Sn nucleation and growth from Sn(II)dissolved in ethylene glycol:Electrochemical behavior and temperature effect

Thermodynamic and kinetic aspects of Sn nucleation and growth processes onto a glassy carbon electrode from SnCl2·2H2O dissolved in ethylene glycol solutions were studied.Typical reduction and oxidation peaks observed in voltammograms have demonstrated the capability of ethylene glycol solutions to electrodeposit Sn.The temperature-dependence of diffusion coefficient values derived from potentiodynamic and potentiostatic studies helped to determine and validate estimations of the activation energy for Sn(II)bulk diffusion.Chronoamperometric results have identified that,the suitable model to describe the early stage of Sn electrodeposition could be composed of Sn three-dimensional nucleation and diffusion-controlled growth and water reduction contributions,which was duly validated by theoretical and experimental approaches.From the model,typical kinetic parameters such as the nucleation frequency of Sn(A),number density of Sn nuclei(N_(0)),and diffusion coefficient of Sn(II)ions(D),were determined.The presence of Sn nuclei with excellent quality and their structures were verified using SEM,EDX,and XRD techniques.

Ribosome-inspired electrocatalysts inducing preferential nucleation and growth of three-dimensional lithium sulfide for high-performance lithium-sulfur batteries

Nucleation of lithium sulfide(Li_(2)S)induced by electrocatalysts plays a crucial role in mitigating the shut-tle effect.However,short-chain polysulfides on electrocatalysts surfaces tend to re-dissolve into elec-trolytes,delaying Li_(2)S supersaturation and its nucleation.In this study,we draw inspiration from the ribosome-driven protein synthesis process in cells to prepare ultrasmall nitrogen-doped MoS_(2) nanocrys-tals anchored on porous nitrogen-doped carbon networks(N-MoS_(2)-NC)electrocatalysts.Excitedly,the ex-situ SEM demonstrates that ribosome-inspired N-MoS_(2)-NC electrocatalysts induce early nucleation and rapid growth of three-dimensional Li_(2)s during discharge.Theoretical calculations reveal that the Li-s bond length in N-MoS_(2)-Li_(2)S(100)is shorter,and the corresponding interfacial formation energy is lower than in MoS_(2)-Li_(2)S(100).This accelerated conversion of lithium polysulfides to Li_(2)S can enhance the utilization of active substances and inhibit the shuttle effect.This study highlights the potential of ribosome-inspired N-MoS_(2)-NC in improving the electrochemical stability of Li-S batteries,providing valuable insights for future electrocatalyst design.

Na_(3)P interphase reduces Na nucleation energy enabling stable anode-less sodium metal batteries

Sodium metal batteries(SMBs)are rising as viable alternatives to lithium-ion systems due to their superior energy density and sodium's relative abundance.However,SMBs face significant impediments,particularly the exceedingly high negative-to-positive capacity ratios(N/P ratios)which severely encumber energy density and hinder their practical application.Herein,a novel nucleophilic Na_(3)P interphase on aluminum foil has been designed to significantly lower the nucleation energy barrier for sodium atom deposition,resulting in a remarkable reduction of nucleation overpotential and efficient mitigation of dendritic growth at high sodium deposition of 5 mA h cm^(−2).The interphase promotes stable cycling in anode-less SMB configurations with a low N/P ratio of 1.4 and high cathode mass loading of 11.5 mg cm^(−2),and demonstrates a substantial increase in high capacity retention of 92.4%after 500 cycles even under 1 C rate condition.This innovation signifies a promising leap forward in the development of high-energy-density,anode-less SMBs,offering a potential solution to the longstanding issues of cycle stability and energy efficiency.

