Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting t...Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting two greenhouse gases(methane and carbon dioxide)into syngas and its promising industrial applications.Nickel(Ni)-based catalysts,with high catalytic activity,low cost,and abundant resources,are considered ideal candidates for industrial applications.In this article,three reaction kinetic models were briefly introduced,namely the Power-Law(PL)model,the Eley-Rideal(ER)model,and the Langmuir-Hinshelwood-Hougen-Watson(LHHW)model.Based on the LHHW model,the reaction kinetics and mechanisms of different catalytic systems were systematically discussed,including the properties of supports,the doping of noble metals and transition metals,the role of promoters,and the influence of the geometric and electronic structures of Ni on the reaction mechanism.Furthermore,the kinetics of carbon deposition and elimination on various catalysts were analyzed.Based on the reaction rate expressions for carbon elimination,the reasons for the high activity of transition metal iron(Fe)-doped catalysts and core-shell structured catalysts in carbon elimination were explained.Based on the detailed collation and comparative analysis of the reaction mechanisms and kinetic characteristics across diverse Ni-based catalytic systems,a theoretical guidance for the designing of high-performance catalysts was provided in this work.展开更多
The curing behavior of composites significantly influences their performance,making it crucial to understand the curing process.This study experimentally measured specific heat capacity,thermal conductivity,glass tran...The curing behavior of composites significantly influences their performance,making it crucial to understand the curing process.This study experimentally measured specific heat capacity,thermal conductivity,glass transition temperature,coefficient of thermal expansion,and cure shrinkage of materials.A simulation model of its curing deformation was established and validated against strain data obtained from fiber Bragg grating experiments.The effects of thickness,heating rate,and cooling rate on the curing temperature field and residual stress field during the molding of thick-section composite plates were analyzed.展开更多
The leaching process and kinetic behavior of lepidolite in hydrochloric acid were explored systematically.The influence of leaching conditions on the leaching efficiency of valuable metals in lepidolite was investigat...The leaching process and kinetic behavior of lepidolite in hydrochloric acid were explored systematically.The influence of leaching conditions on the leaching efficiency of valuable metals in lepidolite was investigated.Under optimized conditions,the leaching efficiencies of Li,K,Rb,Cs and Al are 92.02%,93.31%,88.59%,86.75%and 81.07%,respectively.Kinetics research results show that the leaching process conforms to the shrinking core model that is under the mixed control of chemical reaction and diffusion through the solid product layer.In addition,the contribution of solid product layer diffusion to the leaching gradually expands as the temperature rises,but it is still significantly less than the contribution of chemical reaction.Cost saving in the neutralizing agent and leaching processes makes hydrochloric acid an economical leaching agent for lepidolite.Finally,the Li2CO3 product with a purity of 99.89%was synthesized from the hydrochloric acid leachate.展开更多
The volatilization characteristics and kinetic mechanisms of arsenic were investigated in the temperature range of 623−773 K and pressure ranges of 10−10000 Pa.The experimental results reveal that the evaporation rate...The volatilization characteristics and kinetic mechanisms of arsenic were investigated in the temperature range of 623−773 K and pressure ranges of 10−10000 Pa.The experimental results reveal that the evaporation rate increases with increasing temperature and decreasing pressure.Surface reaction control dominates at low pressures(<100 Pa),whereas diffusion control dominates at high pressures(>5000 Pa).The evaporation behavior is successfully described by an Arrhenius-type model for temperature dependence and Logistic model for pressure dependence.Key kinetic parameters,including the critical pressure,maximum evaporation rate and evaporation coefficient,were calculated.The evaporation coefficient varies between 0.010 and 0.223,and the critical pressures vary between 281 and 478 Pa with temperature.展开更多
The hydrogen reduction kinetics of tungsten trioxide(WO_(3))was investigated via non-isothermal thermogravimetric analysis.Under the local gas-solid reduction conditions,the particle morphology of tungsten powders was...The hydrogen reduction kinetics of tungsten trioxide(WO_(3))was investigated via non-isothermal thermogravimetric analysis.Under the local gas-solid reduction conditions,the particle morphology of tungsten powders was found to be consistent with that of raw material WO_(3).The removal of oxygen from tungsten oxide during hydrogen reduction led to the formation of porous structures between the reduced particles,which were obviously different from the polyhedral single-crystal configuration of tungsten powders obtained via chemical vapor deposition.Moreover,the two-stage hydrogen reduction mechanisms of WO_(3) under the local gas-solid reduction conditions can be described using the composite autocatalytic function.The activation energies of the first and second stages of the hydrogen reduction of WO_(3) were determined to be 121 and 135 kJ/mol,respectively.展开更多
The crystallization and aggregation characteristics of the active layer components in organic solar cells(OSCs)are one of the core factors determining photovoltaic performance,influencing the entire process from light...The crystallization and aggregation characteristics of the active layer components in organic solar cells(OSCs)are one of the core factors determining photovoltaic performance,influencing the entire process from light absorption to charge separation,transport,and ultimately charge collection.Dynamic changes in crystallization and aggregation states can also disrupt the microstructure of the active layer,thus shortening the lifetime of the cell.In this study,a morphology modulation strategy is proposed to regulate the crystallization kinetics of non-fullerene acceptors by employing the polymer molecule PYIT as a nucleating agent.An appropriate amount of PYIT was first completely dissolved with the non-fullerene acceptor Y6 and left to stand for 24 h,followed by the fabrication of layer-by-layer processed OSCs.Experiments demonstrated that high crystallinity of PYIT allows it to act as a crystallization nucleus,promoting the crystallization,orientation consistency,and ordered stacking of the acceptor.These nanoscale structural optimizations facilitate efficient charge transport,enhance exciton dissociation efficiency,and suppress unfavorable energetic disorder.Consequently,not only was the power conversion efficiency(PCE)of D18-Cl/Y6-based layer-by-layer processed OSC increased from 18.08%to 19.13%,but the atmospheric stability and long-term lifetime of the OSCs were also significantly improved.Notably,this strategy is also applicable to indoor OSCs,and the PYIT-optimized device can achieve a PCE of 27.0%under 1000 lux light-emitting diode(LED,3200K)irradiation,which is superior to that of the control device(24.2%).This work develops a crystal engineering strategy that is able to simultaneously optimize the microscopic morphology and charge dynamics properties in OSCs,thereby achieving simultaneous improvement in efficiency and stability.展开更多
