidized at 1000-1350℃. Weight loss data was compared with predictions of the model. A mixed 2-stage mechanism comprised of pore diffusion plus boundary layer gas transfer was shown to generally control the oxidation rate. Pore diffusion was however more effective, especially at graphite contents lower than 10 wt pct under forced convection blowing of the air. Model calculations showed that effective gas diffusion coefficients were in the range of 0.08 to 0.55 cm^2/s. These values can be utilized to determine the corresponding tortuosity factors of 6.85 to 2.22. Activation energies related to the pore diffusion mechanism appeared to be around （46.44±2） kJ/mol. The estimated intermolecular diffusion coefficients were shown to be independent of the graphite content, when the percentage of the graphite exceeded a marginal value of 10.展开更多
A new version of differential evolution （DE） algorithm, in which immune concepts and methods are applied to determine the parameter setting, named immune self-adaptive differential evolution （ISDE）, is proposed to...A new version of differential evolution （DE） algorithm, in which immune concepts and methods are applied to determine the parameter setting, named immune self-adaptive differential evolution （ISDE）, is proposed to improve the performance of the DE algorithm. During the actual operation, ISDE seeks the optimal parameters arising from the evolutionary process, which enable ISDE to alter the algorithm for different optimization problems and improve the performance of ISDE by the control parameters＇ self-adaptation. The .performance of the proposed method is studied with the use of nine benchmark problems and compared with original DE algorithm ~nd-other well-known self-adaptive DE algorithms. The experiments conducted show that the ISDE clearly outperforms the other DE algorithms in all benchmark functions. Furthermore, ISDE is applied to develop the kinetic model for homogeneous mercury. （Hg） oxidation in flue gas, and satisfactory results are obtained.展开更多
Determination of the optimal model parameters for biochemical systems is a time consuming iterative process. In this study, a novel hybrid differential evolution （DE） algorithm based on the differential evolution te...Determination of the optimal model parameters for biochemical systems is a time consuming iterative process. In this study, a novel hybrid differential evolution （DE） algorithm based on the differential evolution technique and a local search strategy is developed for solving kinetic parameter estimation problems. By combining the merits of DE with Gauss-Newton method, the proposed hybrid approach employs a DE algorithm for identifying promising regions of the solution space followed by use of Gauss-Newton method to determine the optimum in the identified regions. Some well-known benchmark estimation problems are utilized to test the efficiency and the robustness of the proposed algorithm compared to other methods in literature. The comparison indicates that the present hybrid algorithm outperforms other estimation techniques in terms of the global searching ability and the con- vergence speed. Additionally, the estimation of kinetic model parameters for a feed batch fermentor is carried out to test the applicability of the proposed algorithm. The result suggests that the method can be used to estimate suitable values of model oarameters for a comolex mathematical model.展开更多
In a thermal simulation experiment of gold tubes of closed-system, calculating with the KINETICS and GOR-ISOTOPE KINETICS software, kinetic parameters of gas generation and methane carbon isotopic fractionation from T...In a thermal simulation experiment of gold tubes of closed-system, calculating with the KINETICS and GOR-ISOTOPE KINETICS software, kinetic parameters of gas generation and methane carbon isotopic fractionation from Triassic-Jurassic hydrocarbon source rocks in the Kuqa depression of Tarim Basin are obtained. The activation energies of methane generated from Jurassic coal, Jurassic mudstone and Triassic mudstone in the Kuqa Depression are 197-268 kJ/mol, 180-260 kJ/mol and 214-289 kJ/mol, respectively, and their frequency factors are 5.265×10^13 s^-1, 9.761×10^11 s^-1 and 2.270×10^14 s^-1. This reflects their differences of hydrocarbon generation behaviors. The kinetic parameters of methane carbon isotopic fractionation are also different in Jurassic coal, Jurassic mudstone and Triassic mudstone, whose average activation energies are 228 kJ/mol, 205 kJ/mol and 231 kJ/mol, respectively. Combined with the geological background, the origin of natural gas in the Yinan-2 gas pool is discussed, and an accumulation model of natural gas is thus established. The Yinan- 2 gas is primarily derived from Jurassic coal-bearing source rocks in the Yangxia Sag. Main gas accumulation time is 5-0 Ma and the corresponding Ro is in the range from 1.25 %-1.95 %. The loss rate of natural gas is 25 %-30 %.展开更多
