Nucleation,which is the initial step of crystallization,critically governs the polymer crystallization behavior,influencing the crystallization temperature,kinetics,and morphology.However,the direct observation of the...Nucleation,which is the initial step of crystallization,critically governs the polymer crystallization behavior,influencing the crystallization temperature,kinetics,and morphology.However,the direct observation of the nucleation process in polymers remains elusive owing to spatial and temporal resolution limitations.This feature article summarizes the recent progress in understanding polymer nucleation within confined and interface-dominated environments,focusing on three representative systems:anodic aluminum oxide templates and nanocomposites containing nanoparticles or nanosheets.The interplay between finite size and interfacial effects has revealed some novel phenomena,such as homogeneous nucleation,surface nucleation,prefreezing,and supernucleation.展开更多
The chemical structure of polyamide 6(PA6)dictates that only 50%of hydrogen bonds participate in crystallization during the crystallization process,resulting in the properties of its products being significantly depen...The chemical structure of polyamide 6(PA6)dictates that only 50%of hydrogen bonds participate in crystallization during the crystallization process,resulting in the properties of its products being significantly dependent on the molding process.Therefore,the design and development of nucleating agents suitable for PA6 holds great practical significance for high-performance PA6 materials.Amide-based nucleating agents can effectively improve the crystallization rate by increasing intermolecular hydrogen bond density.Further introduction of hydroxyl groups can enhance the hydrogen bonding interactions between the nucleating agent and PA6.In this study,a hydroxyl-containing amidebased nucleating agent,BHT,was designed and synthesized using a tyramine-based biomass as the raw material.These results demonstrated that BHT exhibited good structural compatibility with PA6.After adding 1 wt%BHT,the crystallization temperature of PA6 increased from 170.9℃to 193.3℃,the crystallinity increased 16.6%,the heat distortion temperature and Vicat softening temperature rose to 89.5 and 187.8℃,respectively,the haze decreased to 46%,achieving the synergistic optimization of mechanical,thermal,and optical properties.The in situ time-resolved FTIR results indicated that the addition of BHT increased the enthalpy of hydrogen bond formation during the nucleation stage,facilitated the segmental conformation adjustment of PA6,and enhanced the molar concentration of trans-conformations,ultimately leading to an improvement in the crystallization rate.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
This paper investigates elastomer-toughened polypropylene(PP)insulation to meet the application requirements for green noncrosslinked PP cables in high-voltage direct current(HVDC)transmission.It focuses on the format...This paper investigates elastomer-toughened polypropylene(PP)insulation to meet the application requirements for green noncrosslinked PP cables in high-voltage direct current(HVDC)transmission.It focuses on the formation ofβ-crystals in isotactic polypropylene(iPP)by adding aβ-nucleator.It examines how varying concentrations ofβ-nucleator and elastomer(POE)impact the aggregation structure of PP insulation and its conductivity and breakdown characteristics in the DC field.The results indicated that at aβ-nucleator agent content of 0.1 wt%,the samples with various POE contents achieved the highest crystallinity,the maximum proportion ofβ-crystals and the most uniform elastomer distribution.The nucleating agent facilitates the formation ofβ-crystals in PP and enhances the order degree of the elastomer molecular chains,thereby improving their crystallization capabilities.Evaluations of DC performances and trap characteristics reveal that when the amount of theβ-nucleator is set at 0.1 wt%,the sample demonstrates the lowest trap density,an exceptional and lower electric field coefficient of conductivity at elevated electric fields and a superior DC field breakdown strength at 90°C.Compared to samples withoutβ-nucleator,the reduction of DC field breakdown strength for PPBx-0.1 from 25°C to 90°C is approximately 4.86%lower.This improvement is attributed to the ability of theβ-nucleator to improve the aggregation structure between PP and POE while optimising the stability of the two-phase interface.Thus,although DC electrical characteristics are maintained at normal temperatures,the DC characteristics are significantly improved at elevated temperatures.展开更多
The austenite(γ)reversely transformed from lath martensite(LM),lath bainite(LB),granular bainite(GB)and pearlite+ferrite(P+F)in a high-strength steel was studied at high temperatures using in-situ electron backscatte...The austenite(γ)reversely transformed from lath martensite(LM),lath bainite(LB),granular bainite(GB)and pearlite+ferrite(P+F)in a high-strength steel was studied at high temperatures using in-situ electron backscatter diffraction(EBSD).The memory effect of initial γ significantly affects the nucleation of the reverted γ in LM and GB structures,while a weak influence on that of LB and P+F structures.This results in a significant difference in γ grain size after complete austenitization,with the first two obtaining larger γ grains while the latter two are relatively small.Crystallographic analysis revealed that the reverted γ with acicular morphology(γA),most of which maintained the same orientation with the prior γ,dominated the reaustenitization behavior of LM and GB structures through preferential nucleation within γ grains and coalesced growth modes.Although globular reverted γ(γ_(G))with random orientation or large deviation from the prior γ can nucleate at the grain boundaries or within the grains,it is difficult for it to grow and play a role in segmenting and refining the prior γ due to the inhibition of γ_(A) coalescing.For LB and P+F structures,the nucleation rate of intragranular γ_(G) increases with increasing temperature,and always shows a random orientation.These γ_(G) grains can coarsen simultaneously with the intergranular γ_(G),ultimately playing a role in jointly dividing and refining the finalγgrains.Research also found that the differences in the effects of four different microstructures on revertedγnucleation are closely related to the variant selection of the matrix structure,as well as the content and size of cementite(θ).High density of block boundaries induced by weakening of variant selection and many fineθformed in the lath are the key to promoting LB structure to obtain more intragranular γ_(G) formation,as well as the important role of the large-sized θ in P+F structure.展开更多
It is difficult to generate coherent twin boundaries in bulk Al alloys due to their high intrinsic stacking fault energy. Here, we report a strategy to induce high-density growth twins in aluminum alloys through the h...It is difficult to generate coherent twin boundaries in bulk Al alloys due to their high intrinsic stacking fault energy. Here, we report a strategy to induce high-density growth twins in aluminum alloys through the heterogeneous nucleation of twinned Al grains on twin-structured TiC nucleants and the preferred growth of twinned dendrites by laser surface remelting of bulk metals. The solidification structure at the surface shows a mixture of lamellar twinned dendrites with ultra-fine twin boundary spacing (∼2 µm), isolated twinned dendrites, and regular dendrites. EBSD analysis and finite element method (FEM) simulations have been used to understand the competitive growth between twinned and regular dendrites, and the solidification conditions for the preferred growth of twinned dendrites during laser remelting and subsequent rapid solidification are established. It is shown that the reduction in the ratio of temperature gradient G to solidification rate V promotes the formation of lamellar twinned dendrites. The primary trunk spacing of lamellar twinned dendrites is refined by the high thermal gradient and solidification rate. The present work paves a new way to generate high-density growth twins in additive-manufactured Al alloys.展开更多