Driving inward growth of lithium metal in hollow microcapsule hosts by heteroatom‐controlled nucleation

The application of Li metal anodes in rechargeable batteries is impeded by safety issues arising from the severe volume changes and formation of dendritic Li deposits.Three‐dimensional hollow carbon is receiving increasing attention as a host material capable of accommodating Li metal inside its cavity;however,uncontrollable and nonuniform deposition of Li remains a challenge.In this study,we synthesize metal–organic framework‐derived carbon microcapsules with heteroatom clusters(Zn and Ag)on the capsule walls and it is demonstrated that Ag‐assisted nucleation of Li metal alters the outward‐to‐inward growth in the microcapsule host.Zn‐incorporated microcapsules are prepared via chemical etching of zeolitic imidazole framework‐8 polyhedra and are subsequently decorated with Ag by a galvanic displacement reaction between Ag^(+) and metallic Zn.Galvanically introduced Ag significantly reduces the energy barrier and increases the reaction rate for Li nucleation in the microcapsule host upon Li plating.Through combined electrochemical,microstructural,and computational studies,we verify the beneficial role of Ag‐assisted Li nucleation in facilitating inward growth inside the cavity of the microcapsule host and,in turn,enhancing electrochemical performance.This study provides new insights into the design of reversible host materials for practical Li metal batteries.

Nucleation of Supercooled Water by Neutrons: Latitude Dependence and Implications for Cloud Modelling

It has recently been shown that incident particles, neutrons, can initiate the freezing in a supercooled water volume. This new finding may have ramifications for the interpretation of both experimental data on the nucleation of laboratory samples of supercooled water and perhaps more importantly on the interpretation of ice nucleation involved in cloud physics. For example, if some fraction of the cloud nucleation previously attributed to dust, soot, or aerosols has been caused by cosmogenic neutrons, fresh consideration is required in the context of climate models. Moreover, as cosmogenic neutrons, most being muon-induced, have much greater flux at high latitudes, estimates of ice nucleates in these regions may be larger than required to accurately model cloud and condensation properties. This discrepancy has been pointed out in IPCC reports. Our paper discusses the connection between the new concept of neutrons nucleating supercooled water and the need for a new source of nucleation in high latitude clouds, ideally causing others to review current data, or to analyse future data with this idea in mind. .

Highly Reversible Zn Metal Anodes Enabled by Increased Nucleation Overpotential

Dendrite formation severely compromises further development of zinc ion batteries. Increasing the nucleation overpotential plays a crucial role in achieving uniform deposition of metal ions. However, this strategy has not yet attracted enough attention from researchers to our knowledge. Here, we propose that thermodynamic nucleation overpotential of Zn deposition can be boosted through complexing agent and select sodium L-tartrate(Na-L) as example. Theoretical and experimental characterization reveals L-tartrate anion can partially replace H_(2)O in the solvation sheath of Zn^(2+), increasing de-solvation energy. Concurrently, the Na^(+) could absorb on the surface of Zn anode preferentially to inhibit the deposition of Zn^(2+) aggregation. In consequence, the overpotential of Zn deposition could increase from 32.2 to 45.1 mV with the help of Na-L. The Zn-Zn cell could achieve a Zn utilization rate of 80% at areal capacity of 20 mAh cm^(-2). Zn-LiMn_(2)O_(4) full cell with Na-L additive delivers improved stability than that with blank electrolyte. This study also provides insight into the regulation of nucleation overpotential to achieve homogeneous Zn deposition.

Nucleation and growth control for iron-and phosphorus-rich phases from a modified steelmaking waste slag

Recovering the iron(Fe)and phosphorus(P)contained in steelmaking slags not only reduces the environmental burden caused by the accumulated slag,but also is the way to develop a circular economy and achieve sustainable development in the steel industry.We had pre-viously found the possibility of recovering Fe and P resources,i.e.,magnetite(Fe_(3)O_(4)) and calcium phosphate(Ca_(10)P_(6)O_(25)),contained in steel-making slags by adjusting oxygen partial pressure and adding modifier B_(2)O_(3).As a fundamental study for efficiently recovering Fe and P from steelmaking slag,in this study,the crystallization behavior of the CaO-SiO_(2)-FeO-P_(2)O_(5)-B_(2)O_(3) melt has been observed in situ,using a confocal scanning laser microscope(CLSM).The kinetics of nucleation and growth of Fe-and P-rich phases have been calculated using a classical crys-tallization kinetic theory.During cooling,a Fe_(3)O_(4) phase with faceted morphology was observed as the 1st precipitated phase in the isothermal interval of 1300-1150℃,while Ca_(10)P_(6)O_(25),with rod-shaped morphology,was found to be the 2nd phase to precipitate in the interval of 1150-1000℃.The crystallization abilities of Fe_(3)O_(4) and Ca_(10)P_(6)O_(25) phases in the CaO-SiO_(2)-FeO-P_(2)O_(5)-B_(2)O_(3) melt were quantified with the in-dex of(T_(U)−T_(I))/T_(I)(where T_(I) represents the peak temperature of the nucleation rate and TU stands for that of growth rate),and the crystalliza-tion ability of Fe_(3)O_(4) was found to be larger than that of Ca_(10)P_(6)O_(25) phase.The range of crystallization temperature for Fe_(3)O_(4) and Ca_(10)P_(6)O_(25) phases was optimized subsequently.The Fe_(3)O_(4) and Ca_(10)P_(6)O_(25) phases are the potential sources for ferrous feedstock and phosphate fertilizer,respectively.

