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Article

The Influence of the Combined Addition of La–Ce Mixed Rare Earths and Sr on the Microstructure and Mechanical Properties of AlSi10MnMg Alloy

by
Yu Liu
1,
Zhichao Yu
1,
Man Zhang
1,
Qisheng Feng
1,
Dong Zhang
2,
Pengyue Gao
1,* and
Chonghe Li
1,*
1
State Key Laboratory of Advanced Special Steel, Shanghai Key Laboratory of Advanced Ferrometallurgy, School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China
2
Jintuo Technology Co., Ltd., Shanghai 201605, China
*
Authors to whom correspondence should be addressed.
Metals 2024, 14(9), 1050; https://doi.org/10.3390/met14091050
Submission received: 6 August 2024 / Revised: 11 September 2024 / Accepted: 12 September 2024 / Published: 14 September 2024
(This article belongs to the Special Issue Light Alloy and Its Application (2nd Edition))
Browse Figures
Versions Notes

Abstract

:
This study investigated the effect of adding La–Ce mixed rare earths and Sr on the microstructure and mechanical properties of AlSi10MnMg alloy. The experiment utilized different combinations of modifiers, including single La–Ce rare earths, single Sr, and the combined addition of La–Ce mixed rare earths and Sr. This study compared their effects on grain refinement, the modification of the α-Al phase and eutectic silicon phase, and tensile properties and hardness. The results showed that the combined modification of Sr and mixed rare earth elements significantly refined the grains, optimized the morphology of the α-Al phase and eutectic silicon phase, and improved the overall mechanical properties of the aluminum alloy. Under the combined modification, the addition of 0.02 wt.% Sr and 0.1 wt.% RE (La–Ce mixed rare earths) exhibited the most pronounced refining effect. The secondary dendrite arm spacing (SDAS) was reduced by 59.18%. The eutectic silicon phase transformed from coarse needle-like shapes to fine fibrous or granular forms, with an aspect ratio reduction of 69.39%. Meanwhile, the alloy’s tensile strength and hardness were significantly improved. The tensile strength increased to 240 MPa, achieving an increase of 23.08%; the yield strength increased to 111 MPa, achieving an increase of 18.09%; and the elongation reached 7.3%, achieving an increase of 73.81%. This indicates that the proper addition of Sr and mixed rare earths can significantly optimize the microstructure and enhance the mechanical properties of AlSi10MnMg alloy, providing an effective method for the preparation of high-performance heat-treatment-free aluminum alloys.