Curing temperature significantly affects the pozzolanic reaction kinetics of phosphorous slag(PS),thereby governing the early-age(7 d)hydration behavior of PS composite binders at 20,30,and 60℃.The Krstulovic-Dabic k...Curing temperature significantly affects the pozzolanic reaction kinetics of phosphorous slag(PS),thereby governing the early-age(7 d)hydration behavior of PS composite binders at 20,30,and 60℃.The Krstulovic-Dabic kinetic model was applied to identify three characteristic processes:nucleation and growth(NG),phase boundary interaction(I),and diffusion(D).Control mixtures containing inert quartz powder with comparable particle size distributions were prepared for comparison.Pore characteristics of hardened PS pastes at different temperatures were analyzed via mercury intrusion porosimetry,while hydration products were characterized using X-ray diffraction(XRD)and thermogravimetric analysis(TG-DTG).The experimental results indicate that the retarding effect of PS on early cement hydration outweighs its accelerating effect,attributed to the combined influence of nucleation and dilution,with retardation decreasing as temperature increases.PS exhibits early reactivity and continuously consumes calcium hydroxide through the pozzolanic reaction,as evidenced by stable phase assemblages accompanied by reduced CH content in XRD and TG-DTG analyses.At 20℃,increasing PS content maintains the NG→I→D mechanism but slows reaction rates across all stages.Elevated temperatures significantly accelerate the NG process,shifting the dominant mechanism from NG toward D.Simultaneously,enhanced PS reactivity contributes to a refined pore structure and improved compressive strength.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
Inorganic perovskite solar cells(IPSCs),due to their suitable bandgap and superior thermal stability,are ideal candidates for tandem solar cells combined with silicon.However,the development of inorganic perovskite so...Inorganic perovskite solar cells(IPSCs),due to their suitable bandgap and superior thermal stability,are ideal candidates for tandem solar cells combined with silicon.However,the development of inorganic perovskite solar cells has been hindered by suboptimal crystallization dynamics that generate detrimental defects in the perovskite lattice.Here,we propose 4-Methoxyphenylphosphonic Acid(4MPA)as a multifunctional additive to address this challenge.P=O in 4MPA establish strong coordination with undercoordinated Pb^(2+),while-OH engage in O...H-O hydrogen bonding interactions with DMSO,effectively weakening the solvent-[PbX_(6)]^(4-)octahedron interaction.This dual functionality facilitates complete and rapid DMA^(+)-to-Cs^(+)cation exchange while regulating crystallization kinetics,thereby optimizing crystal growth.Furthermore,π-π interactions between benzene rings significantly enhance the moisture resistance of the perovskite layer.The optimized device demonstrates a power conversion efficiency(PCE)of 21.35%,with unencapsulated devices retaining 93,63%of their initial efficiency after 200-hour continuous operation under ambient conditions(35%relative humidity).展开更多
This study investigates four Late Permian Gondwana coals from the Raniganj sub-basin,Damodar Valley and three Early Permian Gondwana coals from the Talcher sub-basin,Mahanadi Valley.The study aims to characterize the ...This study investigates four Late Permian Gondwana coals from the Raniganj sub-basin,Damodar Valley and three Early Permian Gondwana coals from the Talcher sub-basin,Mahanadi Valley.The study aims to characterize the kerogen type,hydrocarbon generation potential,thermal maturity,and organic matter composition,as well as to explore the impact of organic matter characteristics on kerogen kinetic parameters,utilizing multi proxy approach.The study further investigates the influence of the mineral matrix on kerogen decomposition kinetics.Based on the Rock-Eval parameters,Fourier transform infrared spectroscopy(FTIR)parameters,and vitrinite reflectance(R_(o)),the kerogen is primarily classified as immature/early mature TypeⅢkerogen derived from terrestrial land plants,with minor contribution from TypeⅡkerogen having mainly gas generating potential.The source of the organic matter,as determined by stable carbon isotopic composition(δ^(13)C_(org))values and C/N ratios indicates a primary input from C_(3) terrestrial plants.The presence of enriched collotelinites and liptinites,such as sporinite and resinite,provides evidence for the input of terrestrial higher plants,including both herbaceous and arborescent species.Various indices derived from maceral abundances,including the gelification index(GI),tissue preservation index(TPI),and vegetation index(VI),collectively indicate diverse depositional conditions which range from wet forest swamps to shallow water-covered wet forest swamps and even dry forest swamps.The variation in vitrinite macerals influenced the kerogen type and consequently impacted the kinetic parameters,viz.the distribution of activation energies(E_(a)),kerogen transformation ratio(KTR),and hydrocarbon generation rate(HGR).Among the Talcher coals,shaly coals exhibit different kerogen type and kerogen transformation.This dissimilarity can be attributed to variable maceral compositions.Unlike the Talcher samples,all Raniganj samples show consistent kinetic behaviour despite their sample type(coal/shaly coal)or kerogen type(TypeⅢ/mixed TypeⅡ/Ⅲ)owing to comparable liptinite/vitrinite maceral composition.This study reveals that whilst the presence of mineral matrix shifts the apparent E_(a) of kerogen through interactions like adsorption and catalysis,it does not significantly affect the kerogen type,HGR,or KTR of the studied coals.展开更多
In this study,copper extraction from low-grade oxide-sulfide ores was investigated using a leaching method combined with response surface methodology(RSM)to optimize operational conditions and assess leaching kinetics...In this study,copper extraction from low-grade oxide-sulfide ores was investigated using a leaching method combined with response surface methodology(RSM)to optimize operational conditions and assess leaching kinetics.Given copper's extensive industrial applications,sustainable recovery from low-grade ores is critical.Five key parameters-acid concentration,leaching time,particle size,temperature,and solids percentage-were identified as major influences on copper recovery.The results revealed that leaching time and solids percentage,along with interactions between temperature-time and temperature-solids percentage,had the most significant effects.Optimal conditions for 80% copper recovery while minimizing iron recovery below 3% included an acid concentration of 1.21 mol L^(-1),a leaching time of 108 min,a particle size of 438μm,a temperature of 45℃,and a solids percentage of 18.2%.Leaching kinetics were analyzed using shrinking core models,with the Dickinson model best describing the process,showing an activation energy of 32.63 kJ mol^(-1),indicative of mixed diffusion and chemical reaction control.The final kinetic model effectively predicted the influence of key parameters.These findings highlight the importance of optimizing process variables and selecting suitable kinetic models to enhance extraction efficiency,reduce costs,and improve sustainability in copper recovery.展开更多
This study proposes to use the unconfined compressive strength(UCS)and the bender element(BE)tests for determining the strength and the initial small-strain shear modulus of Bangkok soft marine clay improved by cement...This study proposes to use the unconfined compressive strength(UCS)and the bender element(BE)tests for determining the strength and the initial small-strain shear modulus of Bangkok soft marine clay improved by cement and polyester fibers.This study varies the content of admixed cement(1%–20%)and polyester fibers(0–20%),including the curing time(3–28 d)for preparing 360 samples.Moreover,this study uses the Michaelis-Menten kinetics concept to model cement hydration saturation.From the study,it is concluded as follows.The modelled results reveals that at least 10%cement and 1%polyester fiber are recommended to attain the 28-d UCS standards(294 kPa)for highway subgrade materials in Thailand.This also fulfils sustainable construction due to reducing normal-use cement from 20%to 10%.Unfortunately,the addition of polyester fibers into the Bangkok clay with at least 5%cement reduces shear modulus by 1.12–1.32 times.The Abram's relationship between shear modulus and the mixing-water-to-cement ratio is found time-dependent.From the composite theory,the BE detects the polyester fiber zone as a defect in the Bangkok clay(matrix)with 5%–20%cement.So,the 28-d shear modulus in the polyester fiber zone is negative(up to0.034 MPa for 20%fiber),similar to softening phenomenon in concrete cracking(negative stiffness).For the 28-d shear modulus of fiber zone,the optimum cement content is around 2%for the positive influences of polyester fibers.Experimentally,the timedependent normalized UCS for 10%and 20%cement is compatible with other studies,and its development rate increases with the cement content as 0.3017,0.3172 and 0.3204 for 5%,10%and 20%cement,respectively.The 28-d relationship between shear modulus and UCS shows that low-cement soft clay requires high polyester fiber content(5%–20%)to activate UCS improvement.However,the soft clay with enough cement(20%)causes the uniformly distributed UCS improvement.展开更多