Inner-pore reduction nucleation of palladium nanoparticles in highly conductive wurster-type covalent organic frameworks for efficient oxygen reduction electrocatalysis

Covalent organic frameworks(COFs)have emerged as a class of promising supports for electrocatalysis because of their advantages including good crystallinity,highly ordered pores,and structural diversity.However,their poor conductivity represents the main obstruction to their practical application.Here,we reported a novel synthesis strategy for synergistically endowing a triphenylamine-based COFs with improved electrical conductivity and excellent catalytic activity for oxygen reduction,via the in-situ redox deposition and confined growth of palladium nanoparticles inside the porous structure of COFs using reductive triphenylamine frameworks as reducing agent;meanwhile,the triphenylamine unit was oxidized to radical cation structure and affords radical cation COFs with conductivity as high as3.2*10^(-1) S m^(-1).Such a uniform confine palladium nanoparticle on highly conductive COFs makes it an efficient electrocatalyst for four-electron oxygen reduction reaction(4e-ORR),showing excellent activities and fast kinetics with a remarkable half-wave potential(E_(1/2))of 0.865 V and an ultralow Tafel slope of 39.7 mV dec^(-1) in alkaline media even in the absence of extra commercial conductive fillers.The generality of this strategy was proved by preparing the different metal and metal alloy nanoparticles supported on COFs(Au@COF,Pt@COF,AuPd@COF,AgPd@COF,and PtPd@COF)using reductive triphenylamine frameworks as reducing agent.This work not only provides a facile strategy for the fabrication of highly conductive COF supported ORR electrocatalysts,but also sheds new light on the practical application of Zn-air battery.

Simultaneous refinement of α-Mg grains and β-Mg_(17)Al_(12) in Mg-Al based alloys via heterogeneous nucleation on Al_(8)Mn_(4)Sm

Due to the significant differences in the formation temperature and crystal structure between the primaryα-Mg and eutecticβ-Mg_(17)Al_(12),it is a great challenge to achieve simultaneous refinement of the primary and eutectic phases in Mg-Al based alloys via heterogeneous nucleation.Surprisingly,we found that theα-Mg andβ-Mg_(17)Al_(12) in the AZ80 alloy can be simultaneously refined after 0.2 wt.%Sm addition,with the grain size decreasing from∼217±15μm to∼170±10μm and theβ-Mg_(17)Al_(12) morphology changing from a typical continuous network to a nod-like or spherical structure.The simultaneous refinement mechanism is investigated through solidification simulation,transmission electron microscopy(TEM),and differential thermal analysis(DTA).In the AZ80-0.2Sm alloy,many Al8Mn4Sm particles can be observed near the center of theα-Mg grains or inside theβ-Mg_(17)Al_(12).Crystallographic calculations further reveal that the Al8Mn4Sm has good crystallographic matching with both theα-Mg andβ-Mg_(17)Al_(12),so it possesses the potency to serve as heterogeneous nucleation sites for both phases.The promoted heterogeneous nucleation on the Al8Mn4Sm decreases the undercooling required by the nucleation of the primary and eutectic phases,which enhances the heterogeneous nucleation rate,thus causing the simultaneous refinement of theα-Mg andβ-Mg_(17)Al_(12).The orientation relationships between the Al8Mn4Sm and Mg/Mg_(17)Al_(12) are identified,which are[1210]_(Mg)//[010]_(Al8Mn4Sm),(1010)_(Mg)//(301)_(Al8Mn4Sm) and[112]_(Mg_(17)Al_(12))//[010]_(Al8Mn4Sm),(110)_(Mg_(17)Al_(12))//(301)_(Al8Mn4Sm),respectively.Furthermore,the refinement of theβ-Mg_(17)Al_(12) accelerates its dissolution during the solution treatment,which is beneficial for cost saving in industrial applications.Other Al8Mn4RE compounds such as Al8Mn4Y might have the same positive effect on the simultaneous refinement due to the similar physicochemical properties of rare earth elements.This work not only proves the possibility of simultaneously refining the primary and eutectic phases in Mg-Al based alloys via heterogeneous nucleation,but also provides new insights into the development of refiners for cast Mg alloys.

