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     

微重力下Fe-Al-Nb合金液滴的快速凝固机理及其对显微硬度的影响

采用落管无容器处理技术实现了Fe_(67.5)Al_(22.8)Nb_(9.7)三元合金在微重力条件下的快速凝固,获得了直径为40—1000μm的合金液滴.实验中合金液滴的过冷度范围为50—216 K,冷却速率随着液滴直径的减小由1.23×10~3K·s~(-1)增大到5.53×10~5K·s~(-1).研究发现,Fe_(67.5)Al_(22.8)Nb_(9.7)合金液滴的凝固组织均由Nb(Fe,Al)_2相和(αFe)相组成,且随着液滴直径的减小,初生Nb(Fe,Al)_2相由树枝晶转变为等轴晶,共晶组织发生了约3倍的细化且生长特征由层片共晶向碎断共晶转变;硬质初生Nb(Fe,Al)_2相的析出有效提高了合金的显微硬度.与电磁悬浮条件下同过冷合金的凝固组织对比发现,落管条件下的合金液滴凝固组织更细化,使得合金显微硬度提高了2%—6%.     

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     

深过冷液态Al-Ni合金中枝晶与共晶生长机理

在自由落体条件下实现了液态Al-4 wt.%Ni亚共晶、Al-5.69 wt.%Ni共晶和Al-8 wt.%Ni过共晶合金的深过冷与快速凝固. 计算表明, (Al+Al₃Ni)规则纤维状共晶的共生区是4.8–15 wt.%Ni成分范围内不闭合区域, 且强烈偏向Al₃Ni相一侧. 实验发现, 随液滴直径的减小, 合金熔体冷却速率和过冷度增大, (Al)和Al₃Ni相枝晶与其共晶的竞争生长引发了Al-Ni 共晶型合金微观组织演化. 在快速凝固过程中, Al-4 wt.%Ni亚共晶合金发生完全溶质截留效应, 从而形成亚稳单相固溶体. 当过冷度超过58K时, Al-5.69 wt.%Ni 共晶合金呈现从纤维状共晶向初生(Al) 枝晶为主的亚共晶组织演变. 若过冷度连续增大, Al-8 wt.%Ni过共晶合金可以形成全部纤维状共晶组织, 并且最终演变为粒状共晶.     

Morphologies of Fe-66.7 at.%Si alloy solidified in a drop tube

Because of their unusual optical, thermoelectric, and magnetic properties, iron sili- cides have attracted considerable attention in recent years. Among them, particular at- tention has been paid to the orthorhombic semiconducting iron disilicide β-FeSi2 due to its direct band gap of about 0.85 eV at room temperature, which makes it a candidate material to be used in optoelectronic devices in near-infrared light sources and detectors. In addition, β-FeSi2 has good physical and chemical sta…     

深过冷条件下Co_7Mo_6金属间化合物的枝晶生长和维氏硬度研究

采用电磁悬浮和自由落体两种实验技术对二元Co-50%Mo过共晶合金中初生Co_7Mo_6金属间化合物的生长机理和维氏硬度进行了系统研究.电磁悬浮实验中,合金熔体获得的最大过冷度为203 K(0.12T_L),初生Co_7Mo_6枝晶生长速度与过冷度之间呈现幂函数关系.随着过冷度的增大,初生枝晶中Co元素含量单调递增,枝晶尺寸明显减小,并且其维氏硬度逐渐升高.在自由落体状态下,随着液滴直径的减小,合金熔体的过冷度和冷却速率均增大.当液滴直径减小到392μm以下时,初生Co_7Mo_6枝晶从小平面向非小平面形态进行转变.实验发现,深过冷条件下Co_7Mo_6化合物发生了显著的溶质截留效应,其维氏硬度与Co元素分布和形貌特征密切相关.     

Morphologies of Fe-66.7 at.%Si alloy solidified in a drop tube

Solidification of 0.1–1.0 mm diameter droplets of Fe-66.7 at.%Si alloy was achieved in a 3 m drop tube. The XRD, EDS, and SEM measurements reveal that all the droplets are composed of the primary phase α and the α+ε eutectic. With decreasing droplet diameter, the growth mode of the primary phase α changes from faceted to nonfaceted growth and the eutectic changes from needle-like to anomalous eutectic. In addition, the width of the primary phase α decreases with decreasing droplet size. The different cooling rates and undercooling levels corresponding to the samples with different sizes are responsible for the morphology changes. The cooling rates of the samples with different diameters during free fall were calculated and their effects on the microstructure formation were discussed. This kind of transition is also found inside the same sample, which is due to the larger cooling rate on the surface than at the center.     

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.     