The feasibility and kinetics of lead recovery from the slag of traditional lead melting furnace using chloride leaching were investigated.The effects of operating parameters such as leaching time,NaCl concentration,Fe...The feasibility and kinetics of lead recovery from the slag of traditional lead melting furnace using chloride leaching were investigated.The effects of operating parameters such as leaching time,NaCl concentration,FeCl3concentration,liquid/solid ratio,stirring rate,temperature,and particle size on recovery of lead were studied and the optimization was done through the response surface methodology(RSM)based on central composite design(CCD)model.The optimum conditions were achieved as follows:leaching time60min,80°C,stirring rate800r/min,NaCl concentration200g/L,FeCl3concentration80g/L,liquid/solid ratio16,and particle size less than106μm.More than96%of lead was effectively recovered in optimum condition.Based on analysis of variance,the reaction temperature,liquid/solid ratio,and NaCl concentration were determined as the most effective parameters on leaching process,respectively.Kinetics study revealed that chloride leaching of galena is a first-order reaction and the diffusion through solid reaction product and chemical reaction control the mechanism.The activation energy of chloride leaching of galena was determined using Arrhenius model as27.9kJ/mol.展开更多
基金supported by the Central Guidance on Local Science and Technology Development Fund of Hebei Province (No.236Z7601G)the Interdisciplinary Research Program of Natural Science of Hebei University, China (No.DXK202112)。
文摘We present an incorporation of the kinetic Monte Carlo(kMC)simulation with the adjacency matrix(AM)method to investigate structural parameters of randomly branched polymers.The AMs of branched polymers are obtained by the growth generation model,which is employed in the kMC simulation based on Gillespie’s algorithm.Of particular interest is the effect of the branched units on the relevant structural parameters.As an application in randomly hyperbranched polymers formed by AB_(2)type of monomers,average maximum span length,average length of sub-chains,number distribution of branched units,and meansquare radius of gyration are calculated.It is shown that the branched units can give rise to a significant effect on these physical quantities,whereby such a structure-property relationship can be employed to optimize reaction conditions and implement material designs.
基金financially supported by the National Natural Science Foundation of China(Nos.52034002 and U2202254)the Fundamental Research Funds for the Central Universities,China(No.FRF-TT-19-001)。
文摘The sulfation and decomposition process has proven effective in selectively extracting lithium from lepidolite.It is essential to clarify the thermochemical behavior and kinetic parameters of decomposition reactions.Accordingly,comprehensive kinetic study by employing thermalgravimetric analysis at various heating rates was presented in this paper.Two main weight loss regions were observed during heating.The initial region corresponded to the dehydration of crystal water,whereas the subsequent region with overlapping peaks involved complex decomposition reactions.The overlapping peaks were separated into two individual reaction peaks and the activation energy of each peak was calculated using isoconversional kinetics methods.The activation energy of peak 1 exhibited a continual increase as the reaction conversion progressed,while that of peak 2 steadily decreased.The optimal kinetic models,identified as belonging to the random nucleation and subsequent growth category,provided valuable insights into the mechanism of the decomposition reactions.Furthermore,the adjustment factor was introduced to reconstruct the kinetic mechanism models,and the reconstructed models described the kinetic mechanism model more accurately for the decomposition reactions.This study enhanced the understanding of the thermochemical behavior and kinetic parameters of the lepidolite sulfation product decomposition reactions,further providing theoretical basis for promoting the selective extraction of lithium.
文摘Hepatocellular carcinoma presents with three distinct immune phenotypes,including immune-desert,immune-excluded,and immune-inflamed,indicating various treatment responses and prognostic outcomes.The clinical application of multi-omics parameters is still restricted by the expensive and less accessible assays,although they accurately reflect immune status.A comprehensive evaluation framework based on“easy-to-obtain”multi-model clinical parameters is urgently required,incorporating clinical features to establish baseline patient profiles and disease staging;routine blood tests assessing systemic metabolic and functional status;immune cell subsets quantifying subcluster dynamics;imaging features delineating tumor morphology,spatial configuration,and perilesional anatomical relationships;immunohistochemical markers positioning qualitative and quantitative detection of tumor antigens from the cellular and molecular level.This integrated phenomic approach aims to improve prognostic stratification and clinical decision-making in hepatocellular carcinoma management conveniently and practically.
