Dendritic and eutectic growth in Sb<Subscript>60</Subscript>Ag<Subscript>20</Subscript>Cu<Subscript>20</Subscript> ternary alloy

The rapid solidification of Sb60Ag20Cu20 ternary alloy was realized by high undercooling method, and the maximum undercooling is up to 142 K (0.18TL). Within the wide undercooling range of 40-142 K, the solidified microstructures are composed of (Sb), θand ε phases. High undercooling enlarges the solute solubility of (Sb) phase, which causes its crystal lattice to expand and its crystal lattice constants to increase. Primary (Sb) phase grows in two modes at small undercoolings non-faceted dendrite growth is the main growth form; whereas at large undercoolings faceted dendrite growth takes the dominant place. The remarkable difference of crystal structures between (Sb) and θphases leads to (θ Sb) pseudobinary eutectic hard to form, whereas strips of θform when the alloy melt reaches the (θ Sb) pseudobinary eutectic line. The cooperative growth of θand ε phases contributes to the formation of (ε θ) pseudobinary eutectic easily. In addition, the crystallization route has been determined via microstructural characteristic analysis and DSC experiment.     

Formation mechanism of the primary faceted phase and complex eutectic structure within an undercooled Ag–Cu–Ge alloy

The solidified microstructure of bulk undercooled Ag₄₀Cu₃₀Ge₃₀ alloy consists of three parts: primary (Ge) phase, the complex structure of (Ag + Ge) and (Ag + ε ₂) pseudobinary eutectics, and (Ag + Ge + ε ₂) ternary eutectic. In comparison, the pseudobinary eutectic no longer appears in an alloy droplet solidified in a drop tube. Once the undercooling exceeds 225 K and the cooling rate is greater than 2×10³ K s⁻¹, the microstructure of the solidified droplet is totally composed of anomalous ternary eutectic. In both cases, the primary (Ge) phase exhibits various faceted growth morphologies at different undercoolings, such as columnar block, long dendrite, equiaxed dendrite and rod-like crystal. Some refined side branches grow from the equiaxed (Ge) dendritic branches composed of {111} twins, which is ascribed to the rapid epitaxial growth of (Ag + Ge) pseudobinary eutectic from the (Ge) dendritic branches. Moreover, both the primary (Ge) phase and the (Ge) phase in the (Ag + Ge) pseudobinary eutectic are effective heterogeneous nuclei for the (Ag+ε ₂) pseudobinary eutectic. As undercooling increases, the (Ge) phase in the (Ag + Ge+ε ₂) ternary eutectic transforms from faceted to non-faceted phase, while the independent nucleation and growth of the (Ag) and ε ₂ phases in the ternary eutectic displaces their previous cooperative growth. These growth kinetics transitions result in the formation of anomalous ternary eutectic.     

Formation mechanism of primary phases and eutectic structures within undercooled Pb-Sb-Sn ternary alloys

The solidification characteristics of three types of Pb-Sb-Sn ternary alloys with different primary phases were studied under substantial undercooling conditions. The experimental results show that primary (Pb) and SbSn phases grow in the dendritic mode, whereas primary (Sb) phase exhibits faceted growth in the form of polygonal blocks and long strips. (Pb) solid solution phase displays strong affinity with SbSn intermetallic compound so that they produce various morphologies of pseudobinary eutectics, but it can only grow in the divorced eutectic mode together with (Sb) phase. Although (Sb) solid solution phase and SbSn intermetallic compound may grow cooperatively within ternary eutectic microstructures, they seldom form pseudobinary eutectics independently. The (Pb)+(Sb)+SbSn ternary eutectic structure usually shows lamellar morphology, but appears as anomalous eutectic when its volume fraction becomes small. EDS analyses reveal that all of the three primary (Pb), (Sb) and SbSn phases exhibit conspicuous solute trapping effect during rapid solidification, which results in the remarkable extension of solute solubility. Supported by the National Natural Science Foundation of China (Grant Nos. 50121101 and 50395105)     

