NONSTABLE GROWTH OF Al-Si EUTECTIC IN CONSTRAINED CONDITION

Nonstable growth of Al-Si eutectic in constrained condition has been investigated by means of change of the withdrawing rate in an unidirectional solidification system,In constant acceleration growth,a retarded effect of response of eutectic interflake spacing on the growth rate has been observed.The response mechanisms are cluster-branching and local termination extension of Si-phase.In constant deceleration growth,the cluster-branching and termina- tion mechanisms of silicon still control adjustment of the interflake spacing,but the spacing is determined by the initial growth rate and does not respond to the decreasing growth rate.

A NUMERICAL MODEL OF LAMELLAR SPACING OF Al-Si EUTECTIC

A numerical model is established to simulate the concentration field in irregular lamel- lar eutectic of Al-Si system. Both the undercooling and spacing are dependent on the growth rate and the temperature gradient, and increasing growth rate causes an in- crease of undercooling but a decrease of lamellar spacing, while increasing temperature gradient Leads to a decrease of Lamellar spacing. The computed results are in good agreement with experimental observations.

Insight into the experiment and extraction mechanism for separating carbazole from anthracene oil with quaternary ammonium-based deep eutectic solvents

Carbazole is an irreplaceable basic organic chemical raw material and intermediate in industry.The separation of carbazole from anthracene oil by environmental benign solvents is important but still a challenge in chemical engineering.Deep eutectic solvents (DESs) as a sustainable green separation solvent have been proposed for the separation of carbazole from model anthracene oil.In this research,three quaternary ammonium-based DESs were prepared using ethylene glycol (EG) as hydrogen bond donor and tetrabutylammonium chloride (TBAC),tetrabutylammonium bromide or choline chloride as hydrogen bond acceptors.To explore their extraction performance of carbazole,the conductor-like screening model for real solvents (COSMO-RS) model was used to predict the activity coefficient at infinite dilution (γ^(∞)) of carbazole in DESs,and the result indicated TBAC:EG (1:2) had the stronger extraction ability for carbazole due to the higher capacity at infinite dilution (C^(∞)) value.Then,the separation performance of these three DESs was evaluated by experiments,and the experimental results were in good agreement with the COSMO-RS prediction results.The TBAC:EG (1:2) was determined as the most promising solvent.Additionally,the extraction conditions of TBAC:EG (1:2) were optimized,and the extraction efficiency,distribution coefficient and selectivity of carbazole could reach up to 85.74%,30.18 and 66.10%,respectively.Moreover,the TBAC:EG (1:2) could be recycled by using environmentally friendly water as antisolvent.In addition,the separation performance of TBAC:EG (1:2) was also evaluated by real crude anthracene,the carbazole was obtained with purity and yield of 85.32%,60.27%,respectively.Lastly,the extraction mechanism was elucidated byσ-profiles and interaction energy analysis.Theoretical calculation results showed that the main driving force for the extraction process was the hydrogen bonding ((N–H...Cl) and van der Waals interactions (C–H...O and C–H...π),which corresponding to the blue and green isosurfaces in IGMH analysis.This work presented a novel method for separating carbazole from crude anthracene oil,and will provide an important reference for the separation of other high value-added products from coal tar.

Study on the green extraction of corncob xylan by deep eutectic solvent

Corn as one of the world's major food crops,its by-product corn cob is also rich in resources.However,the unreasonable utilization of corn cob often causes the environmental pollution,waste of resources and other problems.As one of the most abundant polymers in nature,xylan is widely used in food,medicine,materials and other fields.Corn cob is rich in xylan,which is an ideal raw material for extracting xylan.However,the intractable lignin is covalently linked to xylan,which increases the difficulty of xylan extraction.It has been reported that the deep eutectic solvent(DES)could preferentially dissolve lignin in biomass,thereby dissolving the xylan.Then,the xylan in the extract was separated by ethanol precipitation method.The xylan precipitate was obtained after centrifugation,while the supernatant was retained.The components of the supernatant after ethanol precipitation were separated by the rotary evaporator.The ethanol,water and DES were collected for the subsequent extraction of corn cob xylan.In this study,a novel way was provided for the green production of corn cob xylan.The DES was used to extract xylan from corn cob which was used as the raw material.The effects of solid-liquid ratio,reaction time,reaction temperature and water content of DES on the extraction rate of corn cob xylan were investigated by the single factor test.Furthermore,the orthogonal test was designed to optimize the xylan extraction process.The structure of corn cob xylan was analyzed and verified.The results showed that the optimum extraction conditions of corn cob xylan were as follows:the ratio of corn cob to DES was 1:15(g:mL),the extraction time was 3 h,the extraction temperature was 60℃,and the water content of DES was 70%.Under these conditions,the extraction rate of xylan was 16.46%.The extracted corn cob xylan was distinctive triple helix of polysaccharide,which was similar to the structure of commercially available xylan.Xylan was effectively and workably extracted from corn cob by the DES method.This study provided a new approach for high value conversion of corn cob and the clean production of xylan.