1. Introduction

AlSi10MnMg alloy is a widely used casting aluminum alloy known for its moderate strength, excellent machinability, strong corrosion resistance, and superior fluidity in the molten state [1]. AlSi10MnMg alloy has been commonly applied in automotive components such as C-pillar reinforcements, side doors, motorcycle rear wheel vibration balance rods, integral subframes, control panels, and sleeves [2]. However, its relatively low strength in the as-cast state restricts its further applications. Grain refinement is a commonly employed method to enhance its strength without compromising the ductility and is one of the most effective ways to improve aluminum alloy toughness [3,4,5,6]. In industrial production, AlSi10MnMg alloy is usually modified by adding Al-Ti-C or Al-Ti-B to improve the mechanical properties and corrosion resistance of aluminum alloys [7,8]. Although these master alloys can refine α-Al grains [9], their effect on eutectic structures and second phases (such as AlSiFe) is limited. Therefore, there is a pressing need for a low-cost and effective method to optimize the comprehensive performance of AlSi10MnMg alloy.
Rare earth elements, as refining agents for Al-Si-based alloys, can significantly optimize the microstructure during solidification. They not only refine α-Al grains but also modify the size and morphology of eutectic structures and second phases [10]. Common rare earth elements used in aluminum alloys include Er, Sc, La, and Ce [11,12,13]. There are numerous examples to enhance the properties of similar Al-Si casting alloys with RE additions, such as Al-Si-Cu alloys, including A356 [14,15], A380 [16], and ADC12 aluminum alloys [17]. REs were often added to these high-strength casting aluminum alloys to improve their properties. Colombo et al. [15] observed that adding 0.3 wt.% Er to A356 aluminum alloy resulted in the formation of A13Er particles as heterogeneous nucleation cores and the refinement of grains. In addition to adding individual rare earth elements, the addition of mixed rare earths has also become the tendency to enhance alloy performance. Saheb et al. [18] added 0.2 wt.% La–Ce mixed rare earths to Al-Si alloy, which dramatically optimized the morphology of the hard and brittle phase Al6(Mn,Fe), effectively increasing alloy toughness and elongation. Parker et al. [19] added small amounts of Sc to pure aluminum and Al-Mg alloys and found that scandium has low solubility in solid aluminum but decomposes into fine Al3Sc precipitates at high temperatures, significantly refining grains and effectively improving alloy fracture toughness and tensile properties. Zhang et al. [20] found that higher cerium and lanthanum additions to Al-Mg alloys facilitated the formation of Al4Ce and Al4La phases during solidification, suppressing the formation of Al8Mg5 phases and effectively enhancing alloy comprehensive performance. Jiang et al. [21] found that 0.2 wt.% of cerium and lanthanum exhibited the most ideal modification effect on Al-Mg-Si alloy. The additions reduced the primary α-Al phase and dendrite spacing; decreased the length, average width, and aspect ratio of eutectic silicon particles; and transformed them into granular and spherical structures, thereby significantly improving the alloy’s strength. However, further increasing cerium and lanthanum deteriorated the alloy’s comprehensive performance, resulting in coarse needle-like eutectic silicon particles and degraded alloy performance. The appropriate addition of rare earth elements can provide a large number of heterogeneous nucleation cores in the α-Al primary phase, significantly reducing the grain size of α-Al and inhibiting dendritic growth. This process refines the dendrites of the alloys.
In industrial applications, in addition to adding rare earth elements, some highly efficient modifiers such as Sr and Na, which are common in aluminum alloys, are also added to aluminum alloys. Lin et al. [22] found that eutectic silicon could be optimally spheroidized and modified by adding Sr during the melting process and holding for two hours. The metamorphic effect of Na could be comparable with that of Sr, as both primarily influenced the modification of eutectic silicon. However, Sr offered several advantages over sodium salt: it provided a more effective metamorphic transformation, had lower oxidative burnout, maintained a longer effective duration, and caused less corrosion to the crucible. Additionally, using Sr was safer and more hygienic, as it did not produce harmful gases to humans or the environment [23].
To date, extensive efforts have been carried out mainly on the separate addition of modifiers to AlSi10MnMg alloy. The combination of multiple modifiers is one of the developing tendencies, considering the demand of improving the performance of Al alloys. Therefore, this study added La–Ce mixed rare earths and Sr to AlSi10MnMg alloy, compared the grain refinement effects, and explored the presence of La–Ce mixed rare earths and Sr in the alloys. The effects of La–Ce mixed rare earths and Sr on the tensile properties, hardness, and fracture morphology of AlSi10MnMg alloy were investigated in detail. The present work holds promise for optimizing industrial preparation procedure and enhancing the comprehensive performance of AlSi10MnMg alloy, providing an effective method for the preparation of high-performance heat-treatment-free aluminum alloys.

2. Materials and Methods

2.1. Materials

The raw materials used in this study were commercially available AlSi10MnMg alloy (purchased from Anhui Yongmaotai Aluminum Co., Ltd., Xuancheng, China), Al-10Sr master alloy (purchased from Suzhou Haichuan Rare Metal Products Co., Ltd., Suzhou, China), and Al-10RE master alloy (purchased from Suzhou Zhengde Rare Earth Materials Co., Ltd., Suzhou, China). All were in the form of blocks. The chemical compositions of the alloys are shown in Table 1.

2.2. Performance Testing and Methods

The experimental process is illustrated in Figure 1. Initially, the AlSi10MnMg alloy was melted using a silicon carbide furnace. Once the temperature reached 720 °C, 0.2 wt.% of refining agent (40% KCl, 35% NaCl, 10% CaF2, and 15% C2Cl6) and 0.3 wt.% of covering agent (50% MgCl2, 40% KCl, 7% BaCl2, and 3% CaF2) were added into the melt. After holding for 30 min, the slag was cleaned off. Thereafter, Al-10Sr master alloy, Al-10RE master alloy, and a combination of Al-10Sr and Al-10RE master alloys were separately added into the melt and held for 30 min. The addition strategy and the sample numbers are illustrated in Table 2 based on the available literature [14,18] and the results of laboratory pre-tests. The melt was then stirred at a stirring rate of 120 rpm for 1 min to mix thoroughly. Finally, the melt was poured into a steel mold that was preheated to 280 °C for casting the cylindrical tension test sample. The dimensions of the casting mold were designed according to GB/T 1173-2013 standards [24]. After casting, the samples were machined to the cylindrical tension test sample (Figure 2).
Moreover, φ16 × 10 mm samples were extracted for microstructure characterization. The extracted samples were polished and etched using a mixed acid solution (45 mL HCl, 15 mL HNO3) for observing the microstructure and grain structures using optical microscopy (OM; Axio Scope A1, from Carl Zeiss Microscopy GmbH, Jena, Germany.) and field emission scanning electron microscopy (SEM; Quanta 450 FEG, from Thermo Fisher Scientific, Hillsboro, OR, USA). X-ray diffraction (XRD; D8 Advance, from Bruker AXS GmbH, Karlsruhe, Germany) and SEM with energy-dispersive X-ray spectroscopy (EDS) were employed to study the presence and distribution of Sr and La–Ce mixed rare earths in the AlSi10MnMg alloy. At least 20 sets were tested for each sample group, and the average values were calculated for each sample group. Subsequently, Image-Pro Plus 6.0 (IPP) software was used to measure the average grain size, secondary dendrite arm spacing (SDAS), and the aspect ratio of eutectic silicon phases. Additionally, five sets of hardness measurements were conducted for each sample using a Vickers hardness tester with a 100 N load applied for 30 s to obtain the average hardness value. The tensile tests were conducted with a speed of 0.5 mm/min using an AGS-X tensile testing machine (five standard samples were tested per set). Fracture sections of the alloys were observed under SEM.