Rapid solidification of Al-Cu-Ag ternary alloy under the free fall condition

The rapid solidification of Al-30%Cu-18%Ag ternary alloy is investigated by using the free fall method. Its solidified microstructure is composed of θ(Al₂Cu), α(Al) and ξ(Ag₂Al) phases. The liquidus temperature and solidus temperature are determined as 778 and 827 K, respectively. The alloy melt undercooled amounts up to ΔT _Max=171 K (0.20T _L). Its microstructural evolution is investigated based on the theoretical analysis of undercooling behavior and nucleation mechanics. It is found that the undercooling increases with the decrease of the diameter of the alloy droplet. When ΔT<78 K, the primary θ(Al₂Cu) phase of the alloy grows into coarse dendrite. When 78 K⩽ΔT⩽171 K, its refined θ(Al₂Cu) phase grows alternatively with α(Al) phase. Once ΔT⩾171 K, its microstructure is characterized by the anomalous (θ+α+ξ) ternary eutectic. Supported by the National Natural Science Foundation of China (Grant Nos. 50121101 and 50395105)     

Ternary eutectic growth of Ag-Cu-Sb alloy within ultrasonic field

The liquid to solid transformation of ternary Ag42.4Cu21.6Sb36 eutectic alloy was accomplished in an ultrasonic field with a frequency of 35 kHz, and the growth mechanism of this ternary eutectic was examined. Theoretical calculations predict that the sound intensity in the liquid phase at the solidification interface increases gradually as the interface moves up from the sample bottom to its top. The growth mode of (ε θ Sb) ternary eutectic exhibits a transition of "divorced eutectic- mixture of anomalous and regular structures-regular eutectic" along the sample axis due to the inhomogeneity of sound field distribution. In the top zone with the highest sound intensity, the cavitation effect promotes the three eutectic phases to nucleate independently, while the acoustic streaming efficiently suppresses the coupled growth of eutectic phases. In the meantime, the ultrasonic field accelerates the solute transportation at the solid-liquid interface, which reduces the solute solubility of eutectic phases.     

深过冷Ag-Cu-Ge三元共晶合金的相组成与凝固特征

在Ag_38.5Cu_33.4Ge_28.1三元共晶合金的深过冷实验中，获得的最大过冷度为175 K(0.22T_E). XRD分析表明，不同过冷条件下其共晶组织均由(Ag),(Ge)和η(Cu₃Ge)三相组成. 在小过冷条件下，三个共晶相协同生长，凝固组织粗大.随着过冷度的增大，共晶组织明显细化，(Ge)相与其他两相分离，以初生相方式生长，而(Ag)相与η相始终呈二相层片共晶方式共生生长. 当过冷度超过80 K时，初生相(Ge)由小过冷时的块状转变为具有小面相特征的枝晶方式生长. 部分小面相(Ge)枝晶出现规则的花状，花瓣数介于5—8之间，并且过冷度越大(Ge)相越容易分瓣. 花状(Ge)枝晶的晶体表面为{111}晶面簇，择优生长方向为〈100〉晶向族. 关键词： 三元共晶 晶体形核 深过冷 快速凝固     

Formation mechanism of anomalous eutectics in highly undercooled Ag--39.9 at%Cu alloy

<正>This paper investigates the solidification behaviour of the Ag—Cu eutectic alloy melt undercooled up to 100 K.It is revealed that lamellar eutectics grow in a dendritic form in the Ag-Cu eutectic melt with undercooling equal to or greater than 76 K.As undercooling increases,the remelted fraction of the primary eutectics during recalescence rises. The severe remelting and the subsequent ripening of the primary eutectic dendrites lead to the formation of anomalous eutectics.     

深过冷Cu60Sn30Pb10偏晶合金的快速凝固

实现了大体积Cu₆₀Sn₃₀Pb₁₀偏晶合金的深过冷与快速凝固. 实验获得的最大过冷度为173 K(0.17T_L). 凝固组织发生了明显的宏观偏析,XRD分析表明,试样上部是由固溶体(Sn),(Pb)相和金属间化合物ε(Cu₃Sn)相组成的三相区,下部为富(Pb)相区. 在小过冷条件下,三相区中ε(Cu₃Sn)相的凝固组织为粗大的枝晶,随着过冷度的增大,ε(Cu₃Sn)相细化成层片状组织,且层片间距随过冷度的增大而减小,而(Sn),(Pb)两相始终以离异共晶的方式存在. 富(Pb)相区中分布有少量的ε(Cu₃Sn)枝晶,枝晶长度随过冷度的增大而增大,且在大过冷条件下发生碎断. (Sn)相在ε(Cu₃Sn)相表面形核、长大,其形态类似于包晶凝固组织. 关键词： 深过冷 快速凝固 偏晶合金 层片组织     