Layered double hydroxides(LDHs)hold great promise as cathode materials for aqueous zinc-ion batteries(AZIBs).Nevertheless,they also face challenges of sluggish kinetics and rapid capacity loss.Herein,a conformational ...Layered double hydroxides(LDHs)hold great promise as cathode materials for aqueous zinc-ion batteries(AZIBs).Nevertheless,they also face challenges of sluggish kinetics and rapid capacity loss.Herein,a conformational entropy regulation strategy has been applied to surmount the shortcomings.A medium-entropy iron-based metal organic framework(MIL-88)derived NiCoFeInZnV-based layered double hydroxide with carbon loaded(ME-NiCoFeInZnV-LDH/C)has been first proposed and prepared with a designed method.The increased entropy optimizes electron conductivity and alleviates structure alteration and diffusion barrier during interactions with charge carriers,due to electron-induced effect and“cocktail”effect.Moreover,the nanosheet assembled hollow prismatic structures could homogenize flux distribution and electric field distribution.Therefore,the electrochemical kinetics,crystal structure stability,and activity could be dramatically improved.Leveraging the advantages of structure and composition regulation,Zn||ME-NiCoFeInZnV-LDH/C zinc battery delivers high specific capacities,rate performance,and cycling stability.This work proposes a novel and feasible medium-entropy strategy to prepare a high-performance cathode for advanced AZIBs,which is of prominent significance for the development of charge storage devices.展开更多
Single-pass and double-pass high-temperature deformation experiments were conducted on 40Cr10Si2Mo steel using a Gleeble-3500 thermal simulator.The static recrystallization(SRX)behavior and recrystallization mechanism...Single-pass and double-pass high-temperature deformation experiments were conducted on 40Cr10Si2Mo steel using a Gleeble-3500 thermal simulator.The static recrystallization(SRX)behavior and recrystallization mechanisms of 40Cr10Si2Mo steel were investigated under deformation temperatures of 900-1100℃,deformation strains of 10%,20%,and 30%,and inter-pass times of 1-120 s.A static recrystallization fraction model was developed.The results showed that the SRX volume fraction increased with higher deformation temperature,larger deformation amount,and longer inter-pass time,with the deformation temperature having the most significant effect on SRX.During the deformation process,different process parameters led to different internal deformation mechanisms of the material.Static recovery and continuous static recrystallization(CSRX)dominated deformation at lower temperatures through progressive lattice rotation.In comparison,at higher temperatures,the deformation mechanism was dominated by CSRX and discontinuous static recrystallization(DSRX).The nucleation mechanisms of the SRX process were grain boundary bulging nucleation and subgrain merging nucleation,with grain boundary bulging present under all conditions.Subgrain merging nucleation could provide an additional nucleation mode at lower deformation temperatures or lower deformation amounts.Based on the traditional Avarmi equation,a modified model coefficient was used to establish the SRX kinetic model for 40Cr10Si2Mo steel.The linear correlation coefficient R^(2) between the predicted and experimental static recrystallization volume fraction was 0.96702,indicating high prediction accuracy.展开更多
Cadmium(Cd)contamination in soils poses substantial environmental and health risks globally,with manganese(Mn)playing a crucial role in regulating Cd mobility through soil adsorption processes and shared crop uptake p...Cadmium(Cd)contamination in soils poses substantial environmental and health risks globally,with manganese(Mn)playing a crucial role in regulating Cd mobility through soil adsorption processes and shared crop uptake pathways.While the importance of understanding Cd-Mn dynamics in soils is widely recognized,quantitative assessments of their correlated desorption processes remain limited.This study employed diffusive gradients in thin-films(DGT)technique combined with DGT-induced fluxes in soils(DIFS)modeling to investigate Cd and Mn availability and desorption dynamics in karst soils from Guangxi,southwestern China.The soil solution concentrations ranged from 0.23–1.82μg/L for Cd and 1.29–8.41 mg/L for Mn.DGT measurements demonstrated nonlinear accumulation patterns for both metals over 48 h duration.DIFS modeling yielded distribution coefficients(Kdl)ranging from 2.50 to 807 mL/g and response time(Tc)between 1.27 and 425 s for both metals.Solid phase resupply was limited by desorption rates of 5.38–229×10^(−5)/s,providing unprecedented insight into the kinetics of metal release in these soils.Analysis of metal desorption rate ratios(k−1-Mn/k−1-Cd)indicated that soil organic matter content,clay content,pH,and metal contents collectively control Cd and Mn desorption kinetics,leading to distinct desorption patterns across soils with varying physicochemical properties.These findings demonstrate rapid equilibrium reestablishment and desorption-limited resupply characteristics of Cd and Mn in karst soils,advancing understanding of correlative metal behaviors in these unique geological settings.展开更多
A high performance thermosetting epoxy resin crosslinkable at room temperature was obtained via directly moulding diglycidyl ether of bisphenol A（DGEBA） and flexibleα,ω-bisamino（n-alkylene）phenyl terminated poly...A high performance thermosetting epoxy resin crosslinkable at room temperature was obtained via directly moulding diglycidyl ether of bisphenol A（DGEBA） and flexibleα,ω-bisamino（n-alkylene）phenyl terminated poly（ethylene glycol）.The influences of the n-alkylene inserted in aminophenyl of flexible amino-terminated polythers（ATPE） on the mechanical properties,fractographs and curing kinetics of the ATPE-DGEBA cured products were studied.The results show that the insertion of n-alkylene group into the aminophenyl group of the ATPE,on one hand,can significantly increase the strain relaxation rate and decrease glass transition temperature of the ATPE-DGEBA cured products,resulting in slight decrease of the Young’s modulus and tensile strength,and significant increase of the toughness and elongation of the ATPE-DGEBA cured products.On the other hand,it can remarkably enhance the reactivity of amine with epoxy,much accelerating the curing rate of the ATPE-DGEBA systems.The activation energy of DGEBA cured by BAPTPE,BAMPTPE and BAEPTPE was 53.1,28.5 and 25.4 kJ·mol;,respectively.The as-obtained ATPE-DGEBA cured products are homogeneous, transparent,and show excellent mechanical properties including tensile strength and toughness.Thus they are promising to have important applications in structure adhesives,casting bulk materials,functional coatings,cryogenic engineering, damping and sound absorbing materials.展开更多
The cure kinetics of diglycidyl ether of bisphenol A （DGEBA） with hyperbranched poly （3-hydroxyphenyl） phosphate（HHPP） as the curing agent was investigated by means of non-isothermal differential scanning calori...The cure kinetics of diglycidyl ether of bisphenol A （DGEBA） with hyperbranched poly （3-hydroxyphenyl） phosphate（HHPP） as the curing agent was investigated by means of non-isothermal differential scanning calorimetry （DSC） at various heating rates. The results were compared with the corresponding results by using 1,3-dihydroxybenzene（DHB） as a model compound. The results show that HHPP can enhance the cure reaction of DGEBA, resulting in the decrease of the peak temperature of the curing curve as well as the decrease of the activation energy because of the flexible --P--O-- groups in the backbone of HHPP. However, both the activation energy of the cured polymer and the peak temperature of the curing curve are increased with DHB as a curing agent. The cure kinetics of the DGEBA/HHPP system was calculated by using the isoconversional method given by Malek. It was found that the two-parameter autocatalytic model（Sestak-Berggren equation） is the most adequate one to describe the cure kinetics of the studied System at various heating rates. The obtained non-isothermal DSC curves from the experimental data show the results being accordant with those theoretically calculated.展开更多