3. Results

3.1. Microstructures

The macroscopic morphology of AlSi10MnMg alloys with different contents of Sr and La–Ce mixed rare earths is shown in Figure 3, and the histogram of the average grain size of the alloys is shown in Figure 4. It can be seen that the average grain size was 1210 μm in the alloy without addition. Through adding Sr and La–Ce mixed rare earths (REs) into the AlSi10MnMg alloy, the average grain size was decreased to below 600 μm, indicating a significant refinement of the grains. The mixed addition (samples #4, #5, and #6) showed better modification effects compared to single modifications (samples #2 and #3). Specifically, the addition of 0.02 wt.% Sr + 0.1 wt.% RE (sample #5) exhibited the most pronounced grain refinement, with an average grain size of 110 μm.
Figure 5 shows the microstructure of AlSi10MnMg alloys modified by different addition contents of Sr and La–Ce mixed rare earths, while Figure 6a depicts the average secondary dendrite arm spacing (SDAS). In Figure 5a (sample #1), the cast AlSi10MnMg alloy exhibited coarse dendritic α-Al phases and significant dispersion. The average size of SDAS reached 49 μm. The microstructure exhibited random grain orientation and segregations. By adding 0.1 wt.% RE, the dendritic α-Al structure was refined (Figure 5b, sample #2), reducing the SDAS size to 35 μm. The dendrite structure became more homogeneous with the presence of parallel dendrite arms. Adding 0.02 wt.% Sr (Figure 5c, sample #3) also refined the dendritic α-Al structure, which was comparable to that achieved by adding 0.1 wt.% RE (Figure 5b, sample #2). Figure 5d–f (samples #4, #5, and #6) depict the microstructure after adding Sr and La–Ce mixed rare earths. It was observed that the α-Al was significantly refined compared to the unmodified alloys and the sample with the sole addition. Simultaneously, the SDAS decreased to 29 μm, 20 μm, and 26 μm. Along with the increasing La–Ce mixed rare earth content, the α-Al and SDAS initially decreased following a gradual increase. Notably, the addition of 0.02 wt.% Sr and 0.10 wt.% RE (Figure 5e, sample #5) resulted in the most pronounced refinement, reducing the SDAS to 20 μm. The dendritic arms distributed closely, which enhanced the dislocation pile-up at the grain boundaries during deformation and thereby improved the alloy’s mechanical properties [25]. When the RE content increased to 0.16 wt.% (Figure 5f, sample #6), the dendritic structure was further regularized. However, the α-Al showed signs of becoming bigger and the SDAS average size increased to 26 μm, indicating grain coarsening and a more incompact arrangement. Therefore, sample #5 achieved the best optimization in this experiment, with the appropriate addition of 0.02 wt.% Sr + 0.1 wt.% RE.
Si is an important constituent element in casting Al-Si alloys, and the presence and quantity of Si in the alloy significantly affect the mechanical properties. Si has limited solubility in Al and exists predominantly in the form of excess phase as the second phase in the alloy. In this experiment, since the Si content in the alloy did not exceed the eutectic composition (11.7 wt.%), no primary silicon was observed under SEM and OM, suggesting all silicon existed as eutectic silicon.
Figure 5 also showed the microstructure of eutectic silicon of AlSi10MnMg alloys modified with different contents of Sr and La–Ce mixed rare earths. Figure 6b presents the aspect ratio of eutectic silicon in AlSi10MnMg alloy with different contents of Sr and La–Ce mixed rare earths. In Figure 5a (sample #1), it can be observed that the eutectic silicon phases in the cast AlSi10MnMg alloy distributed unevenly in a needle-like shape with an aspect ratio of 9.8. By adding 0.1 wt.% RE (Figure 5b) and 0.02 wt.% Sr (Figure 5c), the distinct modification of the eutectic silicon phases could be achieved, resulting in smaller aspect ratios, with averages of 5.9 and 3.7, respectively. Some eutectic silicon particles transformed into short rod-like shapes, and the degree of aggregation diminished. Notably, Sr exhibited a superior modification effect on eutectic silicon compared to the La–Ce mixed rare earth elements. Figure 5d–f (corresponding to samples #4, #5, and #6) depict the microstructures after modification with different contents of Sr and La–Ce mixed rare earths, showing reduced aspect ratios of eutectic silicon (3.4, 3.0, and 5.3) compared to the unmodified state. Among these, the sample with 0.02 wt.% Sr and 0.10 wt.% RE (sample 5#, Figure 5e) exhibited the smallest aspect ratio of eutectic silicon (3.0), demonstrating the most effective modification. However, excessive modification occurred with the addition of 0.16 wt.% RE (sample #6, Figure 5f), RE-enriched areas (bright white areas) appeared in the affected matrix. The aspect ratio of eutectic silicon increased to 5.3, surpassing that of the alloy with Sr as the sole modifier (sample #3), indicating inferior modification effects of this modifier on eutectic silicon phases.
In summary, Sr and mixed La–Ce addition rare earths contributed to the refinement of α-Al structure. According to the experimental results, the addition of 0.02 wt.% Sr and 0.1 wt.% RE resulted in the most significant effects on α-Al. Meanwhile, SDAS was reduced by 59.18% compared to the alloy without adding rare earths.
Figure 7 shows the SEM morphology of the unmodified samples, where it can be seen that the α-Al phase varies in size, the eutectic silicon phase also exhibits a needle-like morphology, and all were unevenly distributed in the as-cast AlSi10MnMg alloy. Figure 8 shows the SEM morphology of AlSi10MnMg alloy with the addition of 0.02 wt.% Sr + 0.10 wt.% RE. It can be observed that the α-Al was refined and showed a more uniform size distribution, along with a significant change in the morphology and size of eutectic silicon phases. The eutectic silicon with long and uneven needle-like shapes (Figure 7) was modified to small, dispersed short rod-like shapes, as shown in Figure 8. EDS spectra indicated that the distribution of Sr elements was overlapped with Si elements. In contrast, the mixed rare earth elements La and Ce distributed dispersedly and homogeneously in the field of view, without RE-enriched areas.
When the addition of mixed rare earth elements to the alloy reached 0.16 wt.%, a secondary phase appeared (Figure 9) in the form of long, discontinuous segments or blocks. As a result of EDS spotting analysis (Table 3), bright white areas are RE-enriched areas.