Asymmetrical contribution of eutectic growth kinetics on the coupled growth behaviour in rapid eutectic solidification

The interface undercooling in classical eutectic growth theories consists of solute and curvature undercooling with different expression formats. However, a significant difference in interface kinetic coefficients arises for a disordered non-facetted solid solution and an ordered facetted intermetallic compound in that different growth kinetics govern the attachment kinetics at the solid–liquid interface, which correspond to a typical eutectic reaction with a solid solution and an intermetallic compound as its terminal eutectic phases. Following the pioneering work of Jackson and Hunt (Trans. Metall. Soc. AIME 236 1129 (1966) ), the kinetic undercooling is supplemented to interface undercooling and two eutectic phases are considered separately so as to diagnose the effect of the asymmetrical contribution of kinetic undercooling on the coupled eutectic growth behaviour. Further analysis indicates that it is the asymmetrical contribution of kinetic undercoolings of the facetted and non-facetted phases that enables the coupled eutectic composition shift to the facetted phase side so as to weaken the solute undercooling of the facetted phase and balance the kinetic contribution in the rapid solidification of coupled eutectics.     

Microstructural evolution during containerless rapid solidification of Co-Si alloys

The Co-12%Si hypoeutectic, Co-12.52%Si eutectic and Co-13%Si hypereutectic alloys are rapidly solidified in a containerless environment in a drop tube. Undercoolings up to 207K (0.14T_E) are obtained, which play a dominant role in dendritic and eutectic growth. The coupled zone around Co-12.52%Si eutectic alloy has been calculated, which covers a composition range from 11.6 to 12.7%Si. A microstructural transition from lamellar eutectic to divorced eutectic occurs to Co-12.52%Si eutectic droplets with increasing undercooling. The lamellar eutectic structure of the Co-12.52%Si alloy consists of εCo and Co_3Si phases at small undercooling. The Co_3Si phase cannot decompose completely into εCo and αCo_2Si phases. As undercooling becomes larger, the Co_3Si phase grows very rapidly from the highly undercooled alloy melt to form a divorced eutectic. The structural morphology of the Co-12%Si alloy droplets transforms from εCo primary phase plus lamellar eutectic to anomalous eutectic, whereas the microstructure of Co-13%Si alloy droplets experiences a `dendritic to equiaxed' structural transition. No matter how large the undercooling is, the εCo solid solution is the primary nucleation phase. In the highly undercooled alloy melts, the growth of εCo and Co_3Si phases is controlled by solutal diffusion.     

Nucleation behaviour and anomalous eutectic formation in highly undercooled Fe2O3-La2O3 eutectic melts

Employing an aero-acoustic levitator, the Fe₂O₃-16.5 mol% La₂O₃ eutectic alloy was levitated, melted, undercooled and then solidified under a containerless condition when a continuous laser beam heating system was incorporated. By revealing the surface and cross-sectional microstructures, copious nucleation is confirmed to take place in the undercooled melts solidified by either an external seeding or spontaneous crystallization. The nucleation behaviour of eutectic alloys is summarized, indicating that copious nucleation may be an intrinsic attribute of a eutectic system with the exact eutectic composition in unconstrained solidification. Considering the complexity level of crystal structures of eutectic oxide phases in the Fe₂O₃-La₂O₃ alloy, the linear kinetic constants are approximately estimated and the growth kinetics are discussed. The sluggish growth kinetics of the perovskite-type phase, that is LaFeO₃ with a higher complexity level in a unit cell leads to a decoupled growth within a single eutectic colony when the melt is undercooled to exceed the critical undercooling ΔT = 125 K. It is the decoupled growth that results in the formation of anomalous eutectics. The present concept based on the kinetic constant of different phases can also be applicable to account for the growth behaviour of other oxide eutectics when considering the stable and metastable eutectic reactions in different solidification conditions. The nucleation behaviour and growth modes in some oxide eutectic systems have been predicted in the free solidification from an undercooled state.     

Solidification mechanism transition of liquid Co–Cu–Ni ternary alloy

We report a solidification mechanism transition of liquid ternary Co₄₅Cu₄₅Ni₁₀ alloy when it solidifies at a critical undercooling of about 344 K. When undercooling at ΔT<344 K, the solidification process is characterized by primary S (Co) dendritic growth and a subsequent peritectic transition. The dendritic growth velocity of S (Co) dendrite increases with the rise of undercooling. However, once ΔT>344 K, the solidification velocity decreases with the increase of undercooling. In this case, liquid/liquid phase separation takes place prior to solidification. The minor L₂ (Cu) droplets hinder the motion of the solidification front, and a monotectic transition may occur in the major L₁ phase. These facts caused by metastable phase separation are responsible for the slow growth at high undercoolings.     