文摘This study explores the thin-layer convective solar drying of Marrubium vulgare L.leaves under conditions typical of sun-rich semi-arid climates.Drying experiments were conducted at three inlet-air temperatures(40℃,50℃,60℃)and two air velocities(1.5 and 2.5 m·s^(-1))using an indirect solar dryer with auxiliary temperature control.Moisture-ratio data were fitted with eight widely used thin-layer models and evaluated using correlation coefficient(r),root-mean-square error(RMSE),and Akaike information criterion(AIC).A complementary heattransfer analysis based on Reynolds and Prandtl numbers with appropriate Nusselt correlations was used to relate flow regime to drying performance,and an energy balance quantified the relative contributions of solar and auxiliary heat.The logarithmic model consistently achieved the lowest RMSE/AIC with r>0.99 across all conditions.Higher temperature and air velocity significantly reduced drying time during the decreasing-rate period,with no constantrate stage observed.On average,solar input supplied the large majority of the thermal demand,while the auxiliary heater compensated short irradiance drops to maintain setpoints.These findings provide a reproducible dataset and a modelling benchmark for M.vulgare leaves,and they support energy-aware design of hybrid solar dryers formedicinal plants in sun-rich regions.
基金supported by the grants PID2020-113371RA-C22 and TED2021-130845A-C32,funded by MCIN/AEI/10.13039/501100011033.M.Marín-García,R.González-OlmosC.Gómez-Canela are members of the GESPA group(Grup d’Enginyeria i Simulacióde Processos Ambientals)at IQS-URL,which has been acknowledged as a Consolidated Research Group by the Government of Catalonia(No.2021-SGR-00321)+1 种基金In addition,M.Marín-García has been awarded a public grant for the Investigo Programme,aimed at hiring young job seekers to undertake research and innovation projects under the Recovery,Transformation,and Resilience Plan(PRTR),European Union Next Generation,for the year 2022,through the Government of Catalonia and the Spanish Ministry for Work and Social Economy(No.100045ID16)Ana Belén Cuenca for her support and expertise,which helped to confirm the proposed reaction mechanism involved in the UV photolysis of cloperastine.
文摘The increasing production and release of synthetic organic chemicals,including pharmaceuticals,into our envi-ronment has allowed these substances to accumulate in our surface water systems.Current purification technolo-gies have been unable to eliminate these pollutants,resulting in their ongoing release into aquatic ecosystems.This study focuses on cloperastine(CPS),a cough suppressant and antihistamine medication.The environmental impact of CPS usage has become a concern,mainly due to its increased detection during the COVID-19 pandemic.CPS has been found in wastewater treatment facilities,effluents from senior living residences,river waters,and sewage sludge.However,the photosensitivity of CPS and its photodegradation profile remain largely unknown.This study investigates the photodegradation process of CPS under simulated tertiary treatment conditions using UV photolysis,a method commonly applied in some wastewater treatment plants.Several transformation prod-ucts were identified,evaluating their kinetic profiles using chemometric approaches(i.e.,curve fitting and the hard-soft multivariate curve resolution-alternating least squares(HS-MCR-ALS)algorithm)and calculating the reaction quantum yield.As a result,three different transformation products have been detected and correctly identified.In addition,a comprehensive description of the kinetic pathway involved in the photodegradation process of the CPS drug has been provided,including observed kinetic rate constants.
文摘The effects of acid surface dissolution on the flotation kinetics of ilmenite(IL)and its common accompanied gangue minerals including olivine-pyroxene(Ol-Px),tremolite-clinochlore(Tr-Cch)and quartz were investigated.The results show that through the surface dissolution the adsorption rate constant for ilmenite increases from 5.272 to 8.441 mol/(g·min)while it decreases for Ol-Px,Tr-Cch and quartz from 6.332,7.309 and 7.774 mol/(g·min)to 5.034,6.223 and 7.371 mol/(g·min),respectively.Also,the flotation experiments on a binary mixture of minerals indicate that after surface dissolution the values of modified rate constant for ilmenite flotation from Ol-Px,Tr-Cch and quartz are enhanced from 36.15,36.52 and 47.86 min-1 to 41.72,45.78 and 56.24 min-1,respectively.This results in the improvement of kinetic selectivity index(SI)in the separation of treated ilmenite from gangue minerals.As evidenced by ICP-MS analysis,the decrease of kinetic parameters for gangue minerals can be due to the removal of Fe^2+,Ca^2+and Mg^2+ions from their surfaces,which results in the lack of enough active sites to interact with collector species.As confirmed by contact angle measurements,this prevents the formation of a stable hydrophobic layer on the minerals surfaces for creating stable attachments between minerals and bubbles.Generally,the improvement of ilmenite flotation kinetics has a negative correlation with the iron content in its accompanied gangue minerals.