3.2. Mechanical Properties and Fracture Analysis

Part of Table 4 and Figure 10 illustrate the mechanical properties of cast AlSi10MnMg alloy before and after modification with different contents of Sr and La–Ce mixed rare earths (a, b, and c). The results indicated that adding appropriate amounts of Sr and RE master alloys enhanced the overall performance of AlSi10MnMg alloy. Sample #5 showed the most significant improvement in comprehensive mechanical properties after composite modification with Sr and La–Ce mixed rare earth elements, with a tensile strength of 240 MPa, which was 23.08% higher than that of unmodified sample #1. The yield strength reached 111 MPa, achieving an increase of 18.09%, and the elongation was significantly improved to 7.3%, with an increase of 73.81%. When the single RE was added (sample #2), the tensile strength increased by 8.21%, and the elongation was improved by 11.90%. For the sample with only the Sr addition (sample #3), the improvement in strength was not as significant as that with the La–Ce mixed rare earth addition, since the tensile strength increased by merely 5.64%. However, the elongation was improved by 21.43%, which was higher than the improvement rate with only the La–Ce rare earth addition. The best strength results were obtained when the composite addition was 0.02 wt.% Sr + 0.10 wt.% RE (sample #5). The tensile strength increased to 240 MPa, achieving an increase of 23.08%; the yield strength increased to 111 MPa, achieving an increase of 18.09%; and the elongation reached 7.3%, achieving an increase of 73.81%. Figure 10d shows the Vickers hardness of cast AlSi10MnMg alloy before and after modification with different contents of Sr and La–Ce mixed rare earths. The Vickers hardness value of sample #1 was 72 HV, while sample #5 exhibited the highest Vickers hardness of 76 HV, achieving an increase of 5.12%. The hardness values of the other samples also showed slight increases, but the rates of change were all less than 5%.
Figure 11 shows SEM pictures of the fracture section of AlSi10MnMg alloy modified with different additions. In Figure 11a, the fracture section of unmodified alloy #1 exhibited numerous cleavage planes and tearing edges, with almost no dimples visible, indicating brittle fracture and poor ductility of the alloy in its unmodified state [26]. After modification with 0.02 wt.% Sr and 0.10 wt.% RE (Figure 11e), the fracture section showed more rounded and deeper dimples, and characteristics of brittle fracture are mitigated. This modification significantly improved the mechanical properties of the alloy, especially its plasticity [27]. It was evident that this composition of modifiers enhanced the mechanical performance of AlSi10MnMg alloy dramatically (sample #5). However, increasing the content of La–Ce mixed rare earths further reduced the number of dimples on the fracture surface, as observed in Figure 11f, where white dot-like features indicated the presence of an RE-enriched area. It was hypothesized that these areas induce localized stress concentration, thereby acting as crack initiation sites, leading to the adverse effect of excessive La–Ce mixed rare earth addition [28].

