RARE METALS Vol. 30, No. 4, Aug 2011, p. 424 DOI: 10.1007/s12598-011-0408-0 Effect of sample diameter on primary and secondary dendrite arm spacings during directional solidification of Pb-26wt.%Bi hypo-peritectic alloy HU Xiaowua, YAN Honga, CHEN Wenjingb, LI Shuangmingc, and FU Hengzhic a School of Mechanical-Electrical Engineering, Nanchang University, Nanchang 330031, China Department of Applied Physics, Northwestern Polytechnical University, Xi’an 710072, China c State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi’an 710072, China b Received 27 September 2010; received in revised form 11 December 2010; accepted 13 December 2010 © The Nonferrous Metals Society of China and Springer-Verlag Berlin Heidelberg 2011 Abstract The microstructure scales of dendrites, such as primary and secondary dendrite arm spacings, control the segregation profiles and the formation of secondary phases within interdendritic regions, which determine the properties of solidified structures. Investigations on primary and secondary dendrite arm spacings of primary α-phase during directionally solidified Pb-26wt%Bi hypo-peritectic alloy were carried out in this research, and systematic studies were conducted using cylindrical samples with different diameters (Φ = 1.8 and 7.0 mm) in order to analyze the effects of sample diameter on the primary and secondary dendrite arm spacings. In this work, the dependence of dendrite arm spacings on growth velocity was established. In addition, the experimental data concerning the primary and secondary dendrite arm spacings were compared with the main predictive dendritic models from the literatures. A comparison between experimental results for dendrite arm spacings of the 1.8-mm-diameter sample and 7.0-mm-diameter sample was also conducted. Keywords: lead bismuth alloys; dendrite arm spacing; directional solidification; dendrites 1. Introduction Peritectic solidification has attracted more attention in experimental and theoretical studies [1-17]. Since many technologically important materials are peritectic, studies on directional solidification of peritectic alloys, such as Sn-Cd [2-3], Sn-Sb [4], Pb-Bi [5-6], Zn-Cu [7-8], Zn-Ag [9], high temperature intermetallics Ti-Al [10] and Ni-Al [11], superconducting materials YBCO [12], magnetic materials Nd-Fe-B [13], and structural materials Fe-Ni [14-15] and Fe-Cr-Ni [16] have been carried out. It is a well-known fact that the dendrite arm spacings can affect not only microsegregation profiles but also the formation of the secondary phase within interdendritic regions, which influences mechanical properties of cast structures. Recently, some investigations on microstructure scales during directional solidification of peritectic alloys were carried out, for example, Ma et al. [7] studied the relationship between the microstructural length scales, the solidification conditions and alloy composition in Zn-Cu peritectic alloys. For Fe-Ni peritectic alloys, the spacing selection of cellular peritectic coupled growth during directional solidification Corresponding author: HU Xiaowu E-mail: xwhmaterials@yahoo.cn was investigated [18], it is found that the cellular spacing of CPCG first decreases and then increases with increasing velocity. Secondary dendrite arm coarsening in peritectic solidification was studied through considering the effects of peritectic reaction and transformation during directional solidification in Zn-Cu, Pb-Bi [19] and Nd-Fe-B [20] peritectic alloys. However, beside the effects of the peritectic reaction and transformation, the effect of sample diameter should be considered due to the intensity of melt convection which varies with different sample diameters that influences the peritectic solidification. Thus, the effects of sample diameter on the primary and secondary dendrite arm spacings of the primary phase during directionally solidified peritectic alloys need to be investigated. In this paper, the Pb-26wt.