Different roles of surfaces’ interaction on lattice mismatched/matched surfaces in facilitating ice nucleation

The freezing of water is one of the most common processes in nature and affects many aspects of human activity. Ice nucleation is a crucial part of the freezing process and usually occurs on material surfaces. There is still a lack of clear physical pictures about the central question how various features of material surfaces affect their capability in facilitating ice nucleation. Via molecular dynamics simulations, here we show that the detailed features of surfaces, such as atomic arrangements, lattice parameters, hydrophobicity, and function forms of surfaces’ interaction to water molecules, generally affect the ice nucleation through the average adsorption energy per unit-area surfaces to individual water molecules, when the lattice of surfaces mismatches that of ice. However, for the surfaces whose lattice matches ice, even the detailed function form of the surfaces’ interaction to water molecules can largely regulate the icing ability of these surfaces. This study provides new insights into understanding the diverse relationship between various microscopic features of different material surfaces and their nucleation efficacy.

Bubble nucleation in spherical liquid cavity wrapped by elastic medium

According to classical nucleation theory, gas nuclei can generate and grow into a cavitation bubble when the liquid pressure exceeds a threshold. However, classical nucleation theory does not include boundary effects. An enclosed spherical liquid cavity surrounded by elastic medium is introduced to model the nucleation process in tissue. Based on the equilibrium pressure relationship of a quasi-static process, the expressions of the threshold and the modified nucleation rate are derived by considering the tissue elasticity. It is shown that the constraint plays an important role in the nucleation process. There is a positive correlation between nucleation threshold pressure and constraint, which can be enhanced by an increasing tissue elasticity and reducing the size of the cavity. Meanwhile, temperature is found to be a key parameter of nucleation process, and cavitation is more likely to occur in confined liquids at temperature T > 100℃. In contrast, less influences are induced by these factors, such as bulk modulus, liquid cavity size, and acoustic frequency. Although these theoretical predictions of the thresholds have been demonstrated by many previous researches, much lower thresholds can be obtained in liquids containing dissolved gases, e.g., the nucleation threshold is about-21 MPa in a liquid of 0.8-nm gas nuclei at room temperature. Moreover, when there is a gas nucleus of 20 nm, the theoretical threshold pressure might be less than1 MPa.

聚丙烯/蒙脱土纳米复合材料的制备与力学性能预测

本文采用熔融挤出法制备了β成核聚丙烯/蒙脱土纳米复合材料,考察了蒙脱土、β成核剂及增容剂用量对复合材料缺口冲击强度和弯曲强度的影响,并用BP神经网络进行预测。结果表明,增加蒙脱土用量有助于复合材料强度的提高但对韧性不利;随β成核剂用量的增加,复合材料的缺口冲击强度略有增加,而弯曲强度存在最优值,即添加β成核剂0.1%时,弯曲强度达到最大值35.06MPa,较不添加时增加了13.68%;随增容剂用量的增加,复合材料的韧性显著增大而强度有所降低,添加30%增容剂,复合材料的缺口冲击强度较不添加时增加了约3倍,而弯曲强度仅降低了28.39%;BP神经网络预测结果表明,该模型能够比较精确的预测该复合材料的力学性能。该研究对于优化聚丙烯基纳米复合材料制备及改进力学性能预测具有借鉴意义。