Due to the low content of alloying elements and the lack of effective nucleation sites,the fusion zone(FZ)of tungsten inert gas(TIG)welded AZ31 alloy typically exhibits undesirable coarse columnar grains,which can res...Due to the low content of alloying elements and the lack of effective nucleation sites,the fusion zone(FZ)of tungsten inert gas(TIG)welded AZ31 alloy typically exhibits undesirable coarse columnar grains,which can result in solidification defects and reduced mechanical properties.In this work,a novel welding wire containing MgO particles has been developed to promote columnar-to-equiaxed transition(CET)in the FZ of TIG-welded AZ31 alloy.The results show the achievement of a fully equiaxed grain structure in the FZ,with a significant 71.9%reduction in grain size to 41 μm from the original coarse columnar dendrites.Furthermore,the combination of using MgO-containing welding wire and pulse current can further refine the grain size to 25.6 μm.Microstructural analyses reveal the homogeneous distribution of MgO particles in the FZ.The application of pulse current results in an increase in the number density of MgO(1-2 μm)from 5.16 × 10^(4) m^(-3) to 6.18 × 10^(4) m^(-3).The good crystallographic matching relationship between MgO and α-Mg matrix,characterized by the orientation relationship of[11(2)0]α-Mg//[0(1)1]MgO and(0002)_(α-Mg)//(111)_(MgO),indicates that the MgO particles can act as effective nucleation sites for α-Mg to reduce nucleation undercooling.According to the Hunt criteria,the critical temperature gradient for CET is greatly enhanced due to the significantly increased number density of MgO nucleation sites.In addition,the correlation with the thermal simulation results reveals a transition in the solidification conditions within the welding pool from the columnar grain zone to the equiaxed grain zone in the CET map,leading to the realization of CET.The exceptional grain refinement has contributed to a simultaneous improvement in the strength and plasticity of welded joints.This study presents a novel strategy for controlling equiaxed microstructure and optimizing mechanical properties in fusion welding or wire and arc additive manufacturing of Mg alloy components.展开更多
The goethite residue generated from zinc hydrometallurgy is classified as hazardous solid waste,produced in large quantities,and results in significant zinc loss.The study was conducted on removing iron from FeSO_(4)-...The goethite residue generated from zinc hydrometallurgy is classified as hazardous solid waste,produced in large quantities,and results in significant zinc loss.The study was conducted on removing iron from FeSO_(4)-ZnSO_(4) solution,employing seed-induced nucleation methods.Analysis of the iron removal rate,residue structure,morphology,and elemental composition involved ICP,XRD,FT-IR,and SEM.The existing state of zinc was investigated by combining step-by-step dissolution using hydrochloric acid.Concurrently,iron removal tests were extended to industrial solutions to assess the influence of seeds and solution pH on zinc loss and residue yield.The results revealed that seed addition increased the iron removal rate by 3%,elevated the residual iron content by 6.39%,and mitigated zinc loss by 29.55%in the simulated solution.Seed-induced nucleation prevented excessive nuclei formation,fostering crystal stable growth and high crystallinity.In addition,the zinc content of surface adsorption and crystal internal embedding in the residue was determined,and the zinc distribution on the surface was dense.In contrast,the total amount of zinc within the crystal was higher.The test results in the industrial solution demonstrated that the introduction of seeds expanded the pH range for goethite formation and growth,and the zinc loss per ton of iron removed was reduced by 50.91 kg(34.12%)and the iron residue reduced by 0.17 t(8.72%).展开更多
Tension-compression asymmetry is a critical concern for magnesium(Mg)alloys,particularly in automo-tive crash structures.This study systematically examines the tension-compression asymmetry of a cast Mg-Gd-Y alloy at ...Tension-compression asymmetry is a critical concern for magnesium(Mg)alloys,particularly in automo-tive crash structures.This study systematically examines the tension-compression asymmetry of a cast Mg-Gd-Y alloy at various strain rates.Experimental results indicate symmetric yielding stress under both tension and compression at all strain rates,along with a reduction in the tension-compression asym-metry of ultimate stress and plastic strain as the strain rate increases.This trend arises from an unusual strain rate-dependent tension-compression asymmetry,characterized by strain rate toughening in tension and negligible strain rate effect in compression.The differing behavior is linked to the distinct twinning mechanisms under tension and compression.The suppression of twinning under tension contributes to the positive strain rate dependence of pyramidal slip,whereas the activation of abundant twins during compression means that pyramidal slip is unnecessary to accommodate c-axis strain,leading to the ab-sence of a strain rate effect in compression.Abundant twins nucleate consistently from yielding to 2%strain,but only after basal and prismaticslip have mediated microplasticity,suggesting that these slip systems reduce the nucleation stress for twinning during compression,resulting in a lower activation stress for twinning compared to tension.This study provides new insights into micromechanisms of the tension-compression asymmetry in cast Mg-Gd-Y alloys and offers practical guidance for the application of these materials in critical components that must endure both tension and compression under varying strain rates.展开更多
Aqueous zinc-ion batteries (AZIBs) are fundamentally challenged by the instability of the electrode/electrolyte interface,predominantly due to irreversible zinc (Zn) deposition and hydrogen evolution.Particularly,the ...Aqueous zinc-ion batteries (AZIBs) are fundamentally challenged by the instability of the electrode/electrolyte interface,predominantly due to irreversible zinc (Zn) deposition and hydrogen evolution.Particularly,the intricate mechanisms behind the electrochemical discrepancies induced by interfacial Zn^(2+)-solvation and deposition behavior demand comprehensive investigation.Organic molecules endowed with special functional groups (such as hydroxyl,carboxyl,etc.) have the potential to significantly optimize the solvation structure of Zn^(2+)and regulate the interfacial electric double layer (EDL).By increasing nucleation overpotential and decreasing interfacial free energy,these functional groups facilitate a lower critical nucleation radius,thereby forming an asymptotic nucleation model to promote uniform Zn deposition.Herein,this study presents a pioneering approach by introducing trace amounts of n-butanol as solvation regulators to engineer the homogenized Zn (H-Zn) anode with a uniform and dense structure.The interfacial reaction and structure evolution are explored by in/ex-situ experimental techniques,indicating that the H-Zn anode exhibits dendrite-free growth,no by-products,and weak hydrogen evolution,in sharp contrast to the bare Zn.Consequently,the H-Zn anode achieves a remarkable Zn utilization rate of approximately 20% and simultaneously sustains a prolonged cycle life exceeding 500 h.Moreover,the H-Zn//NH_(4)V_(4)O^(10)(NVO) full battery showcases exceptional cycle stability,retaining 95.04%capacity retention after 400 cycles at a large current density of 5 A g^(-1).This study enlightens solvation-regulated additives to develop Zn anode with superior utilization efficiency and extended operational lifespan.展开更多