基金Supported by the Research Fund for the Doctoral Program of Higher Education(20050145029)the Science and Technology Talents Fund for Excellent Youth of Liaoning Province(2005221012)
文摘Determination of probable mechanism function and kinetic parameters is important to hydrometallurgical kinetics.In this work,the most probable mechanism function and kinetic parameters of gibbsite dissolution in NaOH solution are studied.The sample,the mixture of synthetic gibbsite and sodium hydroxide solution,was scanned in high-pressure differential scanning calorimetry(DSC) equipment with the heating rate of 10 K·min-1. Integral equation and differential equation of non-isothermal kinetics were solved to fit the data related to DSC curve.According to the calculation results,the most probable mechanism function for pure synthetic gibbsite dissolution in sodium hydroxide solution is presented based on the optimum procedure in the database of the mechanism function.The apparent activation energy obtained is(75±1) kJ·mol-1,the frequency factor is 10 8±1mol·s-1,and the reaction is a second order reaction.
基金The National Nature Science Foundation of China(21173163)
文摘The thermal behavior,non-isothermal thermal decomposition reaction kinetics and specific heat capacity of hexanitro-hexaazaisowurtzitane(HNIW)were studied by differential scanning calorimeter(DSC)and Micro-DSCIapparatus,The kinetic parameters of the thermal decomposition reaction(the apparent activation energy(E,)and pre-exponential factor(A))were calcu-lated by non-isothermal DSC curves.The results show that the differential mlechanism function and values of E,and A of the ther-mal decomposition reaction of HNIW are 3(1-a)[-ln(1-a)]"·,155.04 kJ·mol^(-1)and 10""s^(-1),respectively.The critical tem-perature of thermal explosion of the title compound is 226.60℃.The entropy of activation(AS·),enthalpy of activation(AH·)and free energy of activation(AG·)of this reaction are 11.60J·mol·K^(-1),152.04 kJ·mol^(-1)and 146.29 kJ·mol^(-1),respec-tively.The equation of specific heat capacity of HNIW with temperature is C,=0.2472+0.002705992Tin the temperature range of 283 K to 343K.The values of self-accelerating decomposition temperature,adiabatic time-to-maximum decomposition rate and adiabatic time-to-explosion are 486.5K,54.81s and 54.31s,respectively.Thermal sensitivity probability density distribution curve of HNIW is constructed.
基金Project supported by the Deanship of Scientific Research at Jazan University,the Kingdom of Saudi Arabia(W41-032).
文摘In this paper,Dy^(3+)incorporated BaSi_(2)O_(5)phosphors were synthesized by gel co mbustion method and characterized by X-ray diffraction(XRD).The effects of various heating rate s on thermoluminescence(TL)kinetics and glow peak temperatures of Dy^(3+)incorporated BaSi_(2)O_(5)phosphors exposed toβirradiation at room temperature were investigated.The glow curves of the phosphor exposed toβ-irradiation(0.1-100 Gy)consist of four main peaks located at 87,130,271,and 327℃and exhibit a good linearity between 0.1 and100 Gy.Three experimental techniques including variable heating rate(VHR),repeated initial rise(RIR),peak shape(PS)and computerized glow curve deconvolution(CGCD)were employed to determine TL kinetic parameters.Our findings indicate that the TL glow peaks of the phosphor obey first-order kinetics.Analysis of the main dosimetric peaks through the techniques mentio ned above indicates that activation energies(E)and pre-exponential factor(s)are in the range of 0.80-1.50 eV and 1.15×10^(8)-3.28×10^(13)s^(-1).Additionally,it is found that the temperature of the glow peaks shifts toward the higher temperatures and the TL intensity smoothly decreases as the heating rate increases.The effect on the TL intensities and glow peak temperatu res of the heating rate is discussed in terms of thermal quenching.
基金Project supported by the National Key Basic Research Support Foundation of China (No. G1999011809) the Natural Science Foundation of Zhejiang Province, China (No. RC99035).