不同预时效挤压态Mg−Gd−Y−Zn−Zr合金的再结晶行为和强化机制

通过控制预时效时间制备3种不同状态的试样,研究不同预时效状态对挤压态Mg−9.5Gd−4Y−2.2Zn−0.5Zr(质量分数,%)合金的动态再结晶行为(DRX)和性能的影响。结果表明,欠时效挤压(UAE)样品的细晶体积分数为17.4%,而峰时效挤压(PAE)和过时效挤压(OAE)样品的细晶体积分数分别达到89.7%和50.4%。在晶粒内部和晶界处分布的致密、细小的β颗粒相通过粒子激发形核机制显著提高了形核位点和位错密度。然而,致密针状γ'相抑制位错滑移,延迟DRX形核。PEA和OAE样品中细小晶粒的差异归因于原始颗粒相的数量和尺寸的不同,而其拉伸性能的差异归因于不同的显微组织。由于晶界强化和析出强化机制的贡献更大,PAE样品具有更优异的拉伸性能。

EICP与木质素联合改性粉土边坡抗雨蚀试验研究

通过设置6组试样,采用降雨试验,通过试样的表面侵蚀状况与冲蚀量、表面强度、碳酸钙含量的变化分析了改性后粉土边坡的抗雨蚀性能。试验结果表明:植物源酶诱导碳酸钙沉淀(EICP)与木质素联合改性试样并在表面喷洒EICP溶液后,试样表面完整度更好,表面强度及碳酸钙含量更高,质量损失更小,抗雨蚀能力明显提高,与其他试样的平均值相比,边坡土体侵蚀量降低了75.0%,表面强度提高了33.8%,碳酸钙含量提高了235.2%;坡面喷洒EICP溶液可形成硬壳层,有效避免坡面侵蚀;木质素可为碳酸钙提供成核位点,使分布散乱的碳酸钙附着在木质素上,添加木质素后试样碳酸钙含量提高,且表面强度随碳酸钙含量提高而增大。

纳米凹槽表面结冰的分子动力学模拟研究

采用分子动力学模拟方法建立了水在金表面结冰的模型,在疏水表面上引入亲水纳米凹槽结构,模拟研究了纳米凹槽表面上的冰成核过程,揭示了凹槽深宽比对冰成核的影响规律和机制.结果表明,在疏水表面引入亲水纳米凹槽结构并改变表面的凹槽宽度,可以调节疏水表面的结冰过程.当纳米凹槽与六边形冰结构相匹配时,凹槽内部更容易形成冰核,可以提高疏水表面的冰成核率的效果,其表面成核率接近与亲水表面成核率.当纳米凹槽结构与六边形冰结构不匹配时,凹槽内不易形成冰核,结冰过程受到抑制.为提高疏水表面成核率提供了新方法,为控制疏水表面冰成核位置和冰生长方向提供了新思路.

CO_(2)-海水水合物生成强化方法研究

海水中的盐离子成分阻碍水合物成核进程,使得水合物法海洋碳封存耗时长、封存比率低。结合水合物非均相成核特征考虑,认为在局部区域内实现水合物优先成核,进而带动大片海域内水合物扩展生成的封存方法极具工业可行性。因而,开展海水水合物强化生成方法基础研究是推进水合物法海洋碳封存应用落地的基础。基于此,以高效、高转化率生成水合物为目标,在实验室尺度分别探究了高过冷度、添加剂四丁基溴化铵(TBAB)以及变温速率对海水水合物生成特性的影响。结果表明,受到盐离子抑制作用,400 m深度海水中水合物自然生成难度极大,而提高生成过程的过冷度可增强水合物生成驱动力;热力学添加剂TBAB难以显著改善海水水合物的生成条件,但可使生成速率有所提高;0.3 K/min降温速率下的水合物转化率分别是过冷度作用和添加剂作用下的1.28倍和1.19倍。在后续研究中,应考虑多种强化生成方法的耦合作用效果,开发更能缓解海水水合物生成难题的技术手段。

断层接触非均匀性对米尺度断层黏滑失稳成核过程的控制

非均匀性是野外断层的重要特征,我们利用预制的具备接触非均匀性的米尺度岩石断层开展黏滑实验,模拟野外地震失稳过程.通过观测预制岩石断层发生的多个黏滑事件的应变时空演化,并对比断层接触非均匀性测定结果发现:(1)断层的接触弱段是成核最先启动,即最早发生预滑的区域,随失稳临近,预滑区域扩展且滑动速率增加,与厘米尺度均匀断层相比,准静态过程的预滑扩展不明显,向准动态过程转变突然且迅速;(2)断层的接触强段在成核期间一直处于闭锁状态,应力升高,且随失稳临近增幅加强,强段的屈服是断层从缓慢破裂到快速破裂的转折点,接触强段的持续闭锁在以往的厘米尺度均匀断层黏滑实验中较为少见;(3)加载速率以及加载历史是影响米尺度断层成核持续时间的重要因素,随加载速率变慢,成核持续时间变长,随加载历史变长,断层趋于均匀化,成核持续时间变短.上述研究结果明确提供断层接触非均匀性控制成核过程的直接证据.这不仅有助于将实验结果向可操作的地震预测实践转化,也有助于促进(大陆浅源)地震前兆机理的探索及理解.

