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)     

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.     

High undercooling and rapid dendritic growth of Cu-Sb alloy in drop tube

Droplets of Cu-20%Sb hypoeutectic alloy has been rapidly solidified in drop tube within the containerless condition. With the decrease of droplet diameter, undercooling increases and the microstructures of primary copper dendrite refines. Undercooling up to 207 K (0.17 T _L) is obtained in experiment. Theoretic analysis indicated that because of the broad temperature range of solidification, the rapid growth of primary copper dendrite is controlled by the solutal diffusion. Judging from the calculation of T₀ curve in the phase diagram, it is shown that the critical undercooling of segregationless solidification is δT ₀ = 474 K. At the maximum undercooling of 207 K, the growth velocity of primary copper phase exceeds to 37 mm/s, and the distinct solute trapping occurs.     

Rapid dendritic growth of Al-Ge hypoeutectic alloy in a drop tube

Abstract Dendritic growth in Al-45% Ge hypoeutectic alloy has been investigated during free fall in a 3 m drop tube. Calculationsindicate that the undercooling obtained for the falling Al-45% Ge droplets ranges from 13 K to 201 K. The maximum undercooling attains0. 27 T_L. With the increase of undercooling, the primary (Al) phase undergoes a "columnar dendrite to equiaxed dendrite" structural tran-sition. According to the current rapid dendritic growth theory, the growth of primary (Al) phase is always controlled by solute diffusion.     

Rapid solidification mechanism of Ag60Sb34Cu6 ternary alloy in drop tube

Ternary eutectic growth involves competitive nu-cleation and growth of three solids from one liquid. Thesolidification behavior of ternary eutectic alloy is morecomplex than that of binary eutectic alloy due to the addi-tion of the third component[1—4]. Up to now, most scientificinvestigations on ternary eutectic alloy focus on the influ-ence of changing the component or adding a fourth even afifth element on the performance of the alloy[5—8]. How-ever, the information on crystal growth char…     

Microstructural evolution of ternary Ag33Cu42Ge25 eutectic alloy inside ultrasonic field

Ultrasonic field with a frequency of 20 k Hz is introduced into the solidification process of ternary Ag33Cu42Ge25 eutectic alloy from the sample bottom to its top. The ultrasound stimulates the nucleation of alloy melt and prevents its bulk undercooling. At low ultrasound power of 250 W,the primary ε2phase in the whole alloy sample grows into non-faceted equiaxed grains, which differs to its faceted morphology of long strip under static condition. The pseudobinary(Ag t ε2) eutectic transits from dendrite shape grain composed of rod type eutectic to equiaxed chrysanthemus shape formed by lamellar structure. By contrast, the ultrasound produces no obvious variation in the morphology of ternary(Ag t Ge t ε2) eutectic except a coarsening effect. When ultrasound power rises to 500 W, divorced ternary(Ag t Ge t ε2) eutectic forms at the sample bottom. However, in the upper part, the ultrasonic energy weakens, and it only brings about prominent refining effect to primary ε2phase.The microstructural evolution mechanism is investigated on the cavitation, acoustic streaming and acoustic attenuation.     

Peritectic solidification under high undercooling conditions

The solidification characteristics of highly undercooled Cu-7.77%Co peritectic alloy has been examined by glass fluxing technique. The obtained undercoolings vary from 93 to 203 K(0.14 TL). It is found that the α(Co) phase always nucleates and grows preferentially, which is followed by peritectic transformation. This means that the peritectic phase cannot form directly, even though the alloy melt is undercooled to a temperature far below its peritectic point. The maximum recalescence temperature measured experimentally decreases as undercooling increases , which is lower than the thermodynamic calculation result owing to the actual non-adia-batic nature of recalescence process. The dendritic fragmentation of primary α(Co) phase induced by high undercooling is found to enhance the completion of peritectic transformation. In addition, the LKT/BCT dendrite growth model is modified in order to make it applicable to those binary alloy systems with seriously curved liquidus and solidus lines. The dendrite growth velocities of primary α(Co) phase are subsequently calculated as a function of undercooling on the basis of this model.     