Efficient and reversible separation of NH_(3) by deep eutectic solvents with multiple active sites and low viscosities

The efficient separation and collection of ammonia(NH_(3))during NH_(3) synthesis process is essential to improve the economic efficiency and protect the environment.In this work,ethanolammonium hydrochloride(EtOHACl)and phenol(PhOH)were used to prepare a novel class of deep eutectic solvents(DESs)with multiple active sites and low viscosities.The NH_(3) separation performance of EtOHACl+PhOH DESs was analyzed completely.It is figured out that the NH_(3) absorption rates in EtOHACl+PhOH DESs are very fast.The NH_(3) absorption capacities are very high and reach up to 5.52 and 10.74 mol·kg1 at 11.2 and 100.4 kPa under 298.2 K,respectively.In addition,the EtOHACl+PhOH DESs present highly selective absorption of NH_(3) over N_(2) and H_(2) and good regenerative properties after seven cycles of absorption/desorption.The intrinsic separation mechanism of NH_(3) by EtOHACl+PhOH DESs was further revealed by spectroscopic analysis and quantum chemistry calculations.

Sodium Nitrate/Formamide Deep Eutectic Solvent as Flame-Retardant and Anticorrosive Electrolyte Enabling 2.6 V Safe Supercapacitors with Long Cyclic Stability

Safe operation of electrochemical capacitors(supercapacitors)is hindered by the flammability of commercial organic electrolytes.Non-flammable Water-in-Salt(WIS)electrolytes are promising alternatives;however,they are plagued by the limited operation voltage window(typically≤2.3 V)and inherent corrosion of current collectors.Herein,a novel deep eutectic solvent(DES)-based electrolyte which uses formamide(FMD)as hydrogen-bond donor and sodium nitrate(NaNO_(3))as hydrogen-bond acceptor is demonstrated.The electrolyte exhibits the wide electrochemical stability window(3.14 V),high electrical conductivity(14.01 mScm^(-1)),good flame-retardance,anticorrosive property,and ultralow cost(7%of the commercial electrolyte and 2%of WIS).Raman spectroscopy and Density Functional Theory calculations reveal that the hydrogen bonds between the FMD molecules and NO_(3)^(-)ions are primarily responsible for the superior stability and conductivity.The developed NaNO_(3)/FMD-based coin cell supercapacitor is among the best-performing state-of-art DES and WIS devices,evidenced by the high voltage window(2.6 V),outstanding energy and power densities(22.77 Wh kg^(-1)at 630 W kg^(-1)and 17.37 kW kg^(-1)at 12.55 Wh kg^(-1)),ultralong cyclic stability(86%after 30000 cycles),and negligible current collector corrosion.The NaNO_(3)/FMD industry adoption potential is demonstrated by fabricating 100 F pouch cell supercapacitors using commercial aluminum current collectors.

Oxidative Desulfurization of Fuel Oil with H_(3)PO_(4)-based Deep Eutectic Solvents

A series of Lewis-acid deep eutectic solvents (DESs) were synthesized by stirring phosphoric acid and zincchloride as raw materials at 80℃ to form H_(3)PO_(4)/nZnCl_(2) (n = 0.1, 0.25, 0.5, 0.75, 1). The DESs were characterized byFourier transform infrared spectrophotometry (FT-IR), thermogravimetry/differential thermogravimetry (TG/DTG), andelectron spray ionization mass spectrometry (ESI-MS). The DESs were used as both extractants and catalysts to removedibenzothiophene from fuels via oxidative desulfurization (ODS). Experiments were performed to investigated the influenceof factors such as composition of DES, temperature, oxidant dosage (molar ratio of O:S), DES dosage (volume ratio ofDES:oil), and number of cycles on desulfurization rate. The results indicated that the removal rate of dibenzothiophene (DBT)was affected by the Lewis acidic DESs, with that of H_(3)PO_(4)/0.25∙ZnCl_(2) reaching 96.4% under optimal conditions (Voil=5 mL,VDES=1 mL, an oxidant dosage of 6, T=50 ℃). After six cycles, the desulfurization rate of H_(3)PO_(4)/0.25∙ZnCl_(2) remained above94.1%. The apparent activation energy of dibenzothiophene (DBT) removal reaction was determined by a pseudo-first orderkinetic equation according to the Arrhenius equation to be 32.34 kJ/mol, as estimated. A reaction mechanism is proposedbased on the experimental data and characterization results.