4. Discussion

4.1. The Relationship between Mechanical Properties and Microstructure

Adding Sr and La–Ce mixed rare earths to AlSi10MnMg alloys could improve their mechanical properties, including hardness, tensile strength, elongation, and plasticity. In recent years, researchers have conducted extensive studies on this topic [29,30,31].
Table 4 lists the detailed microstructural parameters with different contents of Sr and La–Ce mixed rare earths, including macroscopic grain size, secondary dendrite arm spacing (SDAS), and eutectic silicon aspect ratio. It was apparent that sample #5 showed the finest grain size, along with the smallest SDAS and eutectic silicon aspect ratio. Grain refinement could increase the strength of the alloy, and the relationship between yield strength σs and average grain diameter can be described by the Hall–Petch relationship [32]:
∆ σ s = k y ∆ ( d − 0.5 )
where k y was the Hall–Petch coefficient and d represented the average grain size of the alloy. The grain refinement significantly increased the number of grain boundaries, thereby increasing the resistance to dislocation movement and enhancing the alloy’s strength. Additionally, finer grains indicated a higher number of grains per unit volume. Therefore, under the same plastic deformation, alloys with finer grains could tolerate greater deformation before fracture, significantly improving their elongation [33].
In addition to grain size, the aspect ratio and morphology of eutectic silicon were also key factors in determining the mechanical properties of aluminum alloys. Unmodified eutectic silicon mainly grows in a step-like manner [34], and under the influence of selective growth of eutectic silicon, it developed into coarse plates and needle-like structures (Figure 7), which is unfavorable for its growth. For eutectic silicon modified with additions, its growth followed the twinning plane reentrant edge (TPRE) mechanism and impurity-induced twinning (IIT) mechanism [35]. According to the TPRE mechanism, Si tended to grow along the <112> direction of twinning reentrant grooves. The IIT mechanism suggested that modifier atoms (La, Ce, Sr, etc.) are absorbed by the solid–liquid interface during growth, then produce a large number of high-density twins, resulting in effective modification [36]. Hegde et al. [37] pointed out that the mechanical properties of Al-Si alloys were closely related to the size, shape, and distribution of eutectic silicon present in the microstructure. These alloys were usually given certain treatments that transform the acicular silicon morphology into fibrous or spherical forms, significantly increasing the elongation and strength. Li et al. [38] showed that by adding rare earths, the refinement and spheroidization of eutectic silicon could be achieved, thus increasing the tensile strength and elongation of the alloy.
In conclusion, Sr and the mixed La–Ce addition were capable of modifying eutectic silicon phases, while Sr showed superior modification effects. Specifically, the addition of 0.02 wt.% Sr and 0.1 wt.% RE exhibited the most pronounced modification of eutectic silicon phases, which achieved an aspect ratio reduction of 69.39%. However, excessive addition of REs coarsened the eutectic silicon phases, even surpassing the counterpart observed in the sample without La–Ce mixed rare earths.
Therefore, when elements such as Sr, La, and Ce were added to the AlSi10MnMg alloy, Sr, La, and Ce atoms were adsorbed on the surface of Si, limiting the growth rate of Si while promoting Si to grow in a branched manner, resulting in fibrous or smaller dot-like, worm-like growth, thereby achieving refinement goals [39]. Therefore, by controlling the size and morphology of eutectic silicon, the mechanical properties of the alloy could be significantly improved. The microstructural results align well with the tensile testing shown in Figure 10. Sample #5 exhibited the smallest grain size, SDAS, and eutectic silicon aspect ratio, thereby demonstrating the highest yield strength and elongation. Furthermore, based on the analysis results before and after modification, the best modification effect was present when 0.02 wt.% Sr + 0.1 wt.% RE were added in the alloy.