文摘Corn field experiments with two treatments, NP and NPK, where N in the form of urea, P in the form of calcium phosphate, and K in the form of KCl were applied at rates of 187.5, 33.3, and 125 kg ha^-1, respectively, on soils derived from Quaternary red clay were conducted in the hilly red soil region of Zhejiang Province, China. Plant grains and stalks were collected for determination of K content. Seven equations were used to describe the kinetics of K release from surface soil samples taken before the corn experiments under electric field strengths of 44.4 and 88.8 V cm^-1 by means of electro-ultrafiltration （EUF） and to determine if their parameters had a practical application. The second-order and Elovich equations excellently described K release; the first-order, power function, and parabolic diffusion equations also described K release well; but the zero-order and exponential equations were not so good at reflecting K release. Five reference standards from the field experiments, including relative grain yield （yield of the NP treatment/yield of the NPK treatment）, relative dry matter yield （dry matter of the NP treatment/dry matter of the NPK treatment）, quantity of K uptake in the NP treatment （no K application）, soil exchangeable K, and soil HNO3-soluble K, were used to test the effectiveness of equation parameters obtained from the slope or intercept of these equations. Correlations of the ymax （the maximum desorbable quantity of K） in the second-order equation and the constant b in the first-order and Elovich equations to all five reference standards were highly significant （P ≤ 0.01）. The constant a in the power function equation was highly significant （P 〈 0.01） for four of the five reference standards with the fifth being significant （P ≤ 0.05）. The constant b in the parabolic equation was also significantly correlated （P ≤ 0.05） to the relative grain yield and soil HNO3-soluble K. These suggested that all of these parameters could be used to estimate the soil K supplying capacity and the crop response to K fertilizer.
文摘Combustion kinetic parameters(i.e.,activation energy and frequency factor) of coal have been proven to relate closely to coal properties;however,the quantitative relationship between them still requires further study.This paper adopts a support vector regression machine(SVR) to generate the models of the non-linear relationship between combustion kinetic parameters and coal quality.Kinetic analyses on the thermo-gravimetry(TG) data of 80 coal samples were performed to prepare training data and testing data for the SVR.The models developed were used in the estimation of the combustion kinetic parameters of ten testing samples.The predicted results showed that the root mean square errors(RMSEs) were 2.571 for the activation energy and 0.565 for the frequency factor in logarithmic form,respectively.TG curves defined by predicted kinetic parameters were fitted to the experimental data with a high degree of precision.
文摘For processing parts made from medium carbon steel, toughness and flexibility are of importance. There- fore, to achieve these properties, the cementite in the steels is spheroidized through heat treatment. Different parameters such as the time and temperature of spheroidizing and the initial microstructure of the steel affect the amount of spheroidized cementite. In the present work, the percent of contribution of two parameters, i.e. initial microstructure and spheroidizing time, to the percent of spheroidization in CK60 steel was investigated using Taguchi robust design. The initial microstructures consisted of martensite, coarse pearlite, fine pearlite and bainite and the chosen spheroidization times were 4, 8, 12, and 16h. Spheroidizing was done at the constant temperature 700℃. After spheroidizing was completed, the samples were prepared in order to observe their microstructure under an optical microscope and to determine the spheroidized percent using MIPTM （metallographic image processing） software. It was found that the spheroidizing time had the most influence （58.5 ~//0） on spheroidized percent and the initial microstructure only had a 31.1% contribution. Finally, the instantaneous growth rate of the carbide was also deduced.
基金Item Sponsored by National Natural Science Foundation of China(U1360202,51472030,51502014)National Key Project of the Scientific and Technical Support Program of China(2011BAE13B07,2012BAC02B01,2011BAC10B02)+2 种基金National Hi-tech Research and Development Program of China(2012AA063202)Fundamental Research Funds for the Central Universities of China(FRF-TP-15-050A2)China Postdoctoral Science Foundation Funded Project(2014M560885)
文摘One-step crystallization is one of the most energy conserving methods for glass-ceramics preparation.However,only a few kinetics studies focused on the glass-ceramics prepared by the one-step crystallization.The onestep crystallization kinetic parameters were studied using differential scanning calorimetry.The activation energy（Ea）and the Avrami parameter（n）were calculated as 152.79kJ·mol-1 and 4.39,respectively.These parameters indicate that continuous nucleation and three-dimensional crystal growth are the dominating mechanisms in the one-step crystallization process of the parent glass.The properties of the obtained glass-ceramics can be compared to the glass-ceramics prepared by the two-stage heat treatment and sintering method.This crystallization kinetics research can be used to evaluate the one-step crystallization potential of a parent glass.