The curing process of two biobased adhesives:pine tanninhexamine(TH)and organosolv lignin non-isocyanate polyurethane(NIPU),suitable for interior nonstructural use,were compared with commercial urea-formaldehyde(UF)ad...The curing process of two biobased adhesives:pine tanninhexamine(TH)and organosolv lignin non-isocyanate polyurethane(NIPU),suitable for interior nonstructural use,were compared with commercial urea-formaldehyde(UF)adhesive.Changes in chemical structure before and after the curing process were observed with Fouriertransform infrared spectroscopy(FTIR).The process of adhesive curing was monitored with differential scanning calorimetry(DSC)and the automated bonding evaluation system(ABES).Both DSC and ABES measurements confirmed UF as the fastest and NIPU as the slowest curing adhesive observed.Taking into account the ABES results,the optimal pressing parameters for the TH adhesive would be 4 min at 175℃,for the NIPU adhesive 7 min at 200℃and for the UF 1.5 min at 100℃.Strong linear correlation was observed between mechanical and chemical curing for the UF and NIPU adhesives,whereas lower correlation was observed for the TH adhesive.At all observed adhesives,the DSC measurements were underestimating the curing process determined by ABES in the first part and overestimating it at the end.The underestimation was the most evident with the TH adhesive and the less with the UF adhesive.When comparing the uncured and cured FTIR spectra of all three types of adhesives,a drastic decrease in the characteristic band of-OH groups at 3330–3400 cm^(−1)and an increase in the signal intensity at 2920 cm^(−1)of aliphatic-CH2-groups were observed.For the UF adhesive,the C=O stretching frequency has shifted from 1632 cm^(−1)for uncured to three different bands at 1766,1701,and 1655 cm^(−1)for cured UF.The sharp band for phenolic alcohols at 1236 cm^(−1)of C–O stretch and hydroxyl O–H functional group at 1009 cm^(−1)and at 684 cm^(−1)of uncured TH adhesive diminished during curing,which indicates that a crosslinking reaction occurs via-OH groups.The peak of the C=O group of urethane bridges at 1697 cm^(−1)for uncured NIPU shifted to lower wavenumber at 1633 cm^(−1)for cured NIPU.展开更多
Using novolac phenolic resin, aniline and formaldehyde as raw materials, benzoxazine-phenolic copolymers with different percentages of benzoxazine rings were prepared. FT-IR was adopted to characterize the molecular s...Using novolac phenolic resin, aniline and formaldehyde as raw materials, benzoxazine-phenolic copolymers with different percentages of benzoxazine rings were prepared. FT-IR was adopted to characterize the molecular structure of the novolac-type phenolic resin and the benzoxazine-phenolic copolymer BP31. In order to understand the curing process of the copolymers, the curing behavior and curing kinetic characteristics were studied by differential scanning calorimetry （DSC）, and the catalytical effect of phenolic hydroxyl on the curing behavior of copolymers was investigated. To investigate the thermal properties of this resin, the thermal degradation behaviors of the cured samples were studied by thermal gravimetric （TG） method, and glass-transition temperatures （Tg） of the cured copolymers were also evaluated by DSC. The dynamic Ozawa method was adopted to determine the kinetic parameters of the curing process as well. The activation energy is 78.8 kJ/mol and the reaction rate constant is in the range from 40.0 to 5.2 （K/min）＂ according to reaction temperatures. The Ozawa exponent decreases from 2.4 to 0.7 with the increase of reaction temperature, and curing mechanism is expounded briefly according to the results. TG result shows that the highest char yield of copolymers is 50.3%. The highest Tg of copolymers is 489 K, which is much higher than that of pure benzoxazine resin.展开更多
Lost circulation, a recurring peril during drilling operations, entails substantial loss of drilling fluid and dire consequences upon its infiltration into the formation. As drilling depth escalates, the formation tem...Lost circulation, a recurring peril during drilling operations, entails substantial loss of drilling fluid and dire consequences upon its infiltration into the formation. As drilling depth escalates, the formation temperature and pressure intensify, imposing exacting demands on plug materials. In this study, a kind of controllable curing resin with dense cross-network structure was prepared by the method of solution stepwise ring-opening polymerization. The resin plugging material investigated in this study is a continuous phase material that offers effortless injection, robust filling capabilities, exceptional retention, and underground curing or crosslinking with high strength. Its versatility is not constrained by fracture-cavity lose channels, making it suitable for fulfilling the essential needs of various fracture-cavity combinations when plugging fracture-cavity carbonate rocks. Notably, the curing duration can be fine-tuned within the span of 3-7 h, catering to the plugging of drilling fluid losing of diverse fracture dimensions. Experimental scrutiny encompassed the rheological properties and curing behavior of the resin plugging system, unraveling the intricacies of the curing process and establishing a cogent kinetic model. The experimental results show that the urea-formaldehyde resin plugging material has a tight chain or network structure. When the concentration of the urea-formaldehyde resin plugging system solution remains below 30%, the viscosity clocks in at a meager 10 mPa·s. Optimum curing transpires at 60℃, showcasing impressive resilience to saline conditions. Remarkably, when immersed in a composite saltwater environment containing 50000 mg/L NaCl and 100000 mg/L CaCl_(2), the urea-formaldehyde resin consolidates into an even more compact network structure, culminating in an outstanding compressive strength of 41.5 MPa. Through resolving the correlation between conversion and the apparent activation energy of the non-isothermal DSC curing reaction parameters, the study attests to the fulfillment of the kinetic equation for the urea-formaldehyde resin plugging system. This discerning analysis illuminates the nuanced shifts in the microscopic reaction mechanism of the urea-formaldehyde resin plugging system. Furthermore, the pressure bearing plugging capacity of the resin plugging system for fractures of different sizes is also studied. It is found that the resin plugging system can effectively resident in parallel and wedge-shaped fractures of different sizes, and form high-strength consolidation under certain temperature conditions. The maximum plugging pressure of resin plugging system for parallel fractures with outlet size 3 mm can reach 9.92 MPa, and the maximum plugging pressure for wedge-shaped fractures with outlet size 5 mm can reach 9.90 MPa. Consequently, the exploration and application of urea-formaldehyde resin plugging material precipitate a paradigm shift, proffering novel concepts and methodologies in resolving the practical quandaries afflicting drilling fluid plugging.展开更多
基金Supported by Innovation Capability Support Program of Shaanxi(2024RS-CXTD-53,2024ZC-KJXX-096)the Key R&D Program of Shaanxi Province(2022QCY-LL-69)Xi’an Science and Technology Project(24GXFW0089)。
文摘Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting two greenhouse gases(methane and carbon dioxide)into syngas and its promising industrial applications.Nickel(Ni)-based catalysts,with high catalytic activity,low cost,and abundant resources,are considered ideal candidates for industrial applications.In this article,three reaction kinetic models were briefly introduced,namely the Power-Law(PL)model,the Eley-Rideal(ER)model,and the Langmuir-Hinshelwood-Hougen-Watson(LHHW)model.Based on the LHHW model,the reaction kinetics and mechanisms of different catalytic systems were systematically discussed,including the properties of supports,the doping of noble metals and transition metals,the role of promoters,and the influence of the geometric and electronic structures of Ni on the reaction mechanism.Furthermore,the kinetics of carbon deposition and elimination on various catalysts were analyzed.Based on the reaction rate expressions for carbon elimination,the reasons for the high activity of transition metal iron(Fe)-doped catalysts and core-shell structured catalysts in carbon elimination were explained.Based on the detailed collation and comparative analysis of the reaction mechanisms and kinetic characteristics across diverse Ni-based catalytic systems,a theoretical guidance for the designing of high-performance catalysts was provided in this work.
