快速凝固Ti-Cu-Fe合金的相组成与组织演变规律

采用落管无容器处理技术实现了Ti_61.2Cu_32.5Fe_6.3三元包共晶合金在自由落体条件下的快速凝固,获得了直径为80—1120μm液滴的凝固组织.实验中获得的过冷度范围为34—293 K,最大过冷度达0.23T_L.研究发现,在自由落体条件下,由于受到无容器、微重力、超高真空等因素的影响,合金熔体的凝固组织中包含Cu_0.8Fe_0.2Ti相、CuTi₂相和CuT₃相,显著偏离了平衡状态.Cu_0.8Fe_0.2Ti为初生相,同时又与CuTi₂相形成两相共晶;CuTi₃相则呈现枝晶形貌,并发生了明显的溶质截留效应.随着过冷度的增大,共晶组织由层片共晶向不规则共晶转变,形貌由长条状共晶团变为椭球状共晶团,最终变为球状共晶胞;Cu_0.8Fe_0.2Ti相枝晶形貌由粗大枝晶变为碎断枝晶,进一步变成不规则的粒状晶粒;CuTi₃相枝晶则由碎块状转变为完整枝晶.     

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     

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.     

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     

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.     

液态五元Zr57Cu20Al10Ni8Ti5合金的微观结构演变与非晶形成机制

利用电磁悬浮无容器处理技术实现了液态五元Zr₅₇Cu₂₀Al₁₀Ni₈Ti₅合金的深过冷与快速凝固,同时通过分子动力学模拟计算揭示了非晶形成的微观机制.实验发现,凝固组织具有明显的核-壳结构特征,核区为非晶相,壳区主要由ZrCu, Zr₂Cu和Zr₈Cu₅晶体相组成.非晶体积分数随合金过冷度的升高逐渐增大,当达到实验最大过冷度300 K (0.26T_L)时,非晶体积分数增至81.3%.由此导出完全非晶凝固所需临界过冷度为334 K. TEM分析显示,过冷度增大并接近临界过冷度时,合金凝固组织中晶体相主要为Zr₈Cu₅相,而ZrCu和Zr₂Cu相的生长被抑制.在达到临界过冷度后,过冷液相的凝固路径由Zr₈Cu₅结晶生长转变为非晶凝固.此外,合金的晶体壳中存在少量的晶间非晶相,而非晶核中...     

无容器条件下Cu-Pb偏晶的快速生长

在落管无容器条件下实现了Cu-10%Pb亚偏晶和Cu_374%Pb偏晶的快速生长. 发现随着液滴 过冷度的增大, 亚偏晶中初生(Cu)相的生长形态经历“粗大枝晶→碎断枝晶→等轴晶”的转 变. 偏晶的组织形态从多个偏晶胞组织演化为单个偏晶胞组织. 理论计算表明，直径在1000 —60 μm之间的亚偏晶和偏晶合金液滴, 最大过冷度分别为269 K (02 TL_L )和245 K (02 TM_M). 亚偏晶合金中初生(Cu)枝晶的最大生长速度为24 m/s , 关键词： 无容器处理 深过冷 晶体生长 相分离     

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.     

液态五元Ni-Zr-Ti-Al-Cu合金快速凝固过程的高速摄影研究

采用电磁悬浮和自由落体两种无容器熔凝技术,并借助高速摄影实时分析方法,研究了液态五元Ni_(40)Zr_(28.5)Ti_(16.5)Al_(10)Cu_5合金的深过冷能力和快速凝固机制.在电磁悬浮条件下,液态合金的过冷度可达290 K(0.21T_L).当深过冷熔体快速凝固时,高速摄影观察发现悬浮液滴表面呈现点状和环状两种区域形核方式.合金的快速凝固组织由初生Ni_3Ti相、次生Ni_(10)Zr_7相和(Ni_(10)Zr_7+Ni_(21)Zr_8)共晶组成.初生Ni3Ti相以枝晶方式生长,枝晶生长速度随熔体过冷度的增大以幂函数关系单调递增,最高可达12 mm/s,同时其体积分数逐渐减小至13.4%,并发生显著组织细化.在自由落体条件下,尽管合金液滴凝固组织的相组成并未发生变化,但随着过冷度的增大,初生Ni_3Ti相的生长被抑制,凝固组织由晶态向非晶态转变,且非晶相的体积分数线性增大.当直径小于275μm时,合金液滴实现了完全非晶态凝固.     

微重力条件下Cu-Zr共晶合金的液固相变研究

采用落管方法实现了液态Cu-10 wt.%Zr亚共晶、Cu-12.27 wt.%Zr共晶和Cu-15 wt.%Zr过共晶合金在微重力无容器条件下的快速共晶与枝晶生长.Cu-12.27 wt.%Zr共晶合金的凝固组织随液滴直径减小由层片规则共晶向不规则共晶转变,且层片间距减小;Cu-10 wt.%Zr亚共晶合金的初生(Cu)相随液滴直径减小由粗大树枝晶向棒状晶转变,且所占体积分数增加,部分区域形成花状凝固组织,(Cu)相枝晶辐射向外生长;Cu-15 wt.%Zr过共晶合金初生相则为金属间化合物Cu_9Zr_2相,呈条状生长,随液滴直径减小冷却速率增大,凝固组织由宏观弯曲生长向球状晶胞转变.理论计算表明,三个合金液固相变枝晶与共晶的生长均由溶质扩散控制.测定Cu-10 wt.%Zr亚共晶合金初生(Cu)相显微硬度随液滴直径减小而增大,三个合金的共晶相随合金初始成分增大而增大.     

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.     

Rapid growth of ternary eutectic under high undercooling conditions

~~Rapid growth of ternary eutectic un der high undercooling conditions1.Offerman, S.E., Dijk, N.H., Sietsma, J.et al., Grain nucleation and growth during phase transformations, Science, 2002, 298: 1003-1005. 2.Warren, J.A., Langer, J.S., Prediction of dendritic spacings in a directional-solidification experiment, Phys.Rev.E, 1993, 47: 2702-2712. 3.Cao, C.D., Wang, N., Wei, B., Containerless rapid solidification of undercooled Cu-Co peritectic alloys, Science in China, Ser.A, …     

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.     

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...     

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.     

RAPID DENDRITIC GROWTH INVESTIGATED WITH ARTIFICIAL NEURAL NETWORK METHOD

Rapid dendritic growth of γ-(Ni, Fe) phase, β-CoSb intermetallic compound and α-Fe phase was realized by undercooling Ni-10%Fe single phase alloy, Co-60.5%Sb intermetallic alloy and Fe-40%Sn hypomonotectic alloy to a substantial extent. Their experimentally measured dendrite growth velocities were 79.5m/s, 12m/s and 0.705m/s, corresponding to undercooling levels of 303K(0.18T_L), 168K(0.11 T_L) and 219K(0.15 T_L) respectively. Since the usual dendrite growth theory deviates significantly from reality at great undercoolings, an artificial neural network incorporated with stochastic fuzzy control was developed to explore rapid dendrite growth kinetics. It leads to the reasonable prediction that dendritic growth always exhibits a maximum velocity at a certain undercooling, beyond which dendrite growth slows down as undercooling increases still further. In the case of Fe-Sn monotectic alloys, α-Fe dendrite growth velocity was found to depend mainly on undercooling rather than alloy composition.     

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)     

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.