Memristive crossbar arrays(MCAs)offer parallel data storage and processing for energy-efficient neuromorphic computing.However,most wafer-scale MCAs that are compatible with complementary metal-oxide-semiconductor(CMO...Memristive crossbar arrays(MCAs)offer parallel data storage and processing for energy-efficient neuromorphic computing.However,most wafer-scale MCAs that are compatible with complementary metal-oxide-semiconductor(CMOS)technology still suffer from substantially larger energy consumption than biological synapses,due to the slow kinetics of forming conductive paths inside the memristive units.Here we report wafer-scale Ag_(2)S-based MCAs realized using CMOS-compatible processes at temperatures below 160℃.Ag_(2)S electrolytes supply highly mobile Ag+ions,and provide the Ag/Ag_(2)S interface with low silver nucleation barrier to form silver filaments at low energy costs.By further enhancing Ag+migration in Ag_(2)S electrolytes via microstructure modulation,the integrated memristors exhibit a record low threshold of approximately−0.1 V,and demonstrate ultra-low switching-energies reaching femtojoule values as observed in biological synapses.The low-temperature process also enables MCA integration on polyimide substrates for applications in flexible electronics.Moreover,the intrinsic nonidealities of the memristive units for deep learning can be compensated by employing an advanced training algorithm.An impressive accuracy of 92.6%in image recognition simulations is demonstrated with the MCAs after the compensation.The demonstrated MCAs provide a promising device option for neuromorphic computing with ultra-high energy-efficiency.展开更多
Carbon nanotube formation exemplifies atomically precise self-assembly,where atomic interactions dynamically engineer nanoscale architectures with emergent properties that transcend classical material boundaries.Howev...Carbon nanotube formation exemplifies atomically precise self-assembly,where atomic interactions dynamically engineer nanoscale architectures with emergent properties that transcend classical material boundaries.However,elucidating the transient molecular intermediates remains a critical mechanistic frontier.This study investigates the atomic-scale nucleation process of single-walled carbon nanotubes(SWCNTs)from acetylene on iron(Fe)clusters,utilizing GFN(-x)TB-based nanoreactor molecular dynamics simulations.The simulations reveal a consistent nucleation pathway,regardless of iron cluster size(Fe_(13),Fe_(38),Fe_(55)),where the chemisorption and dissociation of acetylene molecules on the Fe clusters lead to the formation of C_(2)H and C_(2)intermediates.These species then undergo oligomerization,initiating the growth of carbon chains.As the chains cross-link and cyclize,five-membered carbon rings are preferentially formed,which eventually evolve into six-membered rings and more complex sp2-hybridized carbon networks,resembling the cap structures of nascent SWCNTs.Although the nucleation mechanism remains similar across all cluster sizes,larger clusters show enhanced catalytic activity,leading to higher molecular weight hydrocarbons and more extensive carbocyclic networks due to their higher density of active sites per reacting molecule.Crucially,the study highlights the role of C_(2)H as the key active species in the carbon network formation process.These findings offer critical insights into the initial stages of SWCNT nucleation,contributing to a deeper understanding of the mechanisms driving SWCNT growth and guiding the development of optimized synthetic strategies.展开更多
1.Introduction Al-Zn-Mg-Cu alloy is a typical age-hardening aluminum alloy,its strength and toughness are significantly influenced by precipita-tion behavior.The nucleation mechanisms of precipitates in this alloy are...1.Introduction Al-Zn-Mg-Cu alloy is a typical age-hardening aluminum alloy,its strength and toughness are significantly influenced by precipita-tion behavior.The nucleation mechanisms of precipitates in this alloy are generally categorized into homogeneous and heterogeneous nucleation.Homogeneous nucleation relies on structural and energy fluctuations within the solution to generate the driving force necessary for direct nucleation.展开更多
The crystallization of ionic crystals has traditionally been explained by Gibbs's classical nucleation theory.However,recent observations of intermediate phases during nucleation suggest that the process may be mo...The crystallization of ionic crystals has traditionally been explained by Gibbs's classical nucleation theory.However,recent observations of intermediate phases during nucleation suggest that the process may be more complex,necessitating new theoretical frameworks,though key empirical evidence remains elusive.In this study,we used microdroplets to investigate the crystallization of sodium halides(NaCl,NaBr,and NaI)under homogeneous nucleation conditions across a wide range of supersaturations.In the evaporating droplet,NaCl follows the classical nucleation pathway,whereas NaBr and NaI exhibit the formation of an intermediate phase prior to the nucleation of anhydrous and hydrous single crystals,respectively.Optical and computational analyses indicate that these intermediate phases are liquid crystal phases composed of contact ion pairs.These findings establish a new theoretical framework for crystal nucleation and growth and offer methods to control nucleation pathways,enabling us to achieve desired crystals regardless of specific conditions.展开更多
The unique structure and exceptional properties of two-dimensional(2D)materials offer significant potential for transformative advancements in semiconductor industry.Similar to the reliance on wafer-scale single-cryst...The unique structure and exceptional properties of two-dimensional(2D)materials offer significant potential for transformative advancements in semiconductor industry.Similar to the reliance on wafer-scale single-crystal ingots for silicon-based chips,practical applications of 2D materials at the chip level need large-scale,high-quality production of 2D single crystals.Over the past two decades,the size of 2D single-crystals has been improved to wafer or meter scale,where the nucleation control during the growth process is particularly important.Therefore,it is essential to conduct a comprehensive review of nucleation control to gain fundamental insights into the growth of 2D single-crystal materials.This review mainly focuses on two aspects:controlling nucleation density to enable the growth from a single nucleus,and controlling nucleation position to achieve the unidirectionally aligned islands and subsequent seamless stitching.Finally,we provide an overview and forecast of the strategic pathways for emerging 2D materials.展开更多