%Bi hypo-peritectic alloy was chosen for study. In order to investigate the effect of sample diameter on the microstructural scales, two kinds of alumina tubes with different inner diameters of 1.8 mm and 7.0 mm were used in directional solidification experiments. And the experimental results were compared with current theoretical models suggested for primary spacing and secondary spacing, respec- Hu X.W. et al., Effect of sample diameter on primary and secondary dendrite arm spacings during directional… range, ΔT0 and ΔT ′ can be evaluated by tively. ΔT ′ = m(C0 − Clm ) 2. Dendrite arm spacing models ⎛ DΓ ⎞ ⎟ ⎝ ΔT 0 k ⎠ 1/ 4 λ1 = 4.3ΔT ′1/ 2 ⎜ V −1/ 4G −1/ 2 (Kurz-Fisher model [22]) λ1 = 2 2G −1/ 2 V −1/ 4 (2) ( Lk ΔT0 Γ D ) ⎡ (3) Γ ⎤ ⎥ − mC ( k 1) 0 ⎣ ⎦ 0.41 ⎛D⎞ ⎜ ⎟ ⎝V ⎠ 0.59 (Hunt-Lu model [24]) (4) λ is the primary dendrite arm spacing, k is the equiwhere 1 librium distribution coefficient, D is the diffusion coefficient in the liquid, Г is the Gibbs-Thomson coefficient, V is the growth velocity, G is the temperature gradient, C0 is the alloy composition, m is the liquidus slope, and L is a constant that depends on harmonic perturbations. According to Trivedi’s analysis [23], for dendritic growth, the value of L is equal to 28. ΔT0 and ΔT ′ are the equilibrium and nonequilibrium solidification temperature range and are given as follows: m(k −1)C0 ΔT0 = (5) k GD ⎞ ΔT0 ⎛ ΔT ′ = ⎜ 1 − ⎟ ⎝ V ΔT 0 ⎠ 1 − k (6) For secondary dendrite arm spacing, Feurer and Wunderlin [25] predicted that the secondary dendrite arm spacing, λ2, was proportional to the cube root of solidification time (tf) and gave λ 2 = 5.5( Mt f )1/ 3 (7) with Γ D ln(C lm / C 0 ) m(k − 1)(C lm − C 0 ) (8) and ΔT ′ (9) GV where ΔT ′ is the nonequilibrium solidification range, which is usually larger than the equilibrium solidification tf = is the maximum concentration For a peritectic system, in the final drop of liquid, can be approximately estimated simply as C lm = C p (11) where Cp is the peritectic composition in the liquid at peritectic temperature. This estimate is reasonable on the basis that the arm coarsening for the primary phase should be suppressed by the formation of the peritectic phase surrounding the primary phase if the liquid composition exceeds the peritectic composition Cp. 1/ 4 (Trivedi model [23]) λ1 = 8.18k −0.335 ⎢ (10) Clm The theoretical models proposed for determining the primary dendrite arm spacing [21-24] are shown as Eqs. (1)-(4): 2.83(k ΔT0 DΓ ) 1/ 4 λ1 = (Hunt model [21]) (1) V 1/ 4G 1/ 2 M = 425 3. Experimental The Pb-26wt.%Bi alloy was used, and the master alloy ingot was prepared from 99.95% purity lead and 99.99% purity bismuth in an induction furnace under an argon atmosphere. The samples were machined to 1.8 and 7.0 mm in diameter and 100 mm in length from the as-cast ingot. A vertical Bridgman furnace, which was described in detail elsewhere [26], was used to produce directionally solidified rods of the Pb-26wt.%Bi alloy as follows. The machined rods were inserted into a high purity alumina tube with 1.8- and 7.0-mm inner diameter, respectively, placed into a graphite cylinder of the furnace. After being heated to stabilization at 375°C for 30 min, the sample was then withdrawn into a water-cooled cylinder containing liquid Ga-In-Sn metal (LMC) at a constant velocity (from 5 to 500 μm/s) for 80 mm to ensure a steady-state solidification condition. At the end of each experiment, the alumina tube was dropped into the LMC to quench the solid/liquid interface. The sample temperature measurements were carried out using NiCr-NiSi thermocouple. The measured temperature gradient around the peritectic temperature is about 20 K/mm. The quenched specimens were sectioned transversely and longitudinally, respectively. The microstructures of the polished specimens were revealed using the reagent consisting of 100 mL distilled water (H2O), 10 mL of nitric acid (HNO3) and 4 g of ammonium molybdate ((NH4)6MO7O24⋅ 4H2O). An Olympus TG-3 optical microscope was employed to observe the microstructures of the specimens. The values of the primary dendrite arm spacing (λ1) and secondary dendrite arm spacing (λ2) were measured on the transverse and longitudinal sections, respectively. For accuracy, the measurements were carried out at least on six different regions for each specimen. Figs.1(a) and 1(b) show the schematic diagrams for measuring λ1 and λ2, respectively. 426 RARE METALS, Vol. 30, No. 4, Aug 2011 Fig. 1. Schematic diagrams for measuring λ1 (a) and λ2 (b). 4. Results and discussion Figs. 2 and 3 shows the observed typical microstructures of Pb-26wt.%Bi alloy on the transverse sections with increasing growth velocity in the range of 5-500 μm/s at G = 20 K/mm. The left-hand side is the microstructures of specimens with a 1.8-mm diameter, and the right-hand side is the microstructures of specimens with a 7.0-mm diameter, respectively. Fig. 4 corresponds to the longitudinal microstructures. The formation of dendritic primary α-phase in a matrix of peritectic β-phase and secondary dendrite arms from primary dendrites can be clearly noticed. Fig. 2. Typical microstructures observed at the transverse section of Pb-26wt.