4.2. The Relationship between Ultimate Fracture and Microstructure

The fracture process of cast aluminum–silicon alloys involves three main stages: (1) initiation of brittle phases, (2) formation and growth of microcracks, and (3) propagation of microcracks [40]. In the absence of the formation of an RE-enriched area, the primary factor influencing the initiation stage is the eutectic silicon particles. Under external load, stress concentration at the eutectic Si particles relative to the α-Al matrix is more likely to initiate microcracks and separate from the aluminum matrix. Furthermore, the strong interaction between eutectic silicon particles and slip bands in modified alloy specimens tends to dictate the fracture path during plastic deformation [41]. In the second stage, the decomposition of eutectic silicon particles expands the cracks as strain increases, leading adjacent microcracks to merge into larger cracks [42]. The third stage involves the local connection of microcracks. Fine, circular eutectic silicon particles were distributed uniformly in the modified alloy with smaller SDAS, resulting in more discontinuous grain boundaries. Consequently, enhanced interaction between slip bands and grain boundary plastic flow generates higher strength and elongation properties [43].
When Sr and La–Ce mixed rare earths were not added to the alloy (sample #1), it could be seen that the eutectic silicon phases also exhibited needle-like shapes with uneven distribution in the AlSi10MnMg alloy. These aggregated eutectic silicon phases tended to cleave the matrix during tension, thereby significantly deteriorating the alloy’s comprehensive performance [44]. Due to the coarse and heterogeneous distribution of eutectic silicon, stress concentration might occur during deformation and promote microcrack propagation, thus causing the AlSi10MnMg alloy to fracture [45].
It has been reported that minor RE element addition came to effect in the form of solid solution strengthening in the literature. Liu et al. [46] found that 0.04 wt.% Ce enhanced the strength of the alloy by solid solution strengthening and improved the eutectic silicon morphology. Lin et al. [32] and Dong [47] all pointed out that the induced lattice distortion increased the resistance to dislocation motion due to the larger atomic radius of La and Ce (RLa = 0.1877 nm, RCe = 0.1825 nm) compared to that of Al (RAl = 0.143 nm), thereby enhancing the ultimate fracture strength of the alloy. Therefore, in our study, since the RE-enriched area was not detected in the alloy, when adding 0.02 wt.% of Sr and 0.1 wt.% of La–Ce mixed rare earths, it is natural to expect that the mixed rare earths dissolved into AlSi10MnMg (sample #5), resulting in the lattice distortion and the improved alloy strength.
When the addition of La–Ce mixed rare earths reached 0.16 wt.% (sample #6), RE-enriched areas appeared (Figure 9), which were in the form of long, discontinuous segments or blocks. Figure 9b shows the precipitates composed of La and Ce (RE-enriched area). It was suggested that these La- and Ce-rich phases affect the modification effect of the alloy in the literature [20], resulting in the loss of Sr, La, and Ce originally at the α-Al–eutectic silicon interface. This led to degraded refinement, specifically increases in the dendrite spacing of α-Al and the aspect ratio of eutectic silicon. This was also in agreement with the results of sample #6 in this experiment. Zhang et al. [48] found that the metamorphic effect was best when the addition of the metamorphic element in the aluminum alloy was close to its maximum solid solubility in α-Al. When the rare earth addition exceeds the maximum solidification in α-Al, the RE-enriched area containing Al, Si, and La forms due to the high chemical activity between La, Si, and Al [49], which was harmful to the alloy properties. During the solidification process, the brittle RE-enriched areas were prone to act as crack initiation sites, thereby reducing the alloy’s elongation. Zhou et al. [50] also observed similar phenomena; the content of rare earth elements should not be excessively high. Based on this paper, the amount of La–Ce mixed rare earth elements should not exceed 0.10 wt.%; otherwise, the coarse RE-enriched area will be present (Figure 9).
Therefore, we suggest that the main brittle phase before the formation of RE-enriched areas is the eutectic silicon which exhibited needle-like shapes. The adverse effect on plasticity slowly disappeared along with the increasing Sr and RE contents. With excessive addition of RE, the RE-enriched area was formed, and this brittle and large secondary phase might lead to the generation of cracks, deteriorating the plasticity of the alloys, as indicated by the decreased strength and ductility of sample #6.