pH-dependent multiple equilibria in cobalt sulfate-gluconate baths were calculated using stability constants adopted from literature.Changes of the bath speciation were then discussed in terms of spectrophotometric ex...pH-dependent multiple equilibria in cobalt sulfate-gluconate baths were calculated using stability constants adopted from literature.Changes of the bath speciation were then discussed in terms of spectrophotometric experiments and buffering properties of the solutions(pH 3-10).Cyclic voltammetry indicated changes in electrochemical behavior of cobalt species caused by different ionic compositions of the electrolytes.Tafel slopes were calculated and discussed in relation to electroreduction of cobalt species.Chronoamperometric studies showed 3D instantaneous nucleation of cobalt followed by diffusion-controlled growth,but it was disturbed at higher pH due to the release of cation from gluconate complexes as a limiting step.Diffusion coefficients of cobalt species were found.Changes in the pH were also reflected by modifications of morphology(SEM),development of preferred orientation planes(XRD,texture coefficients)and current efficiency,but not the thickness of the coatings deposited at constant potential of-1.0 V(vs Ag/AgCl).Anodic stripping analysis showed changes in anodic responses originated from the existence of preferentially oriented planes in cobalt layers.展开更多
The active cooling technology of endothermic hydrocarbon fuels is a key way to solve the thermal protection of high-speed aircraft engines,but the condensation coking problem during engine shutdown is a bottleneck tha...The active cooling technology of endothermic hydrocarbon fuels is a key way to solve the thermal protection of high-speed aircraft engines,but the condensation coking problem during engine shutdown is a bottleneck that affects the reusability of aircraft.In this study,a self-designed apparatus was used to separately analyze the condensation coking during the fuel cooling process,and the coking characteristics under different temperature conditions were obtained.The condensation coking mechanism of fuel during cooling process was proposed based on the changes in physical properties of coking precursors obtained by the group contribution method.When the temperature drops to 300℃,not only the gas yield and conversion increase to 71.42% and 89.75% respectively,but the coke mass on the inner surface of the tube also significantly increases from 0.39 to 1.92 mg.Meanwhile,as the temperature further decreases,the morphology of coke gradually transforms into amorphous carbon with a higher degree of graphitization.During the cooling process,due to the liquefaction of coking precursors,their physical properties such as viscosity,density,and saturated vapor pressure undergo sudden changes at 300℃,leading to enhanced intermolecular physical interactions and promoting the physical aggregation of coking precursor molecules,which are deposited on the inner wall of the tube.This work provides a theoretical basis for the subsequent study of condensation coking mechanisms and inhibition methods.展开更多
Four typical admixtures,polycarboxylate superplasticiser(PCE),tartaric acid(TA),sorbitol and polyacrylamide(PAM),were selected to systematically investigate their regulatory mechanisms on the formation of ettringite t...Four typical admixtures,polycarboxylate superplasticiser(PCE),tartaric acid(TA),sorbitol and polyacrylamide(PAM),were selected to systematically investigate their regulatory mechanisms on the formation of ettringite through Fourier transform infrared spectroscopy,X-ray diffraction,particle size analysis and nucleation kinetic model.The experimental results indicate that the admixtures alter the formation of ettringite through physical adsorption,complexation and solution viscosity modulation without changing its chemical structure.Low concentrations of PCE inhibit size growth by forming an adsorption layer on the surface of ettringite,whereas high concentrations of PCE alter the size change of ettringite by modulating the distribution of ionic concentrations.TA significantly reduces the size of ettringite by complexing Ca^(2+).Sorbitol and PAM promote the local growth of ettringite at low concentrations,leading to larger sizes.But at high concentrations,the size growth of ettringite is inhibited due to the increase in viscosity or the enhancement of complexation.Matlab nucleation kinetic modelling further shows that the addition of admixtures enhances the initial nucleation during ettringite synthesis,with values ranging from 14.45%to 114.25%.However,the subsequent nucleation rate of ettringite is significantly affected,decreasing by 12.79%to 71.74%.The results provide a theoretical basis for the design of ettringite materials and the optimisation of the application of admixtures.展开更多
To investigate the nucleation behavior during the single-phased metallic solidification process,the commercial ultrapure ferritic stainless steels with no(Initial steel)and various melt treatments(R1,MR1,Y2,MY1,and M1...To investigate the nucleation behavior during the single-phased metallic solidification process,the commercial ultrapure ferritic stainless steels with no(Initial steel)and various melt treatments(R1,MR1,Y2,MY1,and M1 steels)were used to carry out the differential scanning colorimetry(DSC)and high-temperature confocal laser scanning microscope(HT-CLSM)experiments.Based on the results of DSC experiments,the equilibrium solidification process as well as the relationship among the critical undercooling degree(△T_(c)^(DSC)),latent heat of fusion/crystallization(△H_(f)/△H_(c)),equiaxed grain ratio(ER),and average grain size(△_(ave)^(ingot))was revealed.ER is increased with the decreasing△T_(c)^(DSC)and increasing△H_(f)/△H_(c);however,△_(ave)^(ingot)is decreased with them.Referring to the results of HT-CLSM experiments,the average sizes of micro-/macrostructures(d_(ave)/D_(ave)/)are decreased with the increasing cooling rate,as well as the difference between and apparent critical undercooling degree(△T_(c)^(CLSM))was revealed.The heterogeneous nucleation of the crystal nuclei occurs only if△T_(c)^(CLSM)>△T_(c)^(DSC).Combining with the interfacial wetting-lattice mismatch heterogeneous nucleation model,the dynamic mechanism of the metallic solidification was revealed.The as-cast grains of the melt-treated samples were obviously refined,owing to the much higher actual heterogeneous nucleation rates(I_(heter.,i))obtained through melt treatments,and the heterogeneous nucleation rates(I_(heter.,ij))for all samples are increased with the cooling rates,firmly confirming that the as-cast grains of each sample could be refined by the increasing cooling rates.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.21873109 and 21922308)。
文摘Nucleation,which is the initial step of crystallization,critically governs the polymer crystallization behavior,influencing the crystallization temperature,kinetics,and morphology.However,the direct observation of the nucleation process in polymers remains elusive owing to spatial and temporal resolution limitations.This feature article summarizes the recent progress in understanding polymer nucleation within confined and interface-dominated environments,focusing on three representative systems:anodic aluminum oxide templates and nanocomposites containing nanoparticles or nanosheets.The interplay between finite size and interfacial effects has revealed some novel phenomena,such as homogeneous nucleation,surface nucleation,prefreezing,and supernucleation.