Machine-Learning-Assisted Design of Deep Eutectic Solvents Based on Uncovered Hydrogen Bond Patterns

Non-ionic deep eutectic solvents(DESs)are non-ionic designer solvents with various applications in catalysis,extraction,carbon capture,and pharmaceuticals.However,discovering new DES candidates is challenging due to a lack of efficient tools that accurately predict DES formation.The search for DES relies heavily on intuition or trial-and-error processes,leading to low success rates or missed opportunities.Recognizing that hydrogen bonds(HBs)play a central role in DES formation,we aim to identify HB features that distinguish DES from non-DES systems and use them to develop machine learning(ML)models to discover new DES systems.We first analyze the HB properties of 38 known DES and 111 known non-DES systems using their molecular dynamics(MD)simulation trajectories.The analysis reveals that DES systems have two unique features compared to non-DES systems:The DESs have①more imbalance between the numbers of the two intra-component HBs and②more and stronger inter-component HBs.Based on these results,we develop 30 ML models using ten algorithms and three types of HB-based descriptors.The model performance is first benchmarked using the average and minimal receiver operating characteristic(ROC)-area under the curve(AUC)values.We also analyze the importance of individual features in the models,and the results are consistent with the simulation-based statistical analysis.Finally,we validate the models using the experimental data of 34 systems.The extra trees forest model outperforms the other models in the validation,with an ROC-AUC of 0.88.Our work illustrates the importance of HBs in DES formation and shows the potential of ML in discovering new DESs.

Research Progress of Deep Eutectic Solvents in Extraction of Plant Flavonoids

As a new type of green solvents,deep eutectic solvents(DESs)have the advantages of strong extraction ability,designability,simple preparation,low price,recoverability and biodegradation,and show great application potential in the field of plant flavonoid extraction.In this paper,the definition,classification and preparation methods of DESs were introduced.The effects of DES composition,molar ratio of DES components,water content of DES systems,liquid-material ratio,extraction temperature,extraction time and extraction auxiliary techniques on the extraction yield of plant flavonoids were expounded.The recycling methods of DESs were summarized.Existing problems of DESs in the field of plant flavonoids extraction were pointed out,and further research direction and trend were analyzed and prospected.

Stoichiometry and Stability Constant Values for Copper (II) Chelates with Ethylene Diamine in Deep Eutectic Solvents (DES) (Ethaline) Solutions

In this study we used the deep eutectic solvents (ionic liquids) to investigate the reaction between copper (II) with ethylene diamine (en). Two of the existing methods for analyzing spectrophotometric measurements have been applied for establishing, the stoichiometry and whenever possible, the stability constants of the chelates formed. The method of continuous variations was necessary to determine first whether, the metal ion and the ligand ethylene diamine form one or more than one chelate, when more than one chelate formed, the results obtained depend on the wavelength and for meaningful conclusions the wavelengths were carefully selected. The empirical formulae of the chelates were further substantiated by the molar ratio method. The effect of time and temperature on the formation and stability of these chelates in solution is also studied. The stability constants, K1 and K2 for the copper (II) chelates were calculated, though reliable, and are comparable to literature values.

Nucleation and growth of eutectic cell in hypoeutectic Al-Si alloy

The nucleation and growth of eutectic cell in hypoeutectic Al-Si alloy was investigated using optical microscopy and scanning electron microscopy equipped with electron backscattering diffraction（EBSD）.By revealing the eutectic cells and analyzing the crystallographic orientation,it was found that both the eutectic Si and Al phases in an eutectic cell were not single crystal,representing an eutectic cell consisting of small ＇grains＇.It is also suggested that the eutectic nucleation mode can not be determined based on the crystallographic orientation between eutectic Al phases and the neighboring primary dendrite Al phases.However,the evolution of primary dendrite Al phases affects remarkably the following nucleation and growth of eutectic cell.The coarse flake-fine fibrous transition of eutectic Si morphology involved in impurity elements modification may be independent of eutectic nucleation.