基金supported by the National Natural Science Foundation of China(Grant Nos.12172045,U2241240,and 12221002)the National Program on Key Basic Research Project,China(Grant No.2019-JCJQ-ZD-308-00).
文摘The curing behavior of composites significantly influences their performance,making it crucial to understand the curing process.This study experimentally measured specific heat capacity,thermal conductivity,glass transition temperature,coefficient of thermal expansion,and cure shrinkage of materials.A simulation model of its curing deformation was established and validated against strain data obtained from fiber Bragg grating experiments.The effects of thickness,heating rate,and cooling rate on the curing temperature field and residual stress field during the molding of thick-section composite plates were analyzed.
基金supported by the National Natural Science Foundation of China(No.52122407)the National Key Research&Development Program of China(No.2022YF2906200)the Science and Technology Innovation Program of Hunan Province,China(No.2022RC3048)。
文摘The leaching process and kinetic behavior of lepidolite in hydrochloric acid were explored systematically.The influence of leaching conditions on the leaching efficiency of valuable metals in lepidolite was investigated.Under optimized conditions,the leaching efficiencies of Li,K,Rb,Cs and Al are 92.02%,93.31%,88.59%,86.75%and 81.07%,respectively.Kinetics research results show that the leaching process conforms to the shrinking core model that is under the mixed control of chemical reaction and diffusion through the solid product layer.In addition,the contribution of solid product layer diffusion to the leaching gradually expands as the temperature rises,but it is still significantly less than the contribution of chemical reaction.Cost saving in the neutralizing agent and leaching processes makes hydrochloric acid an economical leaching agent for lepidolite.Finally,the Li2CO3 product with a purity of 99.89%was synthesized from the hydrochloric acid leachate.
基金Yunnan Fundamental Research Project,China(No.202201BE070001-056)。
文摘The volatilization characteristics and kinetic mechanisms of arsenic were investigated in the temperature range of 623−773 K and pressure ranges of 10−10000 Pa.The experimental results reveal that the evaporation rate increases with increasing temperature and decreasing pressure.Surface reaction control dominates at low pressures(<100 Pa),whereas diffusion control dominates at high pressures(>5000 Pa).The evaporation behavior is successfully described by an Arrhenius-type model for temperature dependence and Logistic model for pressure dependence.Key kinetic parameters,including the critical pressure,maximum evaporation rate and evaporation coefficient,were calculated.The evaporation coefficient varies between 0.010 and 0.223,and the critical pressures vary between 281 and 478 Pa with temperature.
基金supported by the National Key Research&Development Program of China(No.2022YFC2904905)the National Natural Science Foundation of China(No.52274400)+1 种基金the Project of Zhongyuan Critical Metals Laboratory,China(No.GJJSGFZD202302)the Science and Technology Project of Henan Province,China(No.232102230044)。
文摘The hydrogen reduction kinetics of tungsten trioxide(WO_(3))was investigated via non-isothermal thermogravimetric analysis.Under the local gas-solid reduction conditions,the particle morphology of tungsten powders was found to be consistent with that of raw material WO_(3).The removal of oxygen from tungsten oxide during hydrogen reduction led to the formation of porous structures between the reduced particles,which were obviously different from the polyhedral single-crystal configuration of tungsten powders obtained via chemical vapor deposition.Moreover,the two-stage hydrogen reduction mechanisms of WO_(3) under the local gas-solid reduction conditions can be described using the composite autocatalytic function.The activation energies of the first and second stages of the hydrogen reduction of WO_(3) were determined to be 121 and 135 kJ/mol,respectively.
基金supported by the National Natural Science Foundation of China (NSFC grant no. 62474028, 52130304, and62222503)the Natural Science Foundation of Sichuan Province(2025ZNSFSC0037, 2025ZNSFSC1460, and 2024NSFSC1447)+1 种基金the National Key R and D Program of China (2023YFB2604101)sponsored by the Sichuan Province Key Laboratory of Display Science and Technology
文摘The crystallization and aggregation characteristics of the active layer components in organic solar cells(OSCs)are one of the core factors determining photovoltaic performance,influencing the entire process from light absorption to charge separation,transport,and ultimately charge collection.Dynamic changes in crystallization and aggregation states can also disrupt the microstructure of the active layer,thus shortening the lifetime of the cell.In this study,a morphology modulation strategy is proposed to regulate the crystallization kinetics of non-fullerene acceptors by employing the polymer molecule PYIT as a nucleating agent.An appropriate amount of PYIT was first completely dissolved with the non-fullerene acceptor Y6 and left to stand for 24 h,followed by the fabrication of layer-by-layer processed OSCs.Experiments demonstrated that high crystallinity of PYIT allows it to act as a crystallization nucleus,promoting the crystallization,orientation consistency,and ordered stacking of the acceptor.These nanoscale structural optimizations facilitate efficient charge transport,enhance exciton dissociation efficiency,and suppress unfavorable energetic disorder.Consequently,not only was the power conversion efficiency(PCE)of D18-Cl/Y6-based layer-by-layer processed OSC increased from 18.08%to 19.13%,but the atmospheric stability and long-term lifetime of the OSCs were also significantly improved.Notably,this strategy is also applicable to indoor OSCs,and the PYIT-optimized device can achieve a PCE of 27.0%under 1000 lux light-emitting diode(LED,3200K)irradiation,which is superior to that of the control device(24.2%).This work develops a crystal engineering strategy that is able to simultaneously optimize the microscopic morphology and charge dynamics properties in OSCs,thereby achieving simultaneous improvement in efficiency and stability.