真空羽流中相变过程DSMC仿真方法研究

真空燃气羽流快速膨胀过程中,其中的H_(2)O和CO_(2)等组元容易发生凝结相变现象.为了研究真空羽流中水蒸气的相变产物冰晶对羽流红外信号、侵蚀等污染效应的影响,开展羽流中相变过程的数值模拟方法研究.基于稀薄两相羽流双向耦合DSMC方法,采用经典成核理论和液滴生长理论,建立了真空羽流的相变过程的数值仿真方法.对水蒸气在拉法尔喷管中自凝结试验的仿真.通过与试验结果的对比,对经典成核理论进行了修正,对成核率给出了10^(3)的修正因子,可以得到与试验符合的仿真结果,表明对成核理论修正后,可以应用到稀薄流动的数值模拟中.对某发动机真空羽流相变流场的仿真,在核心区得到与CFD相近的结果.仿真结果表明,在羽流流场中,由于相变,存在较多的冰晶颗粒,在计算条件下,羽流核心区冰晶数密度最大达到10^(15) m^(-3)的量级,冰晶直径在约10^(-8) m的量级.在真空环境下,随着羽流向倒流区无限制膨胀,倒流区流场内也会出现一定数量的冰晶颗粒,数密度从10^(7)~10^(10)m^(-3)的量级,直径在5.0×10^(-10)m的量级.颗粒在空间的数密度、尺寸等分布与气相分布存在差异,需要开展相关污染效应的影响研究.

利用废岩棉制备高性能泡沫玻璃陶瓷的实验研究

以工业垃圾废岩棉和废玻璃为原料,以CaCO_(3)为发泡剂制备出高强度泡沫玻璃陶瓷。研究了废岩棉和废玻璃的添加量及烧结温度对泡沫玻璃陶瓷材料性能的影响。结果表明:随着废岩棉添加量的增加和烧结温度的提高,熔体黏度会降低,不利于气泡结构的稳定;在废岩棉添加量为40%、750℃烧结温度下得到的样品容重为0.54 g/cm^(3)、孔隙率为62.5%、抗压强度为4.76 MPa;样品主晶相为亚硅酸钙和石英晶相,加入TiO_(2)作为晶核剂后主晶相改变为榍石;TiO_(2)掺量为10%时,在750℃烧结20 min更经济,所得样品容重为0.82 g/cm^(3)、孔隙率为50%、抗压强度为7.76 MPa。

聚偏氟乙烯流延膜的制备与性能

含β晶体的聚偏氟乙烯(PVDF)的极性较强,是一种重要的压电和铁电材料,受到人们的广泛关注。在该工作中,选择了PVDF的3种β晶体成核剂,首先用傅里叶红外光谱(FTIR)比较了3种成核剂对PVDF流延膜中β晶体含量的影响,随后选择成核效率最高的成核剂四苯基溴化膦(TPPB),通过调整流延工艺制备了高β晶体含量的PVDF流延膜,最后利用广角X射线衍射(WAXS)及小角X射线散射(SAXS)技术研究了PVDF流延膜以及其在后拉伸过程中的结晶结构,同时研究了流延膜的力学性能以及弹性回复性能等。研究结果表明,PVDF/TPPB流延膜的β晶体含量和片晶取向程度随着流延膜牵伸比的增加而增大。随着牵伸比的增加,PVDF/TPPB流延膜的屈服应力和杨氏模量增大,弹性回复能力增强。同时,在流延膜的后拉伸过程中,随着拉伸应变的增加,流延膜出现空洞结构,并且温度越低,空洞出现的临界应变越小,这对含β晶体PVDF微孔膜的制备具有指导意义。