5. Conclusions

(1)
The addition of Sr and La–Ce rare earth elements can significantly refine the α-Al and eutectic silicon phases of AlSi10MnMg alloy. Particularly, adding 0.02 wt.% Sr and 0.1 wt.% RE exhibited the most significant refinement of α-Al and SDAS as well as the highest mechanical properties.
(2)
Excessive addition of rare earth elements could give rise to the formation of RE-enriched areas, weaken the grain refinement effect, and generate brittle phases, thus deteriorating the alloy’s ductility.
This study demonstrates that the microstructure and mechanical properties of AlSi10MnMg alloy can be significantly improved by adding Sr and a mixture of rare earth elements in appropriate proportions, providing an effective method to prepare the high-performance non-heat-treated AlSi10MnMg alloy.

Author Contributions

Conceptualization, P.G.; Data curation, Z.Y., M.Z. and D.Z.; Validation and formal analysis, Z.Y. and M.Z.; Funding acquisition, D.Z., P.G. and C.L.; Investigation, Y.L. and Q.F.; Methodology, C.L. and D.Z.; Project administration, Y.L. and Q.F.; Supervision, P.G. and Y.L.; Writing—original draft, Y.L.; Writing—review and editing, D.Z. and C.L. All authors have read and agreed to the published version of the manuscript.

Funding

This work was supported by National Natural Science Foundation of China (No. 52104305, 12305374). Additionally, we thank the anonymous referee of this paper for their constructive suggestions.

Data Availability Statement

The data presented in this study are available on request from the corresponding author. The data are not publicly available due to privacy.

Conflicts of Interest

Author Dong Zhang was employed by the company Jintuo Technology Co., Ltd. The remaining authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.

