深过冷Ni-Sn共晶合金凝固组织的演化及非规则共晶的形成

采用熔融玻璃净化配合循环过热方法使 Ni-Sn共晶合金实现了深过冷快速凝固，并对其凝固组织随初始过冷度（ΔΤ）的演化规律进行了研究.发现当ΔΤ<65K时，凝固组织为规则层片状共晶或羽毛状共晶.ΔΤ>65K时，非规则共晶在凝固组织中出现，随ΔΤ的增大，非规则共晶体积分数逐渐增大，并在ΔΤ>140K时，凝固组织完全由非规则共晶组成.利用单相枝晶再辉后的熔断理论，解释了非规则共晶的形成机制.     

深过冷Ni—Si共晶合金中Ni3Si的生长形态

采用熔融玻璃净化和循环过热相结合的方法，使Ｎｉ－Ｓｉ共晶合金获得了２２４Ｋ的大过冷度，对该合金深过冷快速凝固组织的形成机制和小平面相Ｎｉ３Ｓｉ的生长形态的研究发现，在过冷条件下，共晶组织形成之前，往往会生成组成共晶的两相的初生相，随着过冷度的增大，Ｎｉ３Ｓｉ初生相的生长形态由小平面形态向非小平面形态转变，其转变的临界过冷度约为６０Ｋ。     

深过冷Fe82B17Si1共晶合金的再辉及凝固组织特征

在大气中，采用熔融玻璃净化与循环过热相结合的方法，使Ｆｅ８２Ｂ１７Ｓｉ１共晶合金获得了３４２Ｋ９０．２３８ＴＥ，ＴＥ为共晶温度）的大过冷度，对该合金的冷却再工线及凝固组织研究发现：（１）在６￣１６４Ｋ及２５５￣３４２Ｋ过冷度范围内该合金的冷却曲线仅呈现一次再辉，而在１７４￣２４７Ｋ过冷度范围内其冷却曲线则存在两次再一 范围内的凝固组织分别对应于由准规则共晶和复杂规则共晶组成的混合共晶或混合共晶＋非     

深过冷条件下三元共晶的快速生长

采用熔融玻璃净化方法进行了大体积Ag_42.4Cu_21.6Sb₃₆三元共晶合金的深过冷实验, 获得最大过冷度为114 K(0.16 T_E). 发现在深过冷非平衡条件下三元共晶由ε(Ag₃Sb), (Sb)和θ(Cu₂Sb)三相组成, 而不是平衡相图中预期的(Ag), (Sb)和θ(Cu₂Sb)相. 小过冷条件下, 合金的凝固组织是初生θ相、(ε+θ)和(ε+Sb)二相共晶以及规则(ε+θ+Sb)三元共晶并存的混合形态. 随着过冷度的增大, 初生相和二相共晶逐渐消失, 而且三元共晶发生从规则共晶向不规则共晶的生长形态转变. 当过冷度超过102 K时, 不规则(ε+θ+Sb)三元共晶成为惟一的组织生长形态. 3个共晶相之间发生的竞争形核与生长是出现复杂生长形态的主要原因. 实验与理论计算结果表明, 金属间化合物θ相是领先形核相.     

Pb-15%Sb过共晶合金的深过冷及快速凝固

采用熔剂净化深过冷和洁净容器快速凝固方法,研究了Pb-15%Sb过共晶合金在不同凝固条件下的组织演变.在熔剂净化条件下,随着凝固过冷度△T的增大,初生相Sb的组织形貌由尖角块状向树枝晶转变并不断细化,Sb的宏观偏析减弱,实验测得的最大过冷度为73K;在洁净容器快速凝固条件下,计算获得的最大过冷度为196.2K,初生相Sb的结晶被完全抑制,凝固组织发生了完全的共生生长,出现了快速凝固超细化组织.     