文摘The chemical structure of polyamide 6(PA6)dictates that only 50%of hydrogen bonds participate in crystallization during the crystallization process,resulting in the properties of its products being significantly dependent on the molding process.Therefore,the design and development of nucleating agents suitable for PA6 holds great practical significance for high-performance PA6 materials.Amide-based nucleating agents can effectively improve the crystallization rate by increasing intermolecular hydrogen bond density.Further introduction of hydroxyl groups can enhance the hydrogen bonding interactions between the nucleating agent and PA6.In this study,a hydroxyl-containing amidebased nucleating agent,BHT,was designed and synthesized using a tyramine-based biomass as the raw material.These results demonstrated that BHT exhibited good structural compatibility with PA6.After adding 1 wt%BHT,the crystallization temperature of PA6 increased from 170.9℃to 193.3℃,the crystallinity increased 16.6%,the heat distortion temperature and Vicat softening temperature rose to 89.5 and 187.8℃,respectively,the haze decreased to 46%,achieving the synergistic optimization of mechanical,thermal,and optical properties.The in situ time-resolved FTIR results indicated that the addition of BHT increased the enthalpy of hydrogen bond formation during the nucleation stage,facilitated the segmental conformation adjustment of PA6,and enhanced the molar concentration of trans-conformations,ultimately leading to an improvement in the crystallization rate.
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supported by China Southern Power Grid Company Limited(Grant GDKJXM20222136).
文摘This paper investigates elastomer-toughened polypropylene(PP)insulation to meet the application requirements for green noncrosslinked PP cables in high-voltage direct current(HVDC)transmission.It focuses on the formation ofβ-crystals in isotactic polypropylene(iPP)by adding aβ-nucleator.It examines how varying concentrations ofβ-nucleator and elastomer(POE)impact the aggregation structure of PP insulation and its conductivity and breakdown characteristics in the DC field.The results indicated that at aβ-nucleator agent content of 0.1 wt%,the samples with various POE contents achieved the highest crystallinity,the maximum proportion ofβ-crystals and the most uniform elastomer distribution.The nucleating agent facilitates the formation ofβ-crystals in PP and enhances the order degree of the elastomer molecular chains,thereby improving their crystallization capabilities.Evaluations of DC performances and trap characteristics reveal that when the amount of theβ-nucleator is set at 0.1 wt%,the sample demonstrates the lowest trap density,an exceptional and lower electric field coefficient of conductivity at elevated electric fields and a superior DC field breakdown strength at 90°C.Compared to samples withoutβ-nucleator,the reduction of DC field breakdown strength for PPBx-0.1 from 25°C to 90°C is approximately 4.86%lower.This improvement is attributed to the ability of theβ-nucleator to improve the aggregation structure between PP and POE while optimising the stability of the two-phase interface.Thus,although DC electrical characteristics are maintained at normal temperatures,the DC characteristics are significantly improved at elevated temperatures.
基金financially supported by the National Natural Science Foundation of China(Nos.52271089 and 52001023)the Basic Research and Application Basic Research Foundation of Guangdong Province(Nos.2022A1515240016 and 2023B1515250006)the Fundamental Research Funds for the Central Universities(No.FRF-BD-23-01).
文摘The austenite(γ)reversely transformed from lath martensite(LM),lath bainite(LB),granular bainite(GB)and pearlite+ferrite(P+F)in a high-strength steel was studied at high temperatures using in-situ electron backscatter diffraction(EBSD).The memory effect of initial γ significantly affects the nucleation of the reverted γ in LM and GB structures,while a weak influence on that of LB and P+F structures.This results in a significant difference in γ grain size after complete austenitization,with the first two obtaining larger γ grains while the latter two are relatively small.Crystallographic analysis revealed that the reverted γ with acicular morphology(γA),most of which maintained the same orientation with the prior γ,dominated the reaustenitization behavior of LM and GB structures through preferential nucleation within γ grains and coalesced growth modes.Although globular reverted γ(γ_(G))with random orientation or large deviation from the prior γ can nucleate at the grain boundaries or within the grains,it is difficult for it to grow and play a role in segmenting and refining the prior γ due to the inhibition of γ_(A) coalescing.For LB and P+F structures,the nucleation rate of intragranular γ_(G) increases with increasing temperature,and always shows a random orientation.These γ_(G) grains can coarsen simultaneously with the intergranular γ_(G),ultimately playing a role in jointly dividing and refining the finalγgrains.Research also found that the differences in the effects of four different microstructures on revertedγnucleation are closely related to the variant selection of the matrix structure,as well as the content and size of cementite(θ).High density of block boundaries induced by weakening of variant selection and many fineθformed in the lath are the key to promoting LB structure to obtain more intragranular γ_(G) formation,as well as the important role of the large-sized θ in P+F structure.
基金supported by the National Natural Science Foundation of China(grant no.52371029)the Science and Technology Development Program of Jilin Province,China(grant no.20210402083GH).
文摘It is difficult to generate coherent twin boundaries in bulk Al alloys due to their high intrinsic stacking fault energy. Here, we report a strategy to induce high-density growth twins in aluminum alloys through the heterogeneous nucleation of twinned Al grains on twin-structured TiC nucleants and the preferred growth of twinned dendrites by laser surface remelting of bulk metals. The solidification structure at the surface shows a mixture of lamellar twinned dendrites with ultra-fine twin boundary spacing (∼2 µm), isolated twinned dendrites, and regular dendrites. EBSD analysis and finite element method (FEM) simulations have been used to understand the competitive growth between twinned and regular dendrites, and the solidification conditions for the preferred growth of twinned dendrites during laser remelting and subsequent rapid solidification are established. It is shown that the reduction in the ratio of temperature gradient G to solidification rate V promotes the formation of lamellar twinned dendrites. The primary trunk spacing of lamellar twinned dendrites is refined by the high thermal gradient and solidification rate. The present work paves a new way to generate high-density growth twins in additive-manufactured Al alloys.
基金supported by the National Natural Science Foundation of China(No.51871155).