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Metals 14 01050 g001
Figure 1. Experimental process flowchart.
Figure 1. Experimental process flowchart.
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Figure 2. Dimensions of as-cast alloy tensile test specimens.
Figure 2. Dimensions of as-cast alloy tensile test specimens.
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Figure 3. Macroscopic morphology of AlSi10MnMg alloys with different contents of Sr and La–Ce mixed rare earths: (a) #1, (b) #2, (c) #3, (d) #4, (e) #5, and (f) #6.
Figure 3. Macroscopic morphology of AlSi10MnMg alloys with different contents of Sr and La–Ce mixed rare earths: (a) #1, (b) #2, (c) #3, (d) #4, (e) #5, and (f) #6.
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Figure 4. Macroscopic grain size images of AlSi10MnMg alloys with different contents of Sr and La–Ce mixed rare earths.
Figure 4. Macroscopic grain size images of AlSi10MnMg alloys with different contents of Sr and La–Ce mixed rare earths.
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Figure 5. Microstructural images of AlSi10MnMg alloys with different contents of Sr and La–Ce mixed rare earths: (a) #1, (b) #2, (c) #3, (d) #4, (e) #5, and (f) #6.
Figure 5. Microstructural images of AlSi10MnMg alloys with different contents of Sr and La–Ce mixed rare earths: (a) #1, (b) #2, (c) #3, (d) #4, (e) #5, and (f) #6.
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Figure 6. The parameters of AlSi10MnMg alloys with different contents of Sr and La–Ce mixed rare earths: (a) Average size of secondary dendrite arm spacing (SDAS). (b) Average aspect ratio of eutectic silicon phases.
Figure 6. The parameters of AlSi10MnMg alloys with different contents of Sr and La–Ce mixed rare earths: (a) Average size of secondary dendrite arm spacing (SDAS). (b) Average aspect ratio of eutectic silicon phases.
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Figure 7. SEM images of sample #1 aluminum alloy: (a) SEM image at 2000× magnification. (b) SEM image at 8000× magnification.
Figure 7. SEM images of sample #1 aluminum alloy: (a) SEM image at 2000× magnification. (b) SEM image at 8000× magnification.
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Figure 8. SEM images of sample #5 aluminum alloy: (a) SEM image at 2000× magnification. (b) Enlarged view at position II and elemental distribution.
Figure 8. SEM images of sample #5 aluminum alloy: (a) SEM image at 2000× magnification. (b) Enlarged view at position II and elemental distribution.
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Figure 9. SEM images of sample #6 aluminum alloy: (a) SEM image at 2000× magnification. (b) Enlarged view at position III and elemental distribution. (c) Enlarged view at position IV and elemental distribution.
Figure 9. SEM images of sample #6 aluminum alloy: (a) SEM image at 2000× magnification. (b) Enlarged view at position III and elemental distribution. (c) Enlarged view at position IV and elemental distribution.
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Figure 10. Effects of different contents of Sr and La–Ce mixed rare earths on the properties of AlSi10MnMg alloy: (a) tensile strength, (b) yield strength, (c) elongation, and (d) hardness.
Figure 10. Effects of different contents of Sr and La–Ce mixed rare earths on the properties of AlSi10MnMg alloy: (a) tensile strength, (b) yield strength, (c) elongation, and (d) hardness.
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Figure 11. SEM images of fracture surfaces of AlSi10MnMg alloy modified with different contents of Sr and La–Ce mixed rare earths: (a) #1, (b) #2, (c) #3, (d) #4, (e) #5, and (f) #6.
Figure 11. SEM images of fracture surfaces of AlSi10MnMg alloy modified with different contents of Sr and La–Ce mixed rare earths: (a) #1, (b) #2, (c) #3, (d) #4, (e) #5, and (f) #6.
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Table 1. Addition amounts of main elements in aluminum alloys.
Table 1. Addition amounts of main elements in aluminum alloys.
AlloyChemical Composition (wt.% )
SiFeCuMnMgSrLaCeAl
AlSi10MnMg9.5~11.5≤0.15≤0.030.5~0.80.38~0.5---Balance
Al-10Sr-----9.7~10.4--
Al-10RE------3.4~3.66.4~6.6
Table 2. Actual elemental composition of different samples.
Table 2. Actual elemental composition of different samples.
Alloy No.Alloy Element CompositionsChemical Composition (wt.% ) (±0.001% )
SiFeCuMnMgSrLaCeAl
#1AlSi10MnMg10.3720.1080.0070.6000.454---Balance
#2AlSi10MnMg
+0.10% RE		10.3660.1110.0060.5970.450-0.0340.066
#3AlSi10MnMg
+0.02% Sr		10.3790.1130.0080.6020.4530.020--
#4AlSi10MnMg
+0.02% Sr + 0.04% RE		10.3690.1090.0050.6030.4520.0200.0140.026
#5AlSi10MnMg
+0.02% Sr + 0.10% RE		10.3700.1100.0070.5990.4540.0200.0340.066
#6AlSi10MnMg
+0.02% Sr + 0.16% RE		10.3740.1020.0080.5980.4560.0200.0570.103
Table 3. EDS point element contents at different locations.
Table 3. EDS point element contents at different locations.
AreaEDS SpotComposition (at.% )
AlSiMnFeLaCe
Area III163.4724.909.272.35--
271.3323.71--1.703.25
374.6819.63--1.893.80
473.6521.63--1.523.19
574.1120.49--1.743.66
623.9376.07----
Area IV769.4526.25--1.322.97
865.8824.307.891.93--
Table 4. A summary table of various parameters of AlSi10MnMg alloy with different master alloys added. (All values are averages, and the error margins of the data are represented in the corresponding graphs using error bars.)
Table 4. A summary table of various parameters of AlSi10MnMg alloy with different master alloys added. (All values are averages, and the error margins of the data are represented in the corresponding graphs using error bars.)
Alloy No.Macroscopic Grain Size (μm)
(±10 μm)		SDAS (μm)
(±1 μm)		Eutectic Silicon Aspect Ratio
(±0.1)		UTS (MPa)
(±1 MPa)		YS (MPa)
(±1 MPa)		Elongation (%)
(±0.1)
#11210499.8195944.2
#2550355.92111064.7
#3320323.72061055.1
#4260293.42201066.0
#5110203.02401117.3
#6290265.32321085.6
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Liu, Y.; Yu, Z.; Zhang, M.; Feng, Q.; Zhang, D.; Gao, P.; Li, C. The Influence of the Combined Addition of La–Ce Mixed Rare Earths and Sr on the Microstructure and Mechanical Properties of AlSi10MnMg Alloy. Metals 2024, 14, 1050. https://doi.org/10.3390/met14091050

AMA Style

Liu Y, Yu Z, Zhang M, Feng Q, Zhang D, Gao P, Li C. The Influence of the Combined Addition of La–Ce Mixed Rare Earths and Sr on the Microstructure and Mechanical Properties of AlSi10MnMg Alloy. Metals. 2024; 14(9):1050. https://doi.org/10.3390/met14091050

Chicago/Turabian Style

Liu, Yu, Zhichao Yu, Man Zhang, Qisheng Feng, Dong Zhang, Pengyue Gao, and Chonghe Li. 2024. "The Influence of the Combined Addition of La–Ce Mixed Rare Earths and Sr on the Microstructure and Mechanical Properties of AlSi10MnMg Alloy" Metals 14, no. 9: 1050. https://doi.org/10.3390/met14091050

APA Style

Liu, Y., Yu, Z., Zhang, M., Feng, Q., Zhang, D., Gao, P., & Li, C. (2024). The Influence of the Combined Addition of La–Ce Mixed Rare Earths and Sr on the Microstructure and Mechanical Properties of AlSi10MnMg Alloy. Metals, 14(9), 1050. https://doi.org/10.3390/met14091050

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