Effect of addition of Al-Si eutectic alloy on microstructure and mechanical properties of Mg-12wt%Li alloy

Mg-12 Li, Mg-12 Li-3（Al-Si）, Mg-12 Li-7（Al-Si） and Mg-12 Li-9（Al-Si） alloys（all in wt%） were fabricated by high frequency vacuum induction melting in a water cooled copper crucible. After subsequently hotrolling and annealing, their microstructure and mechanical properties were investigated. Experimental results show that mechanical properties of Mg-12 Li alloy were significantly improved by the addition of Al-Si eutectic alloy. Mg-12 Li-7（Al-Si） alloy shows the highest strength of 196 MPa of the investigated alloys, which is about 1.8 times of the strength of Mg-12 Li alloy, and maintains high elongation of 27%.The improved mechanical property with addition of Al and Si in the eutectic proportion into Mg-12 Li alloy was attributed to the solution strengthening effect of A1 and precipitation hardening effect from AlLi and Mg_2 Si precipitates.

Growth mechanism of primary silicon in cast hypoeutectic Al-Si alloys

The microstructural features of hypoeutectic AI-10%Si alloy were observed using optical microscopy and electron backscatter diffraction. The results show that primary silicon particles are frequently found in hypoeutectic alloys. Hence, the nucleation and growth mechanisms of the precipitation of primary silicon of hypoeutectic Al-10%Si alloy melts were investigated. It was discovered that Si atoms are easy to segregate and form Si-Si clusters, which results in the formation of primary silicon even in eutectic or hypoeutectic Al-Si alloys. In addition, solute redistribution caused by chemical driving force and large pile-ups or micro-segregation of the solute play an important role in the formation of the primary silicon, and the solute redistribution equations were derived from Jackson-Chalmers equations. Once Si solute concentration exceeds eutectic composition, primary silicon precipitates are formed at the front of solid/liquid interface.

Effect of ultrasonic vibration on Fe-containing intermetallic compounds of hypereutectic Al-Si alloys with high Fe content

The Fe-containing intermetallic compounds with high melting point in hypereutectic Al-Si alloys can improve the heat resistance and wear resistance at elevated temperatures. However, the long needle-like Fe-containing compounds in the alloys produced by conventional casting process are detrimental to the strength of matrix. The effect of ultrasonic vibration （USV） on the morphology change of Fe-containing intermetallic compounds in the hypereutectic Al-17Si-xFe （x=2, 3, 4, 5） alloys was systematically studied. The results show that, the Fe-containing intermetallic compounds are mainly composed of long needle-like β-Al5FeSi phase with a small amount of plate-like δ-Al4FeSi2 phase in Al-17Si-2Fe alloy produced by conventional casting process. With the increase of Fe content from 2% to 5% in the alloys, the amount of plate-like or coarse needle-like δ-Al4FeSi2 phase increases while the amount of long needle-like β-Al5FeSi phases decreases. In Al-17Si-5Fe alloy, the Fe-containing intermetallic compounds exist mainly as coarse needle-like δ-Al4FeSi2 phase. After USV treatment, the Fe-containing compounds in the Al-17Si-xFe alloys are refined and exist mainly as δ-Al4FeSi2 particles, with average grain size ranging from 26 μm to 37 μm, and only a small amount of β-Al5FeSi phases remain. The mechanism of USV on the morphology of Fe-containing intermetallic compounds was also discussed.

Microstructure evolution of spray-formed hypereutectic Al-Si alloys in semisolid reheating process

The Al-27%Si alloy was prepared by the spray forming process,and its microstructure evolution during the semisolid reheating process was investigated.The results show that,the primary Si phase coarsens during the reheating process and the coarsening rate increases with the increase of reheating temperature.The eutectic phase is produced in the molten region when quenched in the cold water.The microstructure evolution in the semisolid state can be divided into three stages.The remarkable characteristic of the first stage is only a solid-state phase transformation process.However,the region around the α（Al） matrix gradually melts in the second stage.The primary Si in the liquid phase coarsens obviously,and the eutectic phase is produced in the molten region when the specimens are quenched in cold water.In the last stage,the same thing as that in the second stage happens except that all the α（Al） matrixes are melted.

Grain refining mechanism of Al-3B master alloy on hypoeutectic Al-Si alloys

Al-3B master alloy is a kind of efficient grain refiner for hypoeutectic Al-Si alloys. Experiments were carried out to evaluate the effect of undissolved AlB2 particles in Al-3B master alloy on the grain refinement of Al-7Si. It is found that the number and the settlement of AlB2 particles in the melt all have effect on the grain refining efficiency. On the basis of experiments and theoretical analysis, a new grain refinement mechanism was proposed to explain the grain refinement action of Al-3B on hypoeutectic Al-Si alloys. The formation of ＇Al-AlB2＇ shell structure is the direct reason for grain refinement and the undissolved AlB2 particles is the indirect nucleating base for subsequent α（Al） phase.