深过冷Cu-Ni-Fe三元合金自定向快速凝固

利用熔融玻璃净化结合循环过热,在２５～３０４Ｋ过冷度范围,分析了Ｃｕ－３９％Ｎｉ－６％Ｆｅ（ｗｔ％）三元合金凝固过程过冷组织的演化规律。确定了负温度梯度下实现自定向凝固的过冷度条件：下限为能够抑制快速凝固过程中形成的枝晶熟化的最低过冷度,上限为快速凝固过程中枝晶不发生准球状化转变的最高过冷度;就研究的合金而言,过冷度范围为１１０～１８０Ｋ。在定向凝固的过冷度范围内,无需人为控制固液界面前沿的温度梯度,而且,以点触发试样端部,可以获得单晶     

深过冷Fe82B17Si1共晶合金的再辉及凝固组织特征

在大气中,采用熔融玻璃净化与循环过热相结合的方法,使Fe₈₂B₁₇Si₁共晶合金获得了342K(0．238T_E,T_E为共晶温度)的大过冷度．对该合金的冷却再辉曲线及凝固组织研究发现：(1)在6～164K及255～342K过冷度范围内该合金的冷却曲线仅呈现一次再辉,而在174～247K过冷度范围内其冷却曲线则存在两次再辉,三过冷度范围内的凝固组织分别对应于由准规则共晶和复杂规则共晶组成的混合共晶或混合共晶+非规则共晶、完全非规则共晶、初生α(Fe,Si)相+枝晶间非规则共晶;(2)在过冷条件下,该合金的共晶两相α(Fe,Si)及Fe2B相满足促发形核的非互惠原则;(3)该合金非规则共晶出现的特征过冷度△T₁=63K,完全非规则共晶化的特征过冷度△T₂=164K;(4)该合金非平衡状态下的共晶共生区偏向Fe₂B相一边,它与共晶成分线的交点在△T=154K及△T=264K,其谷值约在△T=207K左右．     

电磁搅拌对Fe—C共晶合金石墨片间距与过冷度的影响

Change in structure of oriented growth of Fe-C eutectic alloys with induction stirring is studied. It is found that eutectic structure coarsens obviously with rotated stirring and graphite lamellar spacing increases with increasing speed gradient of solid/liquid (s/l) interface along the radial direction. It is also found that supercooling at the eutectic front is depressed with increasing growth rate and rotation rate. Assuming a lamellar stationary flow parallel to the growth interface within the liquid boundary layer where the solidification takes place, a simple medel is proposed and compared with the experimental results. A good agreement between the experiment and the theoretical model is found     

深过冷Pb-Sb-Sn合金中初生相和共晶组织形成规律研究

研究了Pb-Sb-Sn三元系中不同相区的合金在深过冷条件下凝固组织形成规律. 实验发现, 初生(Pb)和SbSn相均以枝晶方式生长, 而初生(Sb)相主要呈现为多边形块状和板条状小面相. (Pb)和SbSn相之间的亲和力较强, 易于形成二相共晶, 组织形态丰富多彩. (Pb)和(Sb)相则是以离异共晶方式生长. (Sb)和SbSn相不易单独形成二相共晶, 但在三元共晶组织中可以相互依附生长. (Pb)+ (Sb)+SbSn三元共晶组织通常呈层片状生长, 当其体积分数较小时会形成不规则共晶组织. EDS分析表明, 在深过冷快速凝固条件下, 三种初生相的溶质固溶度均得以扩展, 表现出显著的溶质截留效应.     

Rapid solidification of undercooled Al-Cu-Si eutectic alloys

Under the conventional solidification condition, a liquid aluminium alloy can be hardly undercooled because of oxidation. In this work, rapid solidification of an undercooled liquid Al_80.4Cu_13.6Si₆ ternary eutectic alloy was realized by the glass fluxing method combined with recycled superheating. The relationship between superheating and undercooling was investigated at a certain cooling rate of the alloy melt. The maximum undercooling is 147 K (0.18T _E). The undercooled ternary eutectic is composed of α(Al) solid solution, (Si) semiconductor and θ(CuAl₂) intermetallic compound. In the (Al+Si+θ) ternary eutectic, (Si) faceted phase grows independently, while (Al) and θ non-faceted phases grow cooperatively in the lamellar mode. When undercooling is small, only (Al) solid solution forms as the leading phase. Once undercooling exceeds 73 K, (Si) phase nucleates firstly and grows as the primary phase. The alloy microstructure consists of primary (Al) dendrite, (Al+θ) pseudobinary eutectic and (Al+Si+θ) ternary eutectic at small undercooling, while at large undercooling primary (Si) block, (Al+θ) pseudobinary eutectic and (Al+Si+θ) ternary eutectic coexist. As undercooling increases, the volume fraction of primary (Al) dendrite decreases and that of primary (Si) block increases. Supported by the National Natural Science Foundation of China (Grant Nos. 50121101, 50395105) and the Doctorate Foundation of Northwestern Polytechnical University (Grant No. CX200419)     