Investigation of the Ag2SO4 — BaSO4 binary system from an SOx sensor point of view

The binary phase diagram of Ag₂SO₄ — BaSO₄ system is proposed using X-ray powder diffraction, thermal analysis (DTA/DSC), scanning electron microscopy, and electrical conductivity results. About 5 mol-% BaSO₄ is soluble in β-Ag₂SO₄. The two-phase (Ag₂SO₄+BaSO₄) mixture exists for 10–90 mol-% of BaSO₄ between room temperature and 578 °C. An eutectic of 578 °C exists of the composition 70Ag₂SO₄+30BaSO₄ The conductivity maximum within the solid solubility limits is due to the generation of extrinsic vacancies and lattice expansion as a result of partial substitution of the bigger aliovalent Ba²⁺ for the Ag⁺-ions. The eutectic composition shows the maximum conductivity in the entire binary system due to the minimum in grain size, thereby providing a maximum surface ion conducting path. About 1 min response time of the sensor based on using the eutectic composition, as solid electrolyte, is much shorter than that of the sensor with pure Ag₂SO₄.     

过冷Ni-P合金的凝固行为

以揭示共晶系合金在不同过冷度下凝固时初生相的选择规律和凝固组织形成机理为目的, 用熔融玻璃净化和循环过热相结合的方法, 将Ni_100-xP_x(x=18, 19, 19.6, 20, 21, 原子百分比)合金过冷至平衡液相线以下不同的温度, 用高速红外测温仪记录了试样的凝固冷却曲线, 详尽分析了试样的凝固组织.结果表明, 过冷Ni-P合金快速凝固过程中析出的初生相为α-Ni/Ni₃P耦合共晶时, 整个凝固过程中仅出现一次再辉, 在所形成的异常共晶组织中α-Ni颗粒大小分布均匀;而当某一共晶相优先析出时, 另外一相需要在残留液相中重新形核, 致使凝固过程中出现两次再辉, 相应形成颗粒相大小截然不同的两类异常共晶组织;据此绘制了Ni-P合金初生相为共生共晶的区域. Ni-P合金中α-Ni的生长动力学明显快于Ni₃P, 使得在大过冷度下过共晶合金也以α-Ni作为初生相进行凝固.     

Coordination and solvation of noble metal ions: Infrared spectroscopy of Ag+(H2O)n

Vibrational spectra of mass-selected Ag⁺(H₂O)_n ions are measured by infrared photodissociation spectroscopy and analyzed with the aid of density functional theory calculations. Hydrogen bonding between H₂O molecules is found to be absent for cold Ag⁺(H₂O)₃, but detected for Ag⁺(H₂O)₄ through characteristic changes in the position and intensity of OH-stretching transitions. The third H₂O coordinates directly to Ag⁺, but the fourth H₂O prefers solvation through hydrogen bonding. The preference of the tri-coordinated form is attributed to the inefficient 5s–4d hybridization in Ag⁺, in contrast to the efficient 4s–3d hybridization in Cu⁺. For Ag⁺(H₂O)₄, however, di-coordinated isomers are identified in addition to the tri-coordinated one.     

Al-Cu-Ge合金的热物理性质与快速凝固规律研究

Al-Cu-Ge合金是典型的三元共晶体系,在工业上有重要的应用价值,对其进行研究有助于了解该合金的热物理性质和提高该合金的结构性能.本文选择了Al55Cu10Ge35,Al70Cu10Ge20和Al80Cu10Ge10三种成分合金作为研究对象,对合金的固态比热和热膨胀系数进行了测量,并对比分析了合金在近平衡凝固和落管快速凝固条件下的组织特征和凝固路径.研究发现,合金比热随Al含量的增大和Ge含量的减少而增大.这三种成分合金的软化温度均为666 K,物理热膨胀系数α在370—650 K温度范围内基本一致,约为1.5×10-5K-1.近平衡凝固条件下合金凝固过程中最后一步反应生成的均为(Al)+(Ge)二相共晶而不是三元共晶,这表明(Al)、(Ge)和CuAl2相在这三种成分的Al-Cu-Ge合金中难以同时形核并协同生长.然而,在快速凝固条件下,初生相的形核和生成受到抑制,合金中更易于形成二相共晶和三元共晶组织.     