Dry sliding wear behavior of rheocast hypereutectic Al-Si alloys with different Fe contents

The effect of iron content on wear behavior of hypereutectic Al?17Si?2Cu?1Ni alloy produced by rheocasting process was investigated. The dry sliding wear tests were carried out with a pin-on-disk wear tester. The results show that the wear rate of the rheocast alloy is lower than that of the alloy produced by conventional casting process under the same applied load. The fine particle-likeδ-Al4(Fe,Mn)Si2 and polygonalα-Al15(Fe,Mn)3Si2 phases help to improve the wear resistance of rheocast alloys. As the volume fraction of fine Fe-bearing compounds increases, the wear rate of the rheocast alloy decreases. Moreover, the wear rate of rheocast alloy increases with the increase of applied load from 50 to 200 N. For the rheocast alloy with 3% Fe, oxidation wear is the main mechanism at low applied load (50 N). At higher applied loads, a combination of delamination and oxidation wear is the dominant wear mechanism.

Self tempering effect of near eutectic Al-Si casting with different wall thickness solidified and cooled in permanent die

In order to study the self tempering effect on the solidification of Al-Si alloy, a setup was designed to conduct experiments. The characters of β phases in different thicknesses of Al-Si samples were investigated. The results show that the size distributions of β phases obey the logarithmic normal distribution. The Brinell hardness tests were also carried out. The tested hardness results show that the hardness distribution of the casting cooled in water is evener than that cooled in air, and its averaged value is higher than that cooled in air.

Sr含量对Al-Si合金显微组织和热导率的影响

以纯铝、Al-20Si和Al-10Sr中间合金为原料,Sr为变质剂(含量为0.01%、0.02%、0.04%和0.06%,质量分数),制备了Al-7Si-xSr、Al-12Si-xSr和Al-20Si-xSr合金,研究了Sr含量对Al-Si合金相变储热材料显微组织及热导率的影响。利用Hot Disk热常数分析仪测量合金的热导率,通过扫描电镜观察及分析合金的显微组织。结果表明:在Al-Si合金中添加变质元素Sr会影响合金的热导率,Al-7Si-0.04Sr合金热导率较Al-7Si合金增加了73.47 W·m^(-1)·K^(-1),Al-20Si-0.04Sr合金的热导率较Al-20Si合金增加了24.09 W·m^(-1)·K^(-1),Al-12Si-0.04Sr合金的热导率较Al-12Si合金增加了17.79 W·m^(-1)·K^(-1)。铝硅合金热导率的增长主要与α(Al)、共晶硅和初晶硅的形貌有关。经过Sr变质之后,Al-7Si合金中共晶Si立体形貌均由片层状转变为珊瑚状,Al-12Si和Al-20Si合金中共晶Si立体形貌由片层状转变为枝条状;其中,Al-7Si合金中α(Al)尺寸明显减少、排列紧密,二次枝晶臂间距逐渐减小;Al-20Si合金中的初晶Si尺寸明显减小,其形貌由多角的大块状变为小块状;α(Al)形态的转变不仅能够为自由电子的传输提供快速通道,而且还会使得共晶Si的排列更加规则,减少自由电子发生散射的几率,对合金的热导率影响较大。共晶Si由片层状转变为珊瑚状或枝条状,增加电子的平均自由程,有利于电子的传输。Al-20Si合金的热导率与初晶Si的形态有着重要联系,大尺寸且形状完整的初晶Si会发生晶格振动,会提高合金的热导率。

Effects of Mg content on primary Mg_2Si phase in hypereutectic Al-Si alloys

Hypereutectic Al-Si alloy with variant Mg contents were fabricated by casting,and the effects of Mg content on the microstructure of primary Mg2Si particles in hypereutectic Al-Si alloys were investigated.The results show that the volume fraction of primary Mg2Si particles increases linearly with raising the Mg content,but the average size of Mg2Si particles does not exhibit a corresponding change.When the Mg content is 3%,á1 0 0？ directions have the fastest growth velocity,so that Mg2Si particles are likely to form octahedron shape.When gradually increasing the Mg content,the distributions of Mg and Si atoms on the solid-liquid interface become inhomogeneous,which results in the formation of irregular octahedron structures.Finally,when the Mg content is about 10%,the morphology of primary Mg2Si particles changes from the octahedron shape into various complex structures with a large size.