Metastable phase separation and rapid solidification of undercooled Co_(40)Fe_(40)Cu_(20) alloy

The metastable liquid phase separation and rapid solidification behaviors of Co_(40) Fe_(40) Cu_(20) alloy were investigated by using differential thermal analysis(DTA) in combination with glass fluxing and electromagnetic levitation(EML) techniques. The critical liquid phase separation undercooling for this alloy was determined by DTA to be 174 K. Macrosegregation morphologies are formed in the bulk samples processed by both DTA and EML. It is revealed that undercooling level, cooling rate, convection, and surface tension difference between the two separated phases play a dominant role in the coalescence and segregation of the separated phases. The growth velocity of the(Fe,Co) dendrite has been measured as a function of undercooling up to 275 K. The temperature rise resulting from recalescence increases linearly with the increase of undercooling because of the enhancement of recalescence. The slope change of the recalescence temperature rise versus undercooling at the critical undercooling also implies the occurrence of liquid demixing.     

深过冷三元Ni-Cu-Co合金的快速枝晶生长

研究了深过冷条件下三元Ni₈₀Cu₁₀Co₁₀合金的快速枝晶生长, 采用电磁悬浮无容器处理方法获得了335 K(0.2T_L)的最大过冷度. X射线衍射分析与差示扫描量热分析均表明,凝固组织为α-Ni单相固溶体. 随过冷度增大, 凝固组织显著细化, 并且当过冷度达110 K时，凝固组织的形态由粗大形枝晶转变为等轴晶. 深过冷条件下溶质截留效应增强, 使得微观偏析程度减小. 对不同过冷度下合金枝晶的生长速度进 关键词： 深过冷 枝晶生长 快速凝固 溶质截留     

采用元胞自动机法模拟二元规则共晶生长

基于元胞自动机方法,建立了二元规则共晶生长的数值模拟模型.该模型耦合宏观温度场,考虑了溶质扩散、成分过冷以及曲率过冷等重要因素,实现了二元规则共晶的稳态层片生长.以共晶模型合金为对象,研究了定向凝固条件下不同过冷度、初始层片间距、温度梯度及凝固速率对共晶两相生长形貌及层片间距的影响,再现了两相在溶质扩散及界面能的相互作用下通过形核、分岔、湮没及合并等机理实现共晶层片间距的调整.模拟得到的结果与Jackson-Hunt模型及前人实验结果规律一致.将模型扩展到三维系统,验证了二元规则共晶生长三维模拟的可行性. 关键词： 规则共晶 生长形貌 层片间距 CA方法     

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.     

Solute redistribution profiles during rapid solidification of undercooled ternary Co-Cu-Pb alloy

The solute redistribution and phase separation of liquid ternary Co-35%Cu-32.5%Pb immiscible alloy have been investigated using glass fluxing method. A bulk undercooling of 125 K was achieved and the macrosegregation pattern was characterized by a top Co-rich zone and a bottom Cu-rich zone. The average solute contents of the two separated zones decreased with the increase of undercooling, except for the solute Pb in Cu-rich zone. With the enhancement of undercooling, a morphological transition from dendrites into equaxied grains occurred to the primary α(Co) phase in Co-rich zone. The solute redistribution of Cu in primary α(Co) phase was found to depend upon both the undercooling and composition of Co-rich zone. Stokes migration is shown to be the main dynamic mechanism of droplet movement during liquid phase separation.     

液态三元Fe-Cr-Ni合金中快速枝晶生长与溶质分布规律

采用落管方法实现了液态三元Fe-Cr-Ni合金的深过冷与快速凝固,合金液滴的冷却速率和过冷度均随液滴直径的减小而迅速增大.两种成分合金近平衡凝固组织均为粗大板条状α相.在快速凝固过程中,不同直径Fe_(81.4)Cr_(13.9)Ni_(4.7)合金液滴凝固组织均为板条状α相,其固态相变特征很明显,随着过冷度增大,初生δ相由具有发达主干的粗大枝晶转变为等轴晶.Fe_(81.4)Cr_(4.7)Ni_(13.9)合金液滴凝固组织由α相晶粒组成,随着过冷度增大,初生γ相由具有发达主干的粗大枝晶转变为等轴晶,其枝晶主干长度和二次分枝间距均显著下降,晶粒内溶质的相对偏析度也明显减小,溶质Ni的相对偏析度始终大于溶质Cr.理论计算表明,与γ相相比,δ相枝晶生长速度更大.在实验获得的过冷度范围内,两种Fe-Cr-Ni合金枝晶生长过程均由热扩散控制.     

Phase separation and rapid solidification of liquid Cu<Subscript>60</Subscript>Fe<Subscript>30</Subscript>Co<Subscript>10</Subscript> ternary peritectic alloy