文摘Due to the low content of alloying elements and the lack of effective nucleation sites,the fusion zone(FZ)of tungsten inert gas(TIG)welded AZ31 alloy typically exhibits undesirable coarse columnar grains,which can result in solidification defects and reduced mechanical properties.In this work,a novel welding wire containing MgO particles has been developed to promote columnar-to-equiaxed transition(CET)in the FZ of TIG-welded AZ31 alloy.The results show the achievement of a fully equiaxed grain structure in the FZ,with a significant 71.9%reduction in grain size to 41 μm from the original coarse columnar dendrites.Furthermore,the combination of using MgO-containing welding wire and pulse current can further refine the grain size to 25.6 μm.Microstructural analyses reveal the homogeneous distribution of MgO particles in the FZ.The application of pulse current results in an increase in the number density of MgO(1-2 μm)from 5.16 × 10^(4) m^(-3) to 6.18 × 10^(4) m^(-3).The good crystallographic matching relationship between MgO and α-Mg matrix,characterized by the orientation relationship of[11(2)0]α-Mg//[0(1)1]MgO and(0002)_(α-Mg)//(111)_(MgO),indicates that the MgO particles can act as effective nucleation sites for α-Mg to reduce nucleation undercooling.According to the Hunt criteria,the critical temperature gradient for CET is greatly enhanced due to the significantly increased number density of MgO nucleation sites.In addition,the correlation with the thermal simulation results reveals a transition in the solidification conditions within the welding pool from the columnar grain zone to the equiaxed grain zone in the CET map,leading to the realization of CET.The exceptional grain refinement has contributed to a simultaneous improvement in the strength and plasticity of welded joints.This study presents a novel strategy for controlling equiaxed microstructure and optimizing mechanical properties in fusion welding or wire and arc additive manufacturing of Mg alloy components.
基金Project(2018YFC1900403) supported by the National Key Research and Development Program of ChinaProject(CX20210197) supported by the Postgraduate Scientific Research Innovation Project of Hunan Province,China+1 种基金Project(202206370103) supported by the China Scholarship CouncilProject(2021zzts0115) supported by the Fundamental Research Funds for the Central Universities,China。
文摘The goethite residue generated from zinc hydrometallurgy is classified as hazardous solid waste,produced in large quantities,and results in significant zinc loss.The study was conducted on removing iron from FeSO_(4)-ZnSO_(4) solution,employing seed-induced nucleation methods.Analysis of the iron removal rate,residue structure,morphology,and elemental composition involved ICP,XRD,FT-IR,and SEM.The existing state of zinc was investigated by combining step-by-step dissolution using hydrochloric acid.Concurrently,iron removal tests were extended to industrial solutions to assess the influence of seeds and solution pH on zinc loss and residue yield.The results revealed that seed addition increased the iron removal rate by 3%,elevated the residual iron content by 6.39%,and mitigated zinc loss by 29.55%in the simulated solution.Seed-induced nucleation prevented excessive nuclei formation,fostering crystal stable growth and high crystallinity.In addition,the zinc content of surface adsorption and crystal internal embedding in the residue was determined,and the zinc distribution on the surface was dense.In contrast,the total amount of zinc within the crystal was higher.The test results in the industrial solution demonstrated that the introduction of seeds expanded the pH range for goethite formation and growth,and the zinc loss per ton of iron removed was reduced by 50.91 kg(34.12%)and the iron residue reduced by 0.17 t(8.72%).
基金the National Natural Science Foundation of China(grant Nos.11988102,52301146,51301173,51531002,52171055,52371037,51601193)the National Key Research and Development Program of China(grant No.2016YFB0301104)+1 种基金the Fundamental Research Funds for the Central Universities(grant No.2023JG007)China Postdoctoral Science Foundation(grant No.8206300226).
文摘Tension-compression asymmetry is a critical concern for magnesium(Mg)alloys,particularly in automo-tive crash structures.This study systematically examines the tension-compression asymmetry of a cast Mg-Gd-Y alloy at various strain rates.Experimental results indicate symmetric yielding stress under both tension and compression at all strain rates,along with a reduction in the tension-compression asym-metry of ultimate stress and plastic strain as the strain rate increases.This trend arises from an unusual strain rate-dependent tension-compression asymmetry,characterized by strain rate toughening in tension and negligible strain rate effect in compression.The differing behavior is linked to the distinct twinning mechanisms under tension and compression.The suppression of twinning under tension contributes to the positive strain rate dependence of pyramidal slip,whereas the activation of abundant twins during compression means that pyramidal slip is unnecessary to accommodate c-axis strain,leading to the ab-sence of a strain rate effect in compression.Abundant twins nucleate consistently from yielding to 2%strain,but only after basal and prismaticslip have mediated microplasticity,suggesting that these slip systems reduce the nucleation stress for twinning during compression,resulting in a lower activation stress for twinning compared to tension.This study provides new insights into micromechanisms of the tension-compression asymmetry in cast Mg-Gd-Y alloys and offers practical guidance for the application of these materials in critical components that must endure both tension and compression under varying strain rates.
基金National Natural Science Foundation of China (52301273, 52072411)Science and Technology Innovation Program of Hunan Province (2024RC3222)+3 种基金Key project of scientific research project of Hunan Provincial Department of Education (22A0479)China Postdoctoral Science Foundation (2024M753668)Central South University Innovation-Driven Research Programme (2023CXQD038)Hunan Provincial Postgraduate Research Innovation Programme(CX20240970)。
文摘Aqueous zinc-ion batteries (AZIBs) are fundamentally challenged by the instability of the electrode/electrolyte interface,predominantly due to irreversible zinc (Zn) deposition and hydrogen evolution.Particularly,the intricate mechanisms behind the electrochemical discrepancies induced by interfacial Zn^(2+)-solvation and deposition behavior demand comprehensive investigation.Organic molecules endowed with special functional groups (such as hydroxyl,carboxyl,etc.) have the potential to significantly optimize the solvation structure of Zn^(2+)and regulate the interfacial electric double layer (EDL).By increasing nucleation overpotential and decreasing interfacial free energy,these functional groups facilitate a lower critical nucleation radius,thereby forming an asymptotic nucleation model to promote uniform Zn deposition.Herein,this study presents a pioneering approach by introducing trace amounts of n-butanol as solvation regulators to engineer the homogenized Zn (H-Zn) anode with a uniform and dense structure.The interfacial reaction and structure evolution are explored by in/ex-situ experimental techniques,indicating that the H-Zn anode exhibits dendrite-free growth,no by-products,and weak hydrogen evolution,in sharp contrast to the bare Zn.Consequently,the H-Zn anode achieves a remarkable Zn utilization rate of approximately 20% and simultaneously sustains a prolonged cycle life exceeding 500 h.Moreover,the H-Zn//NH_(4)V_(4)O^(10)(NVO) full battery showcases exceptional cycle stability,retaining 95.04%capacity retention after 400 cycles at a large current density of 5 A g^(-1).This study enlightens solvation-regulated additives to develop Zn anode with superior utilization efficiency and extended operational lifespan.