Cross-section and rate coefficient calculation for electron impact excitation, ionisation and dissociation of H2 and OH molecules

The weighted total cross-section (WTCS) theory is used to calculate electron impact excitation, ionisation and dissociation cross-sections and rate coefficients of OH, H₂, OH⁺, H₂ ⁺, OH^- and H₂ ^- diatomic molecules in the temperature range 1500–15000 K. Calculations are performed for H₂(X, B, C), OH(X, A, B), H₂ ⁺(X), OH⁺(X, a, A, b, c), H₂ ^-(X) and OH^-(X) electronic states for which Dunham coefficients are available. Rate coefficients are calculated from WTCS assuming Maxwellian energy distribution functions for electrons and heavy particles. One and two temperature (θ_e and θ_g respectively for electron and heavy particles kinetic temperatures) results are presented and fitting parameters (a, b and c) are given for each reaction rate coefficient: k(θ) = a (θ^b)exp (-c/θ).     

三维多相场数值模拟共晶CBr4-C2Cl6合金在不同抽拉速度下的形态选择

利用KKSO多相场模型对定向凝固共晶CBr₄-C₂Cl₆合金的三维恒速及变速生长过程进行了研究,再现了不同抽拉速度下共晶形态演化及选择过程,建立了形态选择图,研究了变速过程的界面平均生长速度及界面平均过冷度的变化.结果表明,变速前后的形态选择与恒速下的形态选择一致;变速过程的形态演变、界面平均生长速度和界面平均过冷度的变化均产生滞后效应;界面平均生长速度和界面平均过冷度之间的关系与理论结果符合较好. 关键词： 多相场模型 共晶生长 抽拉速度     

Rapid solidification and dendrite growth of ternary Fe-Sn-Ge and Cu-Pb-Ge monotectic alloys

The phase separation and dendrite growth characteristics of ternary Fe-43.9%Sn- 10%Ge and Cu-35.5%Pb-5%Ge monotectic alloys were studied systematically by the glass fluxing method under substantial undercooling conditions. The maximum undercoolings obtained in this work are 245 and 257 K, respectively, for these two alloys. All of the solidified samples exhibit serious macrosegregation, indicating that the homogenous alloy melt is separated into two liquid phases prior to rapid solidification. The solidification structures consist of four phases including α-Fe, (Sn), FeSn and FeSn2 in Fe-43.9%Sn-10%Ge ternary alloy, whereas only (Cu) and (Pb) solid solution phases in Cu-35.5%Pb-5%Ge alloy under different undercoolings. In the process of rapid monotectic solidification, α-Fe and (Cu) phases grow in a dendritic mode, and the transition "dendrite→monotectic cell" happens when alloy undercoolings become sufficiently large. The dendrite growth velocities of α-Fe and (Cu) phases are found to increase with undercooling according to an exponential relation.     

A Novel Fluorescent Silver Ion Biosensor Based on Nucleic Acid Molecular “Light Switch”

As one of nucleic acid molecular “light switch”, Ru(bipy)₂(dppx)²⁺ is a good probe for the determination of double-helical DNA, which displays intense fluorescence when double-helical DNA is present. However, the fluorescence of Ru(bipy)₂(dppx)²⁺ is quenched when Ag⁺ is added to the Ru(bipy)₂(dppx)²⁺-DNA system. Based on the quenching of the fluorescence of Ru(bipy)₂(dppx)²⁺-DNA system by Ag⁺, a simple, rapid and specific method for Ag⁺ determination was proposed. In the optimum conditions, Ag⁺ concentration versus Ru(bipy)₂(dppx)²⁺ fluorescence intensity gave a linear response in the range from 0.2 to 6.0 μM with a detection limit (3σ) of 3.2 × 10⁻⁸ M. The proposed method has been applied to determine the Ag⁺ in water samples and sulfadiazine silver cream successfully. Because of the intense fluorescence of Ru(bipy)₂dppx²⁺ when DNA is present, the interaction between Ag⁺ and DNA was confirmed by fluorescence microscopy and the phenomenon of the fluorescence images agreed well with the results. The possible mechanism of the reaction was also discussed by circular dichroism spectra and isothermal titration calorimetry.