基金Funded by the Sichuan Province Science and Technology Support Program(No.2025YFNZH0022)the Chengdu Municipal Science and Technology Program(No.2025-YF11-00003-HZ)。
文摘Curing temperature significantly affects the pozzolanic reaction kinetics of phosphorous slag(PS),thereby governing the early-age(7 d)hydration behavior of PS composite binders at 20,30,and 60℃.The Krstulovic-Dabic kinetic model was applied to identify three characteristic processes:nucleation and growth(NG),phase boundary interaction(I),and diffusion(D).Control mixtures containing inert quartz powder with comparable particle size distributions were prepared for comparison.Pore characteristics of hardened PS pastes at different temperatures were analyzed via mercury intrusion porosimetry,while hydration products were characterized using X-ray diffraction(XRD)and thermogravimetric analysis(TG-DTG).The experimental results indicate that the retarding effect of PS on early cement hydration outweighs its accelerating effect,attributed to the combined influence of nucleation and dilution,with retardation decreasing as temperature increases.PS exhibits early reactivity and continuously consumes calcium hydroxide through the pozzolanic reaction,as evidenced by stable phase assemblages accompanied by reduced CH content in XRD and TG-DTG analyses.At 20℃,increasing PS content maintains the NG→I→D mechanism but slows reaction rates across all stages.Elevated temperatures significantly accelerate the NG process,shifting the dominant mechanism from NG toward D.Simultaneously,enhanced PS reactivity contributes to a refined pore structure and improved compressive strength.
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the financial support from the Yunnan Provincial Science and Technology Project at Southwest United Graduate School(Grant No.202302A0370009)the National Natural Science Foundation Joint Fund(Grant No.U21A2072)+4 种基金the National Science Foundation(Grant No.62274099)the Key Project of Tianjin Natural Science Foundation(Grant No.24JCZDJC01360)the China Higher Education Discipline Innovation Overseas Expert Introduction Project(Grant No.B16027)Tianjin Science and Technology Project(Grant No.24ZXZSSS00160)the Special Fund for Basic Scientific Research of the Central Universities。
文摘Inorganic perovskite solar cells(IPSCs),due to their suitable bandgap and superior thermal stability,are ideal candidates for tandem solar cells combined with silicon.However,the development of inorganic perovskite solar cells has been hindered by suboptimal crystallization dynamics that generate detrimental defects in the perovskite lattice.Here,we propose 4-Methoxyphenylphosphonic Acid(4MPA)as a multifunctional additive to address this challenge.P=O in 4MPA establish strong coordination with undercoordinated Pb^(2+),while-OH engage in O...H-O hydrogen bonding interactions with DMSO,effectively weakening the solvent-[PbX_(6)]^(4-)octahedron interaction.This dual functionality facilitates complete and rapid DMA^(+)-to-Cs^(+)cation exchange while regulating crystallization kinetics,thereby optimizing crystal growth.Furthermore,π-π interactions between benzene rings significantly enhance the moisture resistance of the perovskite layer.The optimized device demonstrates a power conversion efficiency(PCE)of 21.35%,with unencapsulated devices retaining 93,63%of their initial efficiency after 200-hour continuous operation under ambient conditions(35%relative humidity).
基金supported by the project grant,MLP-7016-28(EVB)of CSIR-NGRI,India。
文摘This study investigates four Late Permian Gondwana coals from the Raniganj sub-basin,Damodar Valley and three Early Permian Gondwana coals from the Talcher sub-basin,Mahanadi Valley.The study aims to characterize the kerogen type,hydrocarbon generation potential,thermal maturity,and organic matter composition,as well as to explore the impact of organic matter characteristics on kerogen kinetic parameters,utilizing multi proxy approach.The study further investigates the influence of the mineral matrix on kerogen decomposition kinetics.Based on the Rock-Eval parameters,Fourier transform infrared spectroscopy(FTIR)parameters,and vitrinite reflectance(R_(o)),the kerogen is primarily classified as immature/early mature TypeⅢkerogen derived from terrestrial land plants,with minor contribution from TypeⅡkerogen having mainly gas generating potential.The source of the organic matter,as determined by stable carbon isotopic composition(δ^(13)C_(org))values and C/N ratios indicates a primary input from C_(3) terrestrial plants.The presence of enriched collotelinites and liptinites,such as sporinite and resinite,provides evidence for the input of terrestrial higher plants,including both herbaceous and arborescent species.Various indices derived from maceral abundances,including the gelification index(GI),tissue preservation index(TPI),and vegetation index(VI),collectively indicate diverse depositional conditions which range from wet forest swamps to shallow water-covered wet forest swamps and even dry forest swamps.The variation in vitrinite macerals influenced the kerogen type and consequently impacted the kinetic parameters,viz.the distribution of activation energies(E_(a)),kerogen transformation ratio(KTR),and hydrocarbon generation rate(HGR).Among the Talcher coals,shaly coals exhibit different kerogen type and kerogen transformation.This dissimilarity can be attributed to variable maceral compositions.Unlike the Talcher samples,all Raniganj samples show consistent kinetic behaviour despite their sample type(coal/shaly coal)or kerogen type(TypeⅢ/mixed TypeⅡ/Ⅲ)owing to comparable liptinite/vitrinite maceral composition.This study reveals that whilst the presence of mineral matrix shifts the apparent E_(a) of kerogen through interactions like adsorption and catalysis,it does not significantly affect the kerogen type,HGR,or KTR of the studied coals.
基金Open Access funding enabled and organized by Projekt DEAL.
文摘In this study,copper extraction from low-grade oxide-sulfide ores was investigated using a leaching method combined with response surface methodology(RSM)to optimize operational conditions and assess leaching kinetics.Given copper's extensive industrial applications,sustainable recovery from low-grade ores is critical.Five key parameters-acid concentration,leaching time,particle size,temperature,and solids percentage-were identified as major influences on copper recovery.The results revealed that leaching time and solids percentage,along with interactions between temperature-time and temperature-solids percentage,had the most significant effects.Optimal conditions for 80% copper recovery while minimizing iron recovery below 3% included an acid concentration of 1.21 mol L^(-1),a leaching time of 108 min,a particle size of 438μm,a temperature of 45℃,and a solids percentage of 18.2%.Leaching kinetics were analyzed using shrinking core models,with the Dickinson model best describing the process,showing an activation energy of 32.63 kJ mol^(-1),indicative of mixed diffusion and chemical reaction control.The final kinetic model effectively predicted the influence of key parameters.These findings highlight the importance of optimizing process variables and selecting suitable kinetic models to enhance extraction efficiency,reduce costs,and improve sustainability in copper recovery.
基金allocated by National Science,Research and Innovation Fund(NSRF)King Mongkut's University of Technology North Bangkok(project no.KMUTNB-FF-67-B-44 and KMUTNB-FF-67-B-45)supported by the NSRF through the Program Management Unit for Human Resources&Institutional Development,Research and Innovation(grant no.B40G660036).
