Conditions of nucleation in crystallizable polymers: reconnaissance of positions — a critical evaluation

 In view of the enormous difficulties in obtaining reliable experimental data for the purpose of structure simulation with the aid of computer programs (presently being so popular), every classifying endeavor must be considered of great importance. One of the goals of such an endeavor is the demarcation of characteristic temperature ranges. With the aid of thermodynamic considerations an estimate of the restricted temperature range of metastable undercooling, in which the classical theory of homogeneous nucleation, as developed for polymer solutions, is valid also for polymer melts (“thermal nucleation”) can be given. This consideration includes a discussion of the course of the relevant interface tensions along the co-existence lines of the P–T diagram. The so-called spinodal crystallization mode (see [1–3]) is found at lower temperatures and seems to be quite common in polymer crystallization. In this connection the so-called athermal nucleation can be identified with a specific process. However, the present author is not in favor of the term “spinodal mode”. This is explained by a comparison with the meaning of spinodal decomposition into two phases in the ordinary gas–liquid phase transition, which always occurs at the lower bound of the metastable undercooling. Remarkably, spinodal decomposition cannot be defined in the same way for the liquid–solid transition. Anyway, the author tries hard to induce unorthodox trains of thought in the hope to revive the discussion of a difficult matter, which has almost gone to sleep, before a satisfying settlement has been reached. Received: 3 June 1997 Accepted: 19 August 1997     

弱熔体对流对定向凝固中棒状共晶生长的影响

利用渐近方法求出在弱对流熔体中定向凝固棒状共晶生长的浓度场的渐近解,研究了弱熔体对流对定向凝固中棒状共晶生长的影响.结果表明,弱熔体对流对定向凝固中棒状共晶生长有显著的作用;平均界面过冷度不仅与棒状共晶的棒间距、生长速度有关,还与流动强度有关;当生长速度一定时,随着流动强度增大,棒状共晶的平均界面过冷度减小.利用最小过冷原则,获得棒间距与生长速度和流动强度的关系.结果表明,当生长速度比较小时,随着流动强度增大,棒状共晶的棒间距增大;当生长速度比较大时,随着流动强度增大,棒状共晶的棒间距变化减弱;棒状共晶的生长速度越小,流动对棒状共晶生长的影响越大.利用本文的解析结果计算在对流条件下Al-Cu共晶的棒间距,结果显示随着转速增大或径向距离增大,共晶的间距增大,这与Junze等的实验结果相符合.     

定向结晶条件下聚乙二醇6000的强动力学效应

在单向温度场条件下, 采用不同抽拉速度实现了聚乙二醇6000的定向生长、界面形貌的实时观测及界面温度的测量, 进而揭示了其生长机制. 实验结果表明, 随着抽拉速度的增大, 界面的温度逐渐减小, 过冷度逐渐增大. 运用高聚物结晶的次级形核理论模型, 对实验数据进行了计算, 得到在界面过冷度为13.5 K左右时, 生长机制发生了由区域Ⅱ向区域Ⅲ的转变. 实验数据与等温结晶数据的比较发现等温结晶方法中获得过冷度相对较大, 是因为其包含了热过冷. 聚乙二醇6000定向结晶过程中需要的最大动力学过冷度为20 K, 说明由于高聚物的二维形核, 其生长主要由界面动力学控制, 具有较强的动力学效应.     

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     

落管中Ni-Fe-Ti合金的快速凝固机理及其磁学性能

采用落管自由落体方法实现了Ni_(45)Fe_(40)Ti_(15)合金在微重力无容器条件下的快速凝固,获得了直径介于160—1050μm的合金液滴.理论计算表明冷却速率及过冷度随液滴直径减小而增大,并呈指数函数关系,实验获得的最大过冷度为210 K(0.14 T_L).随着过冷度增大,凝固组织中粗大的γ-(Fe,Ni)枝晶逐渐细化,二次枝晶间距减小,溶质Ti在γ-(Fe,Ni)相中的固溶度显著扩展.对不同直径合金液滴的凝固样品进行磁学性能分析,结果表明随着凝固合金液滴直径减小,其饱和磁化强度增大,矫顽力减小,矩形比下降,软磁性能明显提高.     

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%.     

微重力条件下Ni-Cu合金的快速枝晶生长研究

采用落管方法实现了Ni-50%Cu过冷熔体在微重力和无容器条件下的快速枝晶生长.对微重力条件下的晶体形核和快速生长进行了研究，发现随着过冷度的增大，晶体生长形态由粗大枝晶向规划均匀的等轴晶转变.实验中最大冷却速率达到8×103K/s，获得了218K(014TL)的最大过冷度.理论分析表明，过冷熔体中优先发生异质形核，形核率可达1012m-3s-1以上；Ni-50%Cu过冷熔体中的枝晶生长随过冷度的增大发生由溶质扩散控制向热扩散控制的生长动力学机理转变.在68K过冷度条件下，生长界面前沿的偏析程序最大. 关键词： 落管 微重力 深过冷 枝晶 熔体     

单晶合金激光熔凝过程中晶向对单晶完整性的影响

运用几何模型对单晶合金激光熔凝过程中激光扫描方向与[100]方向夹角ξ变化时熔池内的枝晶生长方向和速度进行了计算,研究了ξ增大时不同晶向区域的分布变化规律.发现随着ξ的增大, 0]区域增大,[010]区域减小,且熔池两边不同部分速度差别增强.根据速度变化规律,构造出了熔池不同部位的过冷区域变化图,说明了可能出现新晶粒的趋势变化,并与实验结果进行了比较,揭示了在晶向不同的交界区域产生新晶粒的内在机理. 关键词： 单晶合金 激光熔凝 晶向 组成过冷     

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.     

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.