%Bi hypo-peritectic alloy with 1.8-mm-diameter samples (left) and 7.0-mm-diameter samples (right). Hu X.W. et al., Effect of sample diameter on primary and secondary dendrite arm spacings during directional… 427 Fig. 3. Typical microstructures observed at the transverse section of Pb-26wt.%Bi hypo-peritectic alloy with 1.8-mm-diameter samples (left) and 7.0-mm-diameter samples (right). The primary and secondary dendrite arm spacings were measured accurately through the transverse and longitudinal sections, respectively. Figs. 5 and 6 present the average experimental values of primary and secondary dendrite arm spacings (λ1 and λ2) as a function of tip growth velocity (V), respectively. In Fig. 5, circles present the experimental results of the primary dendrite arm spacing of α-phase in the 7.0-mm-diameter sample, and the λ1 values in the 7.0-mm- diameter sample were published before in Ref. [6]. Triangles correspond to the results of the 1.8-mm-diameter sample. In Fig. 6, squares represent the experimental results of the secondary dendrite arm spacing of α-phase in the 7.0-mmdiameter sample, and the dot line represents a linear fit of these experimental results. Diamonds present the results of the 1.8-mm-diameter sample, and the dash line represents a linear fit for experimental data. 428 RARE METALS, Vol. 30, No. 4, Aug 2011 Fig. 5. Comparison of observed primary dendrite arm spacing of primary α-phase as a function of V with the predictions of the Hunt model, Kurz-Fisher model, Trivedi model and Hunt-Lu model, respectively. Fig. 6. Comparison of the measured λ2 of primary α-phase for Pb-26wt.%Bi hypo-peritectic alloy as a function of V with predictions of the Feurer-Wunderlin (F-W) model Fig. 4. Typical microstructures observed at the longitudinal section of Pb-26wt.%Bi hypo-peritectic alloy with 1.8-mm-diameter samples (left) and 7.0-mm-diameter samples (right). Fig. 5 also shows comparisons between the present experimental results of primary dendrite arm spacing and theoretical predictions furnished by the Hunt model, Kurz-Fisher model, Trivedi model and Hunt-Lu model, given by Eqs. (1-4), respectively. The physical parameters used are given in Table 1. The predictions of the Hunt model and Trivedi model show reasonable agreement, whereas the prediction of the Kurz-Fisher model overestimates the primary spacing, and the prediction of the Hunt-Lu model is far smaller than the experimental results. Because the Hunt-Lu model is used to predict the primary dendrite spacing or cellular spacing with high growth rate, the spacing is thus small. Analyzing the experimental measurements in Fig. 5, it can be found that the primary dendrite arm spacing in both 7.0-mm- and 1.8-mm-diameter samples decreases with increasing growth velocity. Further, Fig. 5 indicates that, for any comparison examined, the experimental scatter of the Hu X.W. et al., Effect of sample diameter on primary and secondary dendrite arm spacings during directional… 7.0-mm-diameter sample lies between the calculation values obtained by the Trivedi model and Hunt model. A similar observation was reported recently concerning directionally solidified hypoeutectic Al-Cu alloys [27]. Comparing with the experimental results of the 7.0-mm-diameter sample, the results of the 1.8-mm-diameter sample do not completely lie between the calculated ranges by the Trivedi model and Hunt model, as shown Fig. 5. In addition, the exponent values of growth rate (V) for average primary dendrite arm spacing (λ) were found to be 0.359 and 0.333 for 7.0-mmand 1.8-mm-diameter samples, respectively. In detail, the relationships between λ1 and V can be given as λ1V0.359 = 468.61 and λ1V0.333 = 308.32 for 7.0-mm- and 1.8-mm-diameter samples, respectively. Table 1. Physical parameters regarding peritectic reaction L + α → β at 187°C for the Pb-Bi system Peritectic temperature, Tp / °C 187 Bi content of α at Tp, Cα / wt.% 22.1 Bi content of β at Tp, Cβ / wt.% 29.2 Bi content of L at Tp, Cp / wt.% 38.2 α-liquidus slope, mα / (°C/wt.%) −5.01 β-liquidus slope, mβ / (°C/wt.