文摘This study proposes to use the unconfined compressive strength(UCS)and the bender element(BE)tests for determining the strength and the initial small-strain shear modulus of Bangkok soft marine clay improved by cement and polyester fibers.This study varies the content of admixed cement(1%–20%)and polyester fibers(0–20%),including the curing time(3–28 d)for preparing 360 samples.Moreover,this study uses the Michaelis-Menten kinetics concept to model cement hydration saturation.From the study,it is concluded as follows.The modelled results reveals that at least 10%cement and 1%polyester fiber are recommended to attain the 28-d UCS standards(294 kPa)for highway subgrade materials in Thailand.This also fulfils sustainable construction due to reducing normal-use cement from 20%to 10%.Unfortunately,the addition of polyester fibers into the Bangkok clay with at least 5%cement reduces shear modulus by 1.12–1.32 times.The Abram's relationship between shear modulus and the mixing-water-to-cement ratio is found time-dependent.From the composite theory,the BE detects the polyester fiber zone as a defect in the Bangkok clay(matrix)with 5%–20%cement.So,the 28-d shear modulus in the polyester fiber zone is negative(up to0.034 MPa for 20%fiber),similar to softening phenomenon in concrete cracking(negative stiffness).For the 28-d shear modulus of fiber zone,the optimum cement content is around 2%for the positive influences of polyester fibers.Experimentally,the timedependent normalized UCS for 10%and 20%cement is compatible with other studies,and its development rate increases with the cement content as 0.3017,0.3172 and 0.3204 for 5%,10%and 20%cement,respectively.The 28-d relationship between shear modulus and UCS shows that low-cement soft clay requires high polyester fiber content(5%–20%)to activate UCS improvement.However,the soft clay with enough cement(20%)causes the uniformly distributed UCS improvement.
基金the funding support from the National Natural Science Foundation of China(Grant No.52202217,52471222)the Natural Science Foundation of Jilin Province(Grant No.YDZJ202201ZYTS375).
文摘Layered double hydroxides(LDHs)hold great promise as cathode materials for aqueous zinc-ion batteries(AZIBs).Nevertheless,they also face challenges of sluggish kinetics and rapid capacity loss.Herein,a conformational entropy regulation strategy has been applied to surmount the shortcomings.A medium-entropy iron-based metal organic framework(MIL-88)derived NiCoFeInZnV-based layered double hydroxide with carbon loaded(ME-NiCoFeInZnV-LDH/C)has been first proposed and prepared with a designed method.The increased entropy optimizes electron conductivity and alleviates structure alteration and diffusion barrier during interactions with charge carriers,due to electron-induced effect and“cocktail”effect.Moreover,the nanosheet assembled hollow prismatic structures could homogenize flux distribution and electric field distribution.Therefore,the electrochemical kinetics,crystal structure stability,and activity could be dramatically improved.Leveraging the advantages of structure and composition regulation,Zn||ME-NiCoFeInZnV-LDH/C zinc battery delivers high specific capacities,rate performance,and cycling stability.This work proposes a novel and feasible medium-entropy strategy to prepare a high-performance cathode for advanced AZIBs,which is of prominent significance for the development of charge storage devices.
基金supported by the National Natural Science Foundation of China(Grant No.52174371)the National Key Research and Development Program of China(Grant No.2021YFB3501003)the Shaanxi Provincial Science and Technology Department Enterprise Joint Fund(Grant No.2021JLM-33).
文摘Single-pass and double-pass high-temperature deformation experiments were conducted on 40Cr10Si2Mo steel using a Gleeble-3500 thermal simulator.The static recrystallization(SRX)behavior and recrystallization mechanisms of 40Cr10Si2Mo steel were investigated under deformation temperatures of 900-1100℃,deformation strains of 10%,20%,and 30%,and inter-pass times of 1-120 s.A static recrystallization fraction model was developed.The results showed that the SRX volume fraction increased with higher deformation temperature,larger deformation amount,and longer inter-pass time,with the deformation temperature having the most significant effect on SRX.During the deformation process,different process parameters led to different internal deformation mechanisms of the material.Static recovery and continuous static recrystallization(CSRX)dominated deformation at lower temperatures through progressive lattice rotation.In comparison,at higher temperatures,the deformation mechanism was dominated by CSRX and discontinuous static recrystallization(DSRX).The nucleation mechanisms of the SRX process were grain boundary bulging nucleation and subgrain merging nucleation,with grain boundary bulging present under all conditions.Subgrain merging nucleation could provide an additional nucleation mode at lower deformation temperatures or lower deformation amounts.Based on the traditional Avarmi equation,a modified model coefficient was used to establish the SRX kinetic model for 40Cr10Si2Mo steel.The linear correlation coefficient R^(2) between the predicted and experimental static recrystallization volume fraction was 0.96702,indicating high prediction accuracy.
基金supported by the National Natural Science Foundation of China(Nos.42330703 and 42177194)Zhejiang Provincial Natural Science Foundation of China(No.LMS25D030001).
文摘Cadmium(Cd)contamination in soils poses substantial environmental and health risks globally,with manganese(Mn)playing a crucial role in regulating Cd mobility through soil adsorption processes and shared crop uptake pathways.While the importance of understanding Cd-Mn dynamics in soils is widely recognized,quantitative assessments of their correlated desorption processes remain limited.This study employed diffusive gradients in thin-films(DGT)technique combined with DGT-induced fluxes in soils(DIFS)modeling to investigate Cd and Mn availability and desorption dynamics in karst soils from Guangxi,southwestern China.The soil solution concentrations ranged from 0.23–1.82μg/L for Cd and 1.29–8.41 mg/L for Mn.DGT measurements demonstrated nonlinear accumulation patterns for both metals over 48 h duration.DIFS modeling yielded distribution coefficients(Kdl)ranging from 2.50 to 807 mL/g and response time(Tc)between 1.27 and 425 s for both metals.Solid phase resupply was limited by desorption rates of 5.38–229×10^(−5)/s,providing unprecedented insight into the kinetics of metal release in these soils.Analysis of metal desorption rate ratios(k−1-Mn/k−1-Cd)indicated that soil organic matter content,clay content,pH,and metal contents collectively control Cd and Mn desorption kinetics,leading to distinct desorption patterns across soils with varying physicochemical properties.These findings demonstrate rapid equilibrium reestablishment and desorption-limited resupply characteristics of Cd and Mn in karst soils,advancing understanding of correlative metal behaviors in these unique geological settings.
基金supported by the National 863 Plan(No.2006AA03A209)New Century Excellent Talent Plan (No.NECT-05-0660) from Ministry of EducationDefense Basic Research Item(No.D1420061057)
文摘A high performance thermosetting epoxy resin crosslinkable at room temperature was obtained via directly moulding diglycidyl ether of bisphenol A（DGEBA） and flexibleα,ω-bisamino（n-alkylene）phenyl terminated poly（ethylene glycol）.The influences of the n-alkylene inserted in aminophenyl of flexible amino-terminated polythers（ATPE） on the mechanical properties,fractographs and curing kinetics of the ATPE-DGEBA cured products were studied.The results show that the insertion of n-alkylene group into the aminophenyl group of the ATPE,on one hand,can significantly increase the strain relaxation rate and decrease glass transition temperature of the ATPE-DGEBA cured products,resulting in slight decrease of the Young’s modulus and tensile strength,and significant increase of the toughness and elongation of the ATPE-DGEBA cured products.On the other hand,it can remarkably enhance the reactivity of amine with epoxy,much accelerating the curing rate of the ATPE-DGEBA systems.The activation energy of DGEBA cured by BAPTPE,BAMPTPE and BAEPTPE was 53.1,28.5 and 25.4 kJ·mol;,respectively.The as-obtained ATPE-DGEBA cured products are homogeneous, transparent,and show excellent mechanical properties including tensile strength and toughness.Thus they are promising to have important applications in structure adhesives,casting bulk materials,functional coatings,cryogenic engineering, damping and sound absorbing materials.