Recalescence behavior and solidification structure of the undercooled Fe82B17Si1 eutectic alloy

By cyclic superheating incorporated with glass fluxing denucleation method the Fes2Bl7Si1 eutectic al-loy was undercooled up to △ T = 342 K. The relations between recalescence behavior and solidification structures weresystematically studied in the undercooling range of 6-342 K. Two critical undercoolings were observed: mixed eutecticwas the unique growth morphology when the undercooling was less than △T1 = 63 K; but the microstructure transformedto complete undercooled anomalous eutectic when the undercooling was greater than △T2 = 164 K. The two eutecticphases α(Fe,Si) and Fe2B conformed to the non-reciprocal nucleation effect. The boundary of the coupled zone of α(Fe, Si)-Fe2 B system shifted toward the Fe2 B side, and intersected the eutectic composition line at △ T = 154 K and△x T= 264 K, whose valley was at about △ T = 207 K.     

Recalescence behavior and solidification structure of the undercooled Fe82B17Sii eutectic alloy

By cyclic superheating incorporated with glass fluxing denucleation method the Fe^B^Si, eutectic alloy was undercooled up to A T = 342 K. The relations between recalescence behavior and solidification structures were systematically studied in the undercooling range of 6—342 K. Two critical undercoolings were observed: mixed eutectic was the unique growth morphology when the undercooling was less than A Ti =63 K; but the microstructure transformed to complete undercooled anomalous eutectic when the undercooling was greater than AT2 = 164 K. The two eutectic phases a(Fe,Si) and Fe^B conformed to the non-reciprocal nucleation effect. The boundary of the coupled zone of a (Fe,Si)-Fe2B system shifted toward the Fe^B side, and intersected the eutectic composition line at A71 = 154 K and A71 = 264 K, whose valley was at about AT = 207 K.     

Phase-selection and metastable phase formation in highly undercooled eutectic Ni_(78.6)Si_(21.4)alloys

A large undercooling (250 K) was achieved in eutectic Ni78.6 Si21.4 melt by the combination of molten-glass denucleation and cyclic superheating. The metastable phase formation process in the bulk undercooled eutectic Ni78.6 Si21.4 melts was investigated. With the increase of undercooling, different metastable phases form in eutectic Ni78.6 Si21.4 melts and part of these metastable phases can be kept at room temperature through slow post-solidification. Under large undercooling, the metastable phases β2-Ni3Si, Ni31Si12 and Ni3Si2 were identified. Especially, the Ni3Si2 phase was obtained in eutectic Ni78.6 Si21.4 alloy for the first time. Based on the principle of free energy minimum and transient nucleation theory, the solidification behavior of melts was analyzed with regard to the metastable phase formation when the melts were in highly undercooled state.     

Rapid eutectic growth during free fall

Rapid eutectic growth of Sb-24%Cu alloy is realized in the drop tube during the free fall under the containerless condition. Based on the analysis of crystal nucleation and eutectic growth in the free fall condition, it is indicated that, with the increase of undercooling, microstructural transition of Sb-24%Cu eutectic alloy proceeds from lamellar to anomalous eutectic structure. Undercoolings of 0 –154 K have been obtained in experiment. The maximum undercooling exceeds to 0.19T_e. Calculated results exhibit that Cu₂Sb compound is the primary nucleation phase, and that the primary Sb dendrite will grow more rapidly than the eutectic structure when undercooling is larger than 40 K. The eutectic coupled zone around Sb-24%Cu eutectic alloy leads strongly to the Cu-rich side and covers a composition range from 23.0% to 32.7%Sb.     