文摘The exact calculation of point kinetic parameters is very important in nuclear reactor safety assessment, and most sophisticated safety codes such as RELAP5, PARCS,DYN3D, and PARET are using these parameters in their dynamic models. These parameters include effective delayed neutron fractions as well as mean generation time.These parameters are adjoint-weighted, and adjoint flux is employed as a weighting function in their evaluation.Adjoint flux calculation is an easy task for most of deterministic codes, but its evaluation is cumbersome for Monte Carlo codes. However, in recent years, some sophisticated techniques have been proposed for Monte Carlo-based point kinetic parameters calculation without any need of adjoint flux. The most straightforward scheme is known as the ‘‘prompt method'' and has been used widely in literature. The main objective of this article is dedicated to point kinetic parameters calculation in Tehran research reactor(TRR) using deterministic as well as probabilistic techniques. WIMS-D5B and CITATION codes have been used in deterministic calculation of forward and adjoint fluxes in the TRR core. On the other hand, the MCNP Monte Carlo code has been employed in the ‘‘prompt method''scheme for effective delayed neutron fraction evaluation.Deterministic results have been cross-checked with probabilistic ones and validated with SAR and experimental data. In comparison with experimental results, the relativedifferences of deterministic as well as probabilistic methods are 7.6 and 3.2%, respectively. These quantities are10.7 and 6.4%, respectively, in comparison with SAR report.
基金supported by the National Basic Research Program of China(Grant No.2012CB955304)the National Natural Science Foundation of China(Grant Nos.41075008 and 40830957)+2 种基金the Special Financial Grant of China Postdoctoral Science Foundation(Grant No.2013T60901)the Arid Meteorology Foundation of the Institute of Arid Meteorology of the China Meteorological Administration(Grant No.IAM201408)the Ten Talents Program of Gansu Meteorology Bureau
文摘A deep understanding of turbulence structure is important for investigating the characteristics of the atmospheric boundary layer,especially over heterogeneous terrain.In the present study,turbulence intensity and turbulent kinetic energy（TKE）parameters are analyzed for different conditions with respect to stability,wind direction and wind speed over a valley region of the Loess Plateau of China during December 2003 and January 2004.The purpose of the study is to examine whether the observed turbulence intensity and TKE parameters satisfy Monin–Obukhov similarity theory（MOST）,and analyze the wind shear effect on,and thermal buoyancy function of,the TKE,despite the terrain heterogeneity.The results demonstrate that the normalized intensity of turbulence follows MOST for all stability in the horizontal and vertical directions,as well as the normalized TKE in the horizontal direction.The shear effect of the wind speed in the Loess Plateau region is strong in winter and could enhance turbulence for all stability conditions.During daytime,the buoyancy and shear effect together constitute the generation of TKE under unstable conditions.At night,the contribution of buoyancy to TKE is relatively small,and mechanical shearing is the main production form of turbulence.
文摘Kinetics of oxidation of MgO-C refractories was investigated by shrinking core modeling of the gas-solid reactions taking place during heating the porous materials to the high temperatures. Samples containing 4.5-17 wt pct graphite were isothermally oxidized at 1000-1350℃. Weight loss data was compared with predictions of the model. A mixed 2-stage mechanism comprised of pore diffusion plus boundary layer gas transfer was shown to generally control the oxidation rate. Pore diffusion was however more effective, especially at graphite contents lower than 10 wt pct under forced convection blowing of the air. Model calculations showed that effective gas diffusion coefficients were in the range of 0.08 to 0.55 cm^2/s. These values can be utilized to determine the corresponding tortuosity factors of 6.85 to 2.22. Activation energies related to the pore diffusion mechanism appeared to be around （46.44±2） kJ/mol. The estimated intermolecular diffusion coefficients were shown to be independent of the graphite content, when the percentage of the graphite exceeded a marginal value of 10.
基金Supported by the National Natural Science Foundation of China （20506003, 20776042） and the National High-Tech Research and Development Program of China （2007AA04Z 164）.