文摘The cure kinetics of diglycidyl ether of bisphenol A （DGEBA） with hyperbranched poly （3-hydroxyphenyl） phosphate（HHPP） as the curing agent was investigated by means of non-isothermal differential scanning calorimetry （DSC） at various heating rates. The results were compared with the corresponding results by using 1,3-dihydroxybenzene（DHB） as a model compound. The results show that HHPP can enhance the cure reaction of DGEBA, resulting in the decrease of the peak temperature of the curing curve as well as the decrease of the activation energy because of the flexible --P--O-- groups in the backbone of HHPP. However, both the activation energy of the cured polymer and the peak temperature of the curing curve are increased with DHB as a curing agent. The cure kinetics of the DGEBA/HHPP system was calculated by using the isoconversional method given by Malek. It was found that the two-parameter autocatalytic model（Sestak-Berggren equation） is the most adequate one to describe the cure kinetics of the studied System at various heating rates. The obtained non-isothermal DSC curves from the experimental data show the results being accordant with those theoretically calculated.
基金the ERA-CoBioTech project WooBAdh(Environmentally-friendly bioadhesives from renewable resources)and by the Slovenian Ministry of Education.Science and Sport and the Slovenian Research Agency within the framework of the program P4-0015.
文摘The curing process of two biobased adhesives:pine tanninhexamine(TH)and organosolv lignin non-isocyanate polyurethane(NIPU),suitable for interior nonstructural use,were compared with commercial urea-formaldehyde(UF)adhesive.Changes in chemical structure before and after the curing process were observed with Fouriertransform infrared spectroscopy(FTIR).The process of adhesive curing was monitored with differential scanning calorimetry(DSC)and the automated bonding evaluation system(ABES).Both DSC and ABES measurements confirmed UF as the fastest and NIPU as the slowest curing adhesive observed.Taking into account the ABES results,the optimal pressing parameters for the TH adhesive would be 4 min at 175℃,for the NIPU adhesive 7 min at 200℃and for the UF 1.5 min at 100℃.Strong linear correlation was observed between mechanical and chemical curing for the UF and NIPU adhesives,whereas lower correlation was observed for the TH adhesive.At all observed adhesives,the DSC measurements were underestimating the curing process determined by ABES in the first part and overestimating it at the end.The underestimation was the most evident with the TH adhesive and the less with the UF adhesive.When comparing the uncured and cured FTIR spectra of all three types of adhesives,a drastic decrease in the characteristic band of-OH groups at 3330–3400 cm^(−1)and an increase in the signal intensity at 2920 cm^(−1)of aliphatic-CH2-groups were observed.For the UF adhesive,the C=O stretching frequency has shifted from 1632 cm^(−1)for uncured to three different bands at 1766,1701,and 1655 cm^(−1)for cured UF.The sharp band for phenolic alcohols at 1236 cm^(−1)of C–O stretch and hydroxyl O–H functional group at 1009 cm^(−1)and at 684 cm^(−1)of uncured TH adhesive diminished during curing,which indicates that a crosslinking reaction occurs via-OH groups.The peak of the C=O group of urethane bridges at 1697 cm^(−1)for uncured NIPU shifted to lower wavenumber at 1633 cm^(−1)for cured NIPU.
基金Project (20050106) supported by the Key Science and Technology Item of Guangdong Province,China
文摘Using novolac phenolic resin, aniline and formaldehyde as raw materials, benzoxazine-phenolic copolymers with different percentages of benzoxazine rings were prepared. FT-IR was adopted to characterize the molecular structure of the novolac-type phenolic resin and the benzoxazine-phenolic copolymer BP31. In order to understand the curing process of the copolymers, the curing behavior and curing kinetic characteristics were studied by differential scanning calorimetry （DSC）, and the catalytical effect of phenolic hydroxyl on the curing behavior of copolymers was investigated. To investigate the thermal properties of this resin, the thermal degradation behaviors of the cured samples were studied by thermal gravimetric （TG） method, and glass-transition temperatures （Tg） of the cured copolymers were also evaluated by DSC. The dynamic Ozawa method was adopted to determine the kinetic parameters of the curing process as well. The activation energy is 78.8 kJ/mol and the reaction rate constant is in the range from 40.0 to 5.2 （K/min）＂ according to reaction temperatures. The Ozawa exponent decreases from 2.4 to 0.7 with the increase of reaction temperature, and curing mechanism is expounded briefly according to the results. TG result shows that the highest char yield of copolymers is 50.3%. The highest Tg of copolymers is 489 K, which is much higher than that of pure benzoxazine resin.
基金financially supported by the National Natural Science Foundation of China (Grant 52374023, 52288101)Taishan Scholar Young Expert (Grant tsqn202306117)。
文摘Lost circulation, a recurring peril during drilling operations, entails substantial loss of drilling fluid and dire consequences upon its infiltration into the formation. As drilling depth escalates, the formation temperature and pressure intensify, imposing exacting demands on plug materials. In this study, a kind of controllable curing resin with dense cross-network structure was prepared by the method of solution stepwise ring-opening polymerization. The resin plugging material investigated in this study is a continuous phase material that offers effortless injection, robust filling capabilities, exceptional retention, and underground curing or crosslinking with high strength. Its versatility is not constrained by fracture-cavity lose channels, making it suitable for fulfilling the essential needs of various fracture-cavity combinations when plugging fracture-cavity carbonate rocks. Notably, the curing duration can be fine-tuned within the span of 3-7 h, catering to the plugging of drilling fluid losing of diverse fracture dimensions. Experimental scrutiny encompassed the rheological properties and curing behavior of the resin plugging system, unraveling the intricacies of the curing process and establishing a cogent kinetic model. The experimental results show that the urea-formaldehyde resin plugging material has a tight chain or network structure. When the concentration of the urea-formaldehyde resin plugging system solution remains below 30%, the viscosity clocks in at a meager 10 mPa·s. Optimum curing transpires at 60℃, showcasing impressive resilience to saline conditions. Remarkably, when immersed in a composite saltwater environment containing 50000 mg/L NaCl and 100000 mg/L CaCl_(2), the urea-formaldehyde resin consolidates into an even more compact network structure, culminating in an outstanding compressive strength of 41.5 MPa. Through resolving the correlation between conversion and the apparent activation energy of the non-isothermal DSC curing reaction parameters, the study attests to the fulfillment of the kinetic equation for the urea-formaldehyde resin plugging system. This discerning analysis illuminates the nuanced shifts in the microscopic reaction mechanism of the urea-formaldehyde resin plugging system. Furthermore, the pressure bearing plugging capacity of the resin plugging system for fractures of different sizes is also studied. It is found that the resin plugging system can effectively resident in parallel and wedge-shaped fractures of different sizes, and form high-strength consolidation under certain temperature conditions. The maximum plugging pressure of resin plugging system for parallel fractures with outlet size 3 mm can reach 9.92 MPa, and the maximum plugging pressure for wedge-shaped fractures with outlet size 5 mm can reach 9.90 MPa. Consequently, the exploration and application of urea-formaldehyde resin plugging material precipitate a paradigm shift, proffering novel concepts and methodologies in resolving the practical quandaries afflicting drilling fluid plugging.