基金supported by the Swedish Strategic Research Foundation(SSF FFL15-0174 to Zhen Zhang)the Swedish Research Council(VR 2018-06030 and 2019-04690 to Zhen Zhang)+1 种基金the Wallenberg Academy Fellow Extension Program(KAW 2020-0190 to Zhen Zhang)the Olle Engkvist Foundation(Postdoc grant 214-0322 to Zhen Zhang).
文摘Memristive crossbar arrays(MCAs)offer parallel data storage and processing for energy-efficient neuromorphic computing.However,most wafer-scale MCAs that are compatible with complementary metal-oxide-semiconductor(CMOS)technology still suffer from substantially larger energy consumption than biological synapses,due to the slow kinetics of forming conductive paths inside the memristive units.Here we report wafer-scale Ag_(2)S-based MCAs realized using CMOS-compatible processes at temperatures below 160℃.Ag_(2)S electrolytes supply highly mobile Ag+ions,and provide the Ag/Ag_(2)S interface with low silver nucleation barrier to form silver filaments at low energy costs.By further enhancing Ag+migration in Ag_(2)S electrolytes via microstructure modulation,the integrated memristors exhibit a record low threshold of approximately−0.1 V,and demonstrate ultra-low switching-energies reaching femtojoule values as observed in biological synapses.The low-temperature process also enables MCA integration on polyimide substrates for applications in flexible electronics.Moreover,the intrinsic nonidealities of the memristive units for deep learning can be compensated by employing an advanced training algorithm.An impressive accuracy of 92.6%in image recognition simulations is demonstrated with the MCAs after the compensation.The demonstrated MCAs provide a promising device option for neuromorphic computing with ultra-high energy-efficiency.
基金supported by the National Key R&D Program of China(2022YFA1604100)the National Natural Science Foundation of China(22302220,22372187,1972157,21972160,22402218)+2 种基金the National Science Fund for Distinguished Young Scholars of China(22225206)the Fundamental Research Program of Shanxi Province(202203021222403)the Youth Innovation Promotion Association CAS(2020179)。
文摘Carbon nanotube formation exemplifies atomically precise self-assembly,where atomic interactions dynamically engineer nanoscale architectures with emergent properties that transcend classical material boundaries.However,elucidating the transient molecular intermediates remains a critical mechanistic frontier.This study investigates the atomic-scale nucleation process of single-walled carbon nanotubes(SWCNTs)from acetylene on iron(Fe)clusters,utilizing GFN(-x)TB-based nanoreactor molecular dynamics simulations.The simulations reveal a consistent nucleation pathway,regardless of iron cluster size(Fe_(13),Fe_(38),Fe_(55)),where the chemisorption and dissociation of acetylene molecules on the Fe clusters lead to the formation of C_(2)H and C_(2)intermediates.These species then undergo oligomerization,initiating the growth of carbon chains.As the chains cross-link and cyclize,five-membered carbon rings are preferentially formed,which eventually evolve into six-membered rings and more complex sp2-hybridized carbon networks,resembling the cap structures of nascent SWCNTs.Although the nucleation mechanism remains similar across all cluster sizes,larger clusters show enhanced catalytic activity,leading to higher molecular weight hydrocarbons and more extensive carbocyclic networks due to their higher density of active sites per reacting molecule.Crucially,the study highlights the role of C_(2)H as the key active species in the carbon network formation process.These findings offer critical insights into the initial stages of SWCNT nucleation,contributing to a deeper understanding of the mechanisms driving SWCNT growth and guiding the development of optimized synthetic strategies.
基金supported by the National Natural Science Foundation of China(Grant Nos.U21A20130 and 52475357).
文摘1.Introduction Al-Zn-Mg-Cu alloy is a typical age-hardening aluminum alloy,its strength and toughness are significantly influenced by precipita-tion behavior.The nucleation mechanisms of precipitates in this alloy are generally categorized into homogeneous and heterogeneous nucleation.Homogeneous nucleation relies on structural and energy fluctuations within the solution to generate the driving force necessary for direct nucleation.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(No.2021R1C1C2006535)supported by the Korea Basic Science Institute(National Research Facilities and Equipment Center)grant funded by the Korea government(MSIT)(No.RS-2024-00403164)supported by the National Research Foundation of Korea grant funded by the Korea government,Ministry of Science and ICT(Development of Nanofiber Yarn Based Compound Sensor as a Comprehensive Wearable Healthcare Solution)(Grant No.RS-2024-00357296).
文摘The crystallization of ionic crystals has traditionally been explained by Gibbs's classical nucleation theory.However,recent observations of intermediate phases during nucleation suggest that the process may be more complex,necessitating new theoretical frameworks,though key empirical evidence remains elusive.In this study,we used microdroplets to investigate the crystallization of sodium halides(NaCl,NaBr,and NaI)under homogeneous nucleation conditions across a wide range of supersaturations.In the evaporating droplet,NaCl follows the classical nucleation pathway,whereas NaBr and NaI exhibit the formation of an intermediate phase prior to the nucleation of anhydrous and hydrous single crystals,respectively.Optical and computational analyses indicate that these intermediate phases are liquid crystal phases composed of contact ion pairs.These findings establish a new theoretical framework for crystal nucleation and growth and offer methods to control nucleation pathways,enabling us to achieve desired crystals regardless of specific conditions.
基金supported by the National Natural Science Foundation of China(12322406,12404208)the National Key R&D Program of China(2022YFA1403503)+2 种基金China Postdoctoral Science Foundation(2024M750970)the Science and Technology Program of Guangzhou(SL2024A04J00033)the Scientific Research lnnovation Project of Graduate School of South China Normal University.