The metastable liquid phase separation and rapid solidification of Cu₆₀Fe₃₀Co₁₀ ternary peritectic alloy were investigated by using the drop tube technique and the differential scanning calorimetry method. It was found that the critical temperature of metastable liquid phase separation in this alloy is 1623.5 K, and the two separated liquid phases solidify as Cu(Fe,Co) and Fe(Cu,Co) solid solutions, respectively. The undercooling and cooling rate of droplets processed in the drop tube increase with the decrease of their diameters. During the drop tube processing, the structural morphologies of undercooled droplets are strongly dependent on the cooling rate. With the increase of the cooling rate, Fe(Cu,Co) spheres are refined greatly and become uniformly dispersed in the Cu-rich matrix. The calculations of Marangoni migration velocity (V _M) and Stokes motion velocity (V _S) of Fe(Cu,Co) droplets indicated that Marangoni migration contributes more to the coarsening and congregation of the minor phase during free fall. At the same undercooling, the V _M/V _S ratio increases drastically as Fe(Cu,Co) droplet size decreases. On the other hand, a larger undercooling tends to increase the V _M/V _S value for Fe(Cu,Co) droplets with the same size. Supported by the National Natural Science Foundation of China (Grant Nos. 50121101 and 50395105) and the Scientific and Technological Creative Foundation of Youth in Northwestern Polytechnical University of China (Grant No. W016223)     

液氮冷却条件下激光快速熔凝Ni-28 wt%Sn合金组织演变

研究了在液氮冷却条件下激光快速熔凝Ni-28 wt%Sn亚共晶合金的组织演化过程. 结果显示, 熔池从上至下可以分为三个区域: 表层为平行激光扫描方向的α-Ni转向枝晶区; 中部为近乎垂直于熔池底部外延生长的α-Ni柱状晶区; 底部为少量的残留α-Ni初生相和大量的枝晶间(α-Ni+Ni₃Sn) 共晶组织. 激光熔凝区组织受原始基材组织的影响很大, 熔池中的α-Ni枝晶生长方向受到了热流方向和枝晶择优取向的双重影响. 与基材中存在的层片状、棒状和少量离异(α-Ni+Ni₃Sn)共晶的混合组织相比, 熔池内的共晶组织皆为细小的规则(α-Ni+Ni₃Sn)层片状共晶, 皆垂直于熔池底部外延生长, 并且从熔池顶部至底部, 共晶层片间距逐渐增大. 分别应用描述快速枝晶生长的Kurz-Giovanola-Trivedi 模型和描述快速共晶生长的Trivedi-Magnin-Kurz模型对熔池表层凝固界面前沿的过冷度进行估算, 发现熔池表层α-Ni 枝晶和(α-Ni+Ni₃Sn)层片共晶的生长过冷度在50.4-112.5 K 之间, 远大于相应深过冷凝固(α-Ni+Ni₃Sn) 反常共晶生长的临界过冷度20 K, 这说明文献报道的临界过冷度并不是反常共晶出现的充分条件.     

液态Ti-Al合金的深过冷与快速枝晶生长

采用电磁悬浮和自由落体两种试验技术研究了液态Ti-25 wt.%Al合金的亚稳过冷能力、晶体形核机制和枝晶生长过程. 试验发现, 即使电磁悬浮无容器状态下仍难以消除润湿角θ ≥60°的异质晶核, 合金熔体过冷度可达210 K (0.11T_L). β-Ti相形核的热力学驱动力随过冷度近似以线性方式增大, 其枝晶生长速度高达11.2 m/s, 从而在慢速冷却条件下实现了快速凝固. 理论计算表明, 随着过冷度的逐步增大, β相枝晶生长从溶质扩散控制转变为热扩散控制. 当过冷度超过100 K时, 非平衡溶质截留效应可使合金熔体发生无偏析凝固. 然而, 单靠深过冷状态不足以抑制β相的后续固态相变. 对于落管中快速凝固的直径77-1048 μm合金液滴, 其冷却速率最高达1.05×10⁵ K/s, 深过冷与快速冷却的耦合作用能更有效地调控凝固组织形成过程.     

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 eutectic growth in undercooled Al-Ge alloy under free fall condition

Eutectic growth in Al-51.6%wt Ge alloy has been investigated during free fall in a drop tube. With decreasing undercooling ΔT, the microstructural evolution has shown a transition from lamellar eutectic to anomalous eutectic. A maximum cooling rate of 4.2×10^4K/s and undercooling of up to 240K (0.35T_E) are obtained in the experiment. The eutectic coupled zone is calculated on the basis of current eutectic and dendritic growth theories, which covers a composition range from 48%－59% Ge and leans towards the Ge-rich side. The two critical undercoolings for the eutectic transition are ΔT_1^*=101K and ΔT_2^*=178K. When ΔT≤ΔT^*_1, the microstructure for Al-51.6% Ge eutectic shows lamellar eutectic. If ΔT≥ΔT^*_2, the microstructure shows anomalous eutectic. In the intermediate range of ΔT^*_1<ΔT<ΔT^*_2, the microstructure is the mixture of the above two types of eutectics.     

Dendrite growth characteristics within liquid Fe-Sb alloy

Bulk samples and small droplets of liquid Fe-10%Sb alloys are undercooled up to 429 K (0.24TL) and 568 K (0.32TL), respectively, with glass fluxing and free fall techniques. The high undercooling does not change the phase constitution, and only the αFe solid solution is found in the rapidly solidified alloy. The experimental results show that when the undercooling is below 296 K, the growth velocity of αFe dendrite rises exponentially with the increase of undercooling and reaches a maximum value 1.38 m/s. S...