Formation of ζ phase in Cu-Ge peritectic alloys

Rapid growth behavior of ζ phase has been investigated in the undercooling experiments of Cu-14%Ge, Cu-15%Ge, Cu-18.5%Ge and Cu-22%Ge alloys. Alloys of the four compositions obtain the maximum undercoolings of 202 K（0.17TL）, 245 K（0.20TL）, 223 K（0.20TL） and 176 K（0.17TL）, respectively. As the content of Ge increases, the microstructural transition of ＂a（Cu） dendrite ＋ ζ＂ peritectic phase → ζ＂ peritectic phase →, ζ dendrite ＋ （ε＋ζ） eutectic＂ takes place in the alloy at small undercooling, while the microstructural transition of ＂fragmented α （Cu）dendrite ＋ ζ peritectic phase →, ζ peritectic phase →ζ dendrite ＋ ε phase＂ happens in the alloy at large undercooling. EDS analysis of the Ge content in peritectic phase indicates that undercooling enlarges the solid solubility of ζ rdendrite, which leads to a decrease in the Ge content in ζ phase as undercooling increases. In the Cu-18.5%Ge alloy composed of ζ peritectic phase, the Ge content in ζ phase increases when undercooling increases, which is due to the restraint of the Ge enrichment on the grain boundaries by high undercooling effect.     

Rapid dendrite growth in quaternary Ni-based alloys

Dendritic growth is one of the most common micro-structural formation mechanisms during crystal growth. Its morphology provides the kinetics information of crystal growth. Therefore, it is valuable to perform the research on rapid dendrite growth in order…     

Primary dendrite growth of Ni<Subscript>3</Subscript>Sn intermetallic compound during rapid solidification of undercooled Ni-Sn-Ge alloy

Liquid Ni-31.7%Sn-2.5%Ge alloy was highly undercooled by up to 238 K(0.17TL) with glass fluxing and drop tube techniques.The dendritic growth velocity of primary Ni3Sn compound shows a power-law relation to undercooling and achieves a maximum velocity of 380 mm/s.The addition of Ge reduces its growth velocity as compared with the binary Ni75Sn25 alloy.A structural transition from coarse dendrites into equiaxed grains occurs once undercooling exceeds a critical value of about 125 K,which is accompanied by both grain refinement and solute trapping.The Ni3Sn intermetallic compound behaves like a normal solid solution phase showing nonfaceted growth during rapid solidification.     

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.     

旋转磁场及快速凝固对Pb-Bi合金凝固组织的影响

研究了不同转速的旋转磁场对Pb-Bi合金凝固组织的影响,对于Pb-52%Bi亚共晶,旋转磁场能碎断枝晶,细化晶粒;对于Pb-66%Bi过共晶,旋转磁场能消除比重偏析。另外,采用硅油净化法结合水淬使Pb-52%Bi亚共晶和Pb-60.9%Bi过共晶分别获得了47 K和66 K的较大过冷度,对于Pb-52%Bi亚共晶,金属间化合物ε相枝晶细化显著;对于Pb-60.9%Bi过共晶,组织中没出现初生相Bi,只有细密的共晶组织。对于Pb-52%Bi亚共晶在快速凝固的同时加旋转磁场,过冷度由47 K增大为55 K,ε相呈细小颗粒弥散分布。     

Phase selection during solidification of undercooled Ni70.2Si29.8 eutectic alloy

High undercooling (about 392 K) was achieved in the bulk eutectic Ni_70.2Si_29.8 alloy melt through glass fluxing combined with cyclic superheating. It is found that the metastable phases Ni₃Si₂ and NiSi are obtained through slow post-solidification when undercooling exceeds 240 K. The metastable phases are confirmed by using the method of X-ray diffraction and differential scanning calorimetry (DSC). Based on the principle of the free energy minimum and the transient nucleation theory, the phase selection of melt is investigated with regard to the metastable phases formation in the bulk undercooled eutectic Ni_70.2Si_29.8 melts. The formation of metastable phases from undercooled Ni_70.2Si_29.8 melts is ascribed to competitive nucleation with the undercooling, i.e. high undercooling facilitates the preferential nucleation of metastable phases.     

Solidification microstructure and phase constitution of Fe-7.5%Mo-16.5%Si ternary quasiperitectic alloy

Solidification of Fe-7.5%Mo-16.5%Si ternary quasiperitectic alloy is investigated by using differential scanning calorimetry (DSC) and drop tube containerless processing techniques.The primary phase is identified as R (Fe5Mo3Si2) and the quasiperitectic phases are τ1 (Fe5MoSi4) and Fe3Si.With the decrease of droplet diameter, the cooling rate and undercooling of the droplets in-crease rapidly.The experiment result indicates that the solidification microstructure is composed of remnant primary phase, qua-sip...     