Entropy as a selection rule for crystal growth in undercooled binary eutectic melts

A solution entropy model was developed for the undercooled binary eutectic alloy systems. As an extension of Taylor and Fidler et al.’s model, the present model considered the change of phase composition with the increase of undercooling. Furthermore, the sub-regular solution model and the interaction parameter (I _AB ) were also introduced. In this paper, the extended model is used to calculate the solution entropy for binary eutectic phases under the undercooled condition, and the application scope of the model is also extended. Not only the growth manner of eutectic phases, but also the transition of morphologies may be predicted and explained by calculating the solution entropy of eutectic phases under the non-equilibrium condition with the developed model. Experimental results show that the developed model is valid for the undercooled Ni-Si and Ni-Sn eutectic alloy systems. Supported by the National Natural Science Foundation of China (Grant No. 50395103) and Doctorate Foundation of Northwestern Polytechnical University (Grant No. CX200506)     

Phase separation and microstructural characteristics of undercooled Cu-Pb immiscible alloy

Bulk samples of Cu-80%Pb hypermonotectic alloy were undercooled by up to 270 K (0.21 TL) with glass fluxing technique. The undercooling behavior and the final microstructure were investigated experimentally. It was found that the macrosegregation decreased with the increase of undercooling exponentially. When undercooling reached 270 K, the volume fraction of macrosegregation was reduced by one order of magnitude. Meanwhile, high undercooling brought about significant changes to the microstructural morphology of S(Cu) phase. At small undercoolings, S(Cu) phase grew in dendritic manner. As undercooling increased, S(Cu) dendrite transformed gradually to spherical shell. This morphology transition was ascribed to the concurrent action of the phase separation within miscibility gap and the subsequent solidification process of L2 (Pb) matrix. As an essential step to model the final microstructure, theoretical calculations related to the nucleation of L1 (Cu) droplets were carried out.     

Phase-selection and metastable phase formation in highly undercooled eutectic Ni78.6Si21.4 alloys

A large undercooling (250 K) was achieved in eutectic Ni_78.6Si_21.4 melt by the combination of molten-glass denucleation and cyclic superheating. The metastable phase formation process in the bulk undercooled eutectic Ni_78.6Si_21.4 melts was investigated. With the increase of undercooling, different metastable phases form in eutectic Ni_78.6Si_21.4 melts and part of these metastable phases can be kept at room temperature through slow post-solidification. Under large undercooling, the metastable phases β₂-Ni₃Si, Ni₃₁Si₁₂ and Ni₃Si₂ were identified. Especially, the Ni₃Si₂ phase was obtained in eutectic Ni_78.6Si_21.4 alloy for the first time. Based on the principle of free energy minimum and transient nucleation theory, the solidification behavior of melts was analyzed with regard to the metastable phase formation when the melts were in highly undercooled state.     

Phase-selection and metastable phase formation in highly undercooled eutectic Ni78.6Si21.4 alloys

A large undercooling (250 K) was achieved in eutectic Ni_78.6Si_21.4 melt by the combination of molten-glass denucleation and cyclic superheating. The metastable phase formation process in the bulk undercooled eutectic Ni_78.6Si_21.4 melts was investigated. With the increase of undercooling, different metastable phases form in eutectic Ni_78.6Si_21.4 melts and part of these metastable phases can be kept at room temperature through slow post-solidification. Under large undercooling, the metastable phases β₂-Ni₃Si, Ni₃₁Si₁₂ and Ni₃Si₂ were identified. Especially, the Ni₃Si₂ phase was obtained in eutectic Ni_78.6Si_21.4 alloy for the first time. Based on the principle of free energy minimum and transient nucleation theory, the solidification behavior of melts was analyzed with regard to the metastable phase formation when the melts were in highly undercooled state.     

Determination of the critical nucleation frequency in undercooled metal melt

By studying the effect of thermodynamic and kinetic factors on the nucleation frequency of under cooled metals, the expressions for heterogeneous and homogenous critical nucleation frequencies have been established. The results show that the homogenous critical nucleation frequency per unit volume is directly proportional to the ratio of the cooling rate to the volume of liquid metal. As the value of the equilibrium contact angle function f(θ) of the most effective catalyst is constant, the heterogeneous critical nucleation frequency per unit area of the catalyst surface is di rectly proportional to the ratio of the cooling rate to the sum of the surface area of the most effective catalyst surface ( Rc/ VSv). When Rc/VSv is constant, the heterogeneous critical nucleation frequency per unit area of the catalyst surface is inversely proportional to f(θ)0.53; the critical nucleation frequency per unit continuous mass of the metal melt for both the homogenous and heterogeneous nucleation can be expressed in terms of a general formula. The critical nucleation fre quency is slightly influenced by the nature of the metal. The obtained theoretical result agrees well with the homogenous critical nucleation frequency estimated by Turnbull.