文摘A new version of differential evolution （DE） algorithm, in which immune concepts and methods are applied to determine the parameter setting, named immune self-adaptive differential evolution （ISDE）, is proposed to improve the performance of the DE algorithm. During the actual operation, ISDE seeks the optimal parameters arising from the evolutionary process, which enable ISDE to alter the algorithm for different optimization problems and improve the performance of ISDE by the control parameters＇ self-adaptation. The .performance of the proposed method is studied with the use of nine benchmark problems and compared with original DE algorithm ~nd-other well-known self-adaptive DE algorithms. The experiments conducted show that the ISDE clearly outperforms the other DE algorithms in all benchmark functions. Furthermore, ISDE is applied to develop the kinetic model for homogeneous mercury. （Hg） oxidation in flue gas, and satisfactory results are obtained.
基金Supported by the National Natural Science Foundation of China （60804027, 61064003） and Fuzhou University Research Foundation （FZU-02335, 600338 and 600567）.
文摘Determination of the optimal model parameters for biochemical systems is a time consuming iterative process. In this study, a novel hybrid differential evolution （DE） algorithm based on the differential evolution technique and a local search strategy is developed for solving kinetic parameter estimation problems. By combining the merits of DE with Gauss-Newton method, the proposed hybrid approach employs a DE algorithm for identifying promising regions of the solution space followed by use of Gauss-Newton method to determine the optimum in the identified regions. Some well-known benchmark estimation problems are utilized to test the efficiency and the robustness of the proposed algorithm compared to other methods in literature. The comparison indicates that the present hybrid algorithm outperforms other estimation techniques in terms of the global searching ability and the con- vergence speed. Additionally, the estimation of kinetic model parameters for a feed batch fermentor is carried out to test the applicability of the proposed algorithm. The result suggests that the method can be used to estimate suitable values of model oarameters for a comolex mathematical model.
基金supported by the National Natural Science Foundation of China(No.40572085)Open Fund of State Key Laboratory of Organic Geochemistry,Guangzhou Institute of Geochemistry,Chinese Academy of Sciences(No.OGL-200403)+2 种基金State Key Technologies R&D Program during the 10th Five-Year Plan Period(No.2001BA605A02-03-01 and 2004BA616A02-01-01)New-century Excellent Talent Program of Ministry of Education(No.NCET-06-0204)China Postdoctoral Science Foundation(No.2002031282).
文摘In a thermal simulation experiment of gold tubes of closed-system, calculating with the KINETICS and GOR-ISOTOPE KINETICS software, kinetic parameters of gas generation and methane carbon isotopic fractionation from Triassic-Jurassic hydrocarbon source rocks in the Kuqa depression of Tarim Basin are obtained. The activation energies of methane generated from Jurassic coal, Jurassic mudstone and Triassic mudstone in the Kuqa Depression are 197-268 kJ/mol, 180-260 kJ/mol and 214-289 kJ/mol, respectively, and their frequency factors are 5.265×10^13 s^-1, 9.761×10^11 s^-1 and 2.270×10^14 s^-1. This reflects their differences of hydrocarbon generation behaviors. The kinetic parameters of methane carbon isotopic fractionation are also different in Jurassic coal, Jurassic mudstone and Triassic mudstone, whose average activation energies are 228 kJ/mol, 205 kJ/mol and 231 kJ/mol, respectively. Combined with the geological background, the origin of natural gas in the Yinan-2 gas pool is discussed, and an accumulation model of natural gas is thus established. The Yinan- 2 gas is primarily derived from Jurassic coal-bearing source rocks in the Yangxia Sag. Main gas accumulation time is 5-0 Ma and the corresponding Ro is in the range from 1.25 %-1.95 %. The loss rate of natural gas is 25 %-30 %.
文摘The feasibility and kinetics of lead recovery from the slag of traditional lead melting furnace using chloride leaching were investigated.The effects of operating parameters such as leaching time,NaCl concentration,FeCl3concentration,liquid/solid ratio,stirring rate,temperature,and particle size on recovery of lead were studied and the optimization was done through the response surface methodology(RSM)based on central composite design(CCD)model.The optimum conditions were achieved as follows:leaching time60min,80°C,stirring rate800r/min,NaCl concentration200g/L,FeCl3concentration80g/L,liquid/solid ratio16,and particle size less than106μm.More than96%of lead was effectively recovered in optimum condition.Based on analysis of variance,the reaction temperature,liquid/solid ratio,and NaCl concentration were determined as the most effective parameters on leaching process,respectively.Kinetics study revealed that chloride leaching of galena is a first-order reaction and the diffusion through solid reaction product and chemical reaction control the mechanism.The activation energy of chloride leaching of galena was determined using Arrhenius model as27.9kJ/mol.