%) −2.17 Distribution coefficient of α, kα 0.579 Distribution coefficient of β, kβ 0.764 Gibbs-Thomson coefficient, Г / mK 1.3 × 10−7 Diffusion coefficient in liquid, D / (cm2⋅s−1) 1.3 × 10−5 −1 Temperature gradient, G / (K⋅mm ) 20 Fig. 6 shows comparisons between the theoretical predictions for secondary spacing furnished by the F-W model, given by Eqs. (7)-(11) with the present experimental results. A good agreement can be observed for the 7.0-mm-diameter sample, but a slight overestimation for the 1.8-mm-diameter sample. In both cases, the secondary dendrite arm spacing decreases with increasing growth velocity. It can be seen in Fig. 6 that exponent values of 0.231 and 0.18 are suggested to relate the secondary spacing of primary α-phase variation with the growth velocity for 7.0-mm- and 1.8-mm-diameter samples, respectively. Thus, the relationships between λ2 and V can be given as λ2V0.231 = 77.50 and λ2V0.18 = 41.37 for 7.0-mm- and 1.8-mm-diameter samples. The exponent values of V for primary and secondary spacings of the previous theoretical models and the present experimental results are shown in Table 2. In order to investigate the effect of sample diameter on the primary and secondary dendrite arm spacings of primary α-phase during directionally solidifying of Pb-26wt.%Bi hypo-peritectic alloy, the samples with diameters of 1.8 mm and 7.0 mm were unidirectionally solidified at various 429 Table 2. Exponent values of V for primary and secondary spacings Model K1* K2* Ref. Hunt 0.25 — [21] Kurz-Fisher 0.25 — [22] Trivedi 0.25 — [23] Hunt-Lu 0.59 — [24] Feurer-Wunderin — 0.33 [25] Bouchard-Kirkaldy 0.5 0.66 [28] Trivedi-Sombounsok 0.5 0.5 [29] This work for 1.8-mm diameter 0.333 0.18 — This work for 7-mm diameter 0.359 0.231 — * K1 is the exponent value of V for λ1 and K2 is the exponent value of V for λ2. growth velocities (ranging from 5 to 500 μm/s). When comparing the average values of λ1 obtained in the 1.8-mmdiameter samples with those from the 7.0-mm-diameter samples, a tendency of reduction of primary dendrite arm spacing can be observed for all the growth velocities. For the same V, λ1 is reduced (about 30%) in the 1.8-mm-diameter sample. The same tendency will occur for secondary dendrite arm spacing, too. For the Pb-Bi peritectic system, the dendrite arm spacings are influenced by the peritectic reaction and transformation [30]. The peritectic reaction is controlled by the solute diffusion through the liquid, while the peritectic transformation is controlled by the solute diffusion through the peritectic phase. In the case of 7.0-mm-diameter samples, the solute convection in the interdendritic regions is stronger than that in 1.8-mm-diameter samples. This stronger solute convection results in a faster diffusion of the Bi component in the primary α-phase interdendritic regions, which controls the rate and degree of peritectic reaction and transformation of primary α-phase to peritectic β-phase. And the thin-arm dissolution is performed by the peritectic reaction and transformation. As a result, it is expected that stronger solute convection in a larger sample diameter can enhance the dissolution of thin-arms of primary α-phase, which thus leads to larger dendrite arm spacings of α-phase, including primary and secondary dendrite arm spacings. 5. Conclusions Directional solidification experiments were conducted on Pb-26wt.%Bi hypo-peritectic alloy using samples with diameters of 7.0 mm and 1.8 mm to investigate the effect of sample diameter on the primary and secondary dendrite arm spacings of primary α-phase. The major conclusions derived from the present study are shown as follows. 430 RARE METALS, Vol. 30, No. 4, Aug 2011 (1) The primary (λ1) and secondary (λ2) dendrite arm spacings of primary α-phase were found to be dependent on growth velocity and observed to decrease as the growth velocity increased. (2) Using the method of linear fitting experimental data, the relationships between λ1 and V can be given as λ1V0.359 = 468.61 μm1.359/s0.359 and λ1V0.333 = 308.32 μm1.333/s0.333 for 7.0-mm- and 1.8-mm-diameter samples, respectively. And the relationships between λ2 and V are given as follows: λ2V0.231 = 77.50 μm1.231/s0.231 for the 7.0-mm-diameter sample and λ2V0.18 = 41.37 μm1.18/s0.18 for the 1.8-mm-diameter sample. (3) Both the Hunt model and Trivedi model match the experimental results for primary dendrite arm spacing in both 7.0-mm- and 1.8-mm-diameter samples. However, the Kurz-Fisher model predictions overestimate the primary spacings. The prediction of the F-W model is compared with the experimental results of secondary dendrite arm spacing in 7.0-mm- and 1.8-mm-diameter samples, a reasonable agreement is obtained for the former case, and a little overestimation is generated for the latter case. (4) Comparing the values of λ1 and λ2 obtained in the 1.8-mm-diameter sample with those from the 7.0-mm-diameter sample, a tendency of reduction of dendrite arm spacings can be observed. It seems that the solute convection currents induced inside the interdendritic regions of a sample with a larger diameter (7.0 mm) are responsible for the reduction in these dendritic spacings. 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