文摘The unique structure and exceptional properties of two-dimensional(2D)materials offer significant potential for transformative advancements in semiconductor industry.Similar to the reliance on wafer-scale single-crystal ingots for silicon-based chips,practical applications of 2D materials at the chip level need large-scale,high-quality production of 2D single crystals.Over the past two decades,the size of 2D single-crystals has been improved to wafer or meter scale,where the nucleation control during the growth process is particularly important.Therefore,it is essential to conduct a comprehensive review of nucleation control to gain fundamental insights into the growth of 2D single-crystal materials.This review mainly focuses on two aspects:controlling nucleation density to enable the growth from a single nucleus,and controlling nucleation position to achieve the unidirectionally aligned islands and subsequent seamless stitching.Finally,we provide an overview and forecast of the strategic pathways for emerging 2D materials.
文摘pH-dependent multiple equilibria in cobalt sulfate-gluconate baths were calculated using stability constants adopted from literature.Changes of the bath speciation were then discussed in terms of spectrophotometric experiments and buffering properties of the solutions(pH 3-10).Cyclic voltammetry indicated changes in electrochemical behavior of cobalt species caused by different ionic compositions of the electrolytes.Tafel slopes were calculated and discussed in relation to electroreduction of cobalt species.Chronoamperometric studies showed 3D instantaneous nucleation of cobalt followed by diffusion-controlled growth,but it was disturbed at higher pH due to the release of cation from gluconate complexes as a limiting step.Diffusion coefficients of cobalt species were found.Changes in the pH were also reflected by modifications of morphology(SEM),development of preferred orientation planes(XRD,texture coefficients)and current efficiency,but not the thickness of the coatings deposited at constant potential of-1.0 V(vs Ag/AgCl).Anodic stripping analysis showed changes in anodic responses originated from the existence of preferentially oriented planes in cobalt layers.
基金support from the National Natural Science Foundation of China (22308233,92060101)the Natural Science Foundation of Sichuan Province of China (2024NSFSC1162)+1 种基金the Source of Origin Project of Beijing Power Machinery Research Institutethe Sichuan Province Science Fund for Distinguished Young Scholars (2021JDJQ0011)。
文摘The active cooling technology of endothermic hydrocarbon fuels is a key way to solve the thermal protection of high-speed aircraft engines,but the condensation coking problem during engine shutdown is a bottleneck that affects the reusability of aircraft.In this study,a self-designed apparatus was used to separately analyze the condensation coking during the fuel cooling process,and the coking characteristics under different temperature conditions were obtained.The condensation coking mechanism of fuel during cooling process was proposed based on the changes in physical properties of coking precursors obtained by the group contribution method.When the temperature drops to 300℃,not only the gas yield and conversion increase to 71.42% and 89.75% respectively,but the coke mass on the inner surface of the tube also significantly increases from 0.39 to 1.92 mg.Meanwhile,as the temperature further decreases,the morphology of coke gradually transforms into amorphous carbon with a higher degree of graphitization.During the cooling process,due to the liquefaction of coking precursors,their physical properties such as viscosity,density,and saturated vapor pressure undergo sudden changes at 300℃,leading to enhanced intermolecular physical interactions and promoting the physical aggregation of coking precursor molecules,which are deposited on the inner wall of the tube.This work provides a theoretical basis for the subsequent study of condensation coking mechanisms and inhibition methods.
基金Funded by the National Natural Science Foundation of China(Nos.51578412,51878479,52078372,and 52478272)the International Science and Technology Cooperation Project of the Key R&D Program of Science and Technology Innovation Yongjiang 2035(No.2024H023)。
文摘Four typical admixtures,polycarboxylate superplasticiser(PCE),tartaric acid(TA),sorbitol and polyacrylamide(PAM),were selected to systematically investigate their regulatory mechanisms on the formation of ettringite through Fourier transform infrared spectroscopy,X-ray diffraction,particle size analysis and nucleation kinetic model.The experimental results indicate that the admixtures alter the formation of ettringite through physical adsorption,complexation and solution viscosity modulation without changing its chemical structure.Low concentrations of PCE inhibit size growth by forming an adsorption layer on the surface of ettringite,whereas high concentrations of PCE alter the size change of ettringite by modulating the distribution of ionic concentrations.TA significantly reduces the size of ettringite by complexing Ca^(2+).Sorbitol and PAM promote the local growth of ettringite at low concentrations,leading to larger sizes.But at high concentrations,the size growth of ettringite is inhibited due to the increase in viscosity or the enhancement of complexation.Matlab nucleation kinetic modelling further shows that the addition of admixtures enhances the initial nucleation during ettringite synthesis,with values ranging from 14.45%to 114.25%.However,the subsequent nucleation rate of ettringite is significantly affected,decreasing by 12.79%to 71.74%.The results provide a theoretical basis for the design of ettringite materials and the optimisation of the application of admixtures.
基金supported by the National Natural Science Foundation of China(Grant Nos.52274339,52174321,52074186,and 52104337)Natural Science Foundation of Jiangsu Province(Grant No.BK20231317)China Baowu Low-Carbon Metallurgy Innovation Fund(Grant No.BWLCF202108).
文摘To investigate the nucleation behavior during the single-phased metallic solidification process,the commercial ultrapure ferritic stainless steels with no(Initial steel)and various melt treatments(R1,MR1,Y2,MY1,and M1 steels)were used to carry out the differential scanning colorimetry(DSC)and high-temperature confocal laser scanning microscope(HT-CLSM)experiments.Based on the results of DSC experiments,the equilibrium solidification process as well as the relationship among the critical undercooling degree(△T_(c)^(DSC)),latent heat of fusion/crystallization(△H_(f)/△H_(c)),equiaxed grain ratio(ER),and average grain size(△_(ave)^(ingot))was revealed.ER is increased with the decreasing△T_(c)^(DSC)and increasing△H_(f)/△H_(c);however,△_(ave)^(ingot)is decreased with them.Referring to the results of HT-CLSM experiments,the average sizes of micro-/macrostructures(d_(ave)/D_(ave)/)are decreased with the increasing cooling rate,as well as the difference between and apparent critical undercooling degree(△T_(c)^(CLSM))was revealed.The heterogeneous nucleation of the crystal nuclei occurs only if△T_(c)^(CLSM)>△T_(c)^(DSC).Combining with the interfacial wetting-lattice mismatch heterogeneous nucleation model,the dynamic mechanism of the metallic solidification was revealed.The as-cast grains of the melt-treated samples were obviously refined,owing to the much higher actual heterogeneous nucleation rates(I_(heter.,i))obtained through melt treatments,and the heterogeneous nucleation rates(I_(heter.,ij))for all samples are increased with the cooling rates,firmly confirming that the as-cast grains of each sample could be refined by the increasing cooling rates.