Solidification characteristics of Pb-Sb hypereutectic alloy within ultrasonic field

The solidification of Pb-16%Sb hypereutectic alloy is investigated within ultrasonic field with a fre-quency of 15 kHz. It is found that the ultrasonic field promotes crystal nucleation and terminates the further bulk undercooling of the alloy melt. Theoretical analysis shows that the cavitation effect and the forced bulk vibration are the main factors that reduce the undercooling level. With the increase of ul-trasound intensity, the primary (Sb) phase experiences a growth mode transition from faceted to non-faceted branched growth, and the macrosegregation of primary (Sb) phase is gradually sup-pressed. In addition, the microstructures of Pb-Sb eutectic exhibit a conspicuous coarsening with in-creasing ultrasound intensity, and a structural transition of “lamellar eutectic—anomalous eutectic” occurs when ultrasound intensity rises up to 1.6 W/cm2. The ultrasonic field also changes the solute distribution adjacent to the solidification front, which lowers the Pb contents in primary (Sb) phase.     

Dynamic solidification of Sn-38.1% Pb eutectic alloy within ultrasonic field

The dynamic solidification of Sn-38.1% Pb eutectic alloy within an ultrasonic field is investigated at a frequency of 35 kHz.As the sample height H is reduced,the effect of ultrasound on macrosegregation becomes more prominent,and the volume fraction of spherical eutectic cells increases correspondingly.When H equals the wavelength λ in liquid alloy,the introduction of ultrasound enlarges the distribution region of the primary (Sn) phase,but reduces the domains of the Sn-Pb eutectic and primary (Pb) phases.Meanwhile,a "dendritic-equiaxed" structural transition occurs in the primary (Sn) phase,and its grain size is significantly reduced within the ultrasonic field.Once H decreases to λ/2 and λ/4,the ultrasonic field promotes crystal nucleation and suppresses further undercooling of the bulk liquid alloy.Theoretical analyses indicate that the local high pressure induced by the cavitation effect and the stirring effect due to acoustic streaming are the main factors dominating the eutectic growth mechanism during dynamic solidification.     

深过冷Ni-P共晶合金凝固动力学分析

根据经典的形核和生长理论，通过实验分析了深过冷Ni-P共晶合金的凝固行为．实验发现，深过冷Ni-P共晶合金的凝固组织由粒状的共晶团和棒状的规则共晶所组成．随过冷度的增加，共晶团的组织逐渐细化，同时深过冷熔体晶核生长速率很大，异质形核在凝固过程中起控制性的作用．深过冷熔体的单点形核和长大现象作为特例用以描述界面的生长速率对其凝固组织的影响。     

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)     

宽带激光熔覆铸造WCp /Ni基合金复合涂层结合界面组织特征

研究了宽带激光熔覆铸造WCp /Ni基合金复合涂层结合界面组织特征。结果表明结合界面微区组织特征为细小的共晶体组织、过渡层组织以及白亮带组织。白亮带及过渡层中主要含有Fe ,Cr,Ni,Si等元素。白亮带主要是单相的γ - (Fe ,Cr ,Ni,Si)固溶体组织。从熔覆区→过渡层→白亮带的平均显微硬度值呈梯度分布。复合涂层结合界面主要元素、微观组织结构和显微硬度呈梯度分布的特征 ,提高了涂层与基材之间的匹配性 ,缓解应力集中 ,避免裂纹形成 ,实现了基材与涂层良好的冶金结合。     

Al-Cu-Mn合金铸锭均匀化工艺及组织性能分析

采用光学金相显微镜、扫描电子显微镜及能谱分析、电导率等检测手段,对铸态和均匀化态的2219合金微观组织、第二相分布及电导率进行研究分析。结果表明,2219合金铸态组织存在着枝晶偏析,在晶界上聚集大量的Al₂Cu相,并有长条状的脆性相Al₇Cu₂（Fe、Mn）穿插在晶界上。经525 ℃均匀化处理22 h后,晶界上Al₂Cu相回溶到基体中,枝晶网络被破坏,枝晶偏析消除,Cu元素从晶界到晶内的分布趋于平稳;处于亚稳态的溶质原子从过饱和固溶体中析出,在晶内呈细小、弥散地分布,基体溶质原子固溶度降低,电子散射作用减弱,电导率提高10 %IACS。