Developing a die casting magnesium alloy with excellent mechanical performance by controlling intermetallic phase

1. Overview:

• Title: Developing a die casting magnesium alloy with excellent mechanical performance by controlling intermetallic phase
• Authors: Fanzhi Meng, Shuhui Lv, Qiang Yang, Pengfei Qin, Jinghuai Zhang, Kai Guan, Yuanding Huang, Norbert Hort, Baishun Li, Xiaojuan Liu, Jian Meng
• Publication Year: 2019
• Publishing Journal: Journal of Alloys and Compounds
• Keywords: Magnesium alloys, Intermetallic phase, Transmission electron microscopy (TEM), Simulation, Alloy design concept

2. Research Background:

• Social/Academic Context of the Research Topic:
  • Magnesium (Mg) alloys possess significant weight saving potential, making them increasingly attractive for automotive industries aiming to improve fuel economy and vehicle performance.
  • However, their application remains limited due to unsatisfactory mechanical performance compared to conventional metal materials.
  • Adding rare earth (RE) elements to Mg alloys is known to improve creep performance and mechanical properties, especially at elevated temperatures.
  • Mg-4Al-4RE (AE44) alloy, a representative RE-containing Mg alloy, has been used in engine cradles, prompting further research and development efforts to enhance its mechanical performance.
• Limitations of Existing Research:
  • Despite improvements in AE44 alloy's mechanical performance, its strength and creep resistance still require significant enhancement.
  • This is necessary to meet the stiffness-limited mass ratio demands in comparison to next-generation steel, high-strength aluminum alloys, and high-property carbon fiber/polymer composites.
  • Al-RE intermetallic compounds, primarily located at grain boundaries in Mg-Al-RE alloys, are effective in impeding dislocation motion and grain boundary sliding, contributing to high strength, particularly at high temperatures.
  • Previous research has focused on the influence of single RE elements on intermetallic phases and mechanical properties of Mg-Al-RE-based alloys, revealing that different RE elements lead to variations in intermetallic phase components and mechanical performance.
  • Studies indicate that both alloy strength and creep resistance decrease with increasing blocky Al₂RE particles in Mg-Al-Ce, Mg-Al-Nd, and Mg-Al-Sm systems.
• Necessity of the Research:
  • Mg-Al-La system was identified as having the highest strength and creep resistance among Mg-Al-RE systems.
  • Microstructural analysis revealed Al₁₁La₃ as the dominant intermetallic phase in Mg-Al-La, with fewer Al₂La particles.
  • This highlights the potential to develop alloys with superior mechanical performance by regulating RE elements and controlling intermetallic phase components.
  • The research aims to explore the possibility of changing and controlling intermetallic components by strictly controlling alloy compositions to achieve optimal mechanical performance in a given alloy system.
  • Specifically, for the Mg-Al-La system, the research focuses on discovering new intermetallic phases by meticulously controlling the Al/La ratio to develop high-performance Mg alloys.

3. Research Purpose and Research Questions:

• Research Purpose:
  • To develop a new alloy design concept for creating a magnesium alloy with outstanding mechanical performance and low cost.
  • This concept is based on strictly controlling intermetallic phase components by modifying alloy compositions.
  • The goal is to design an alloy that exhibits superior strength-ductility balance and cost-effectiveness compared to existing commercial and experimental die casting Mg alloys and even A380 aluminum alloy.
• Key Research Questions:
  • Can the intermetallic components in a given alloy system be changed and controlled by strictly controlling the alloy's compositions?
  • What is the crystal structure of the new intermetallic phase formed in the Mg-Al-La system by meticulously controlling the Al/La ratio?
  • How does this newly developed alloy, ALaM440, compare in terms of mechanical performance and cost to existing die casting magnesium alloys and A380 aluminum alloy?
  • What are the strengthening mechanisms associated with the controlled intermetallic phase in the ALaM440 alloy?
• Research Hypotheses:
  • By precisely controlling the Al/La ratio in the Mg-Al-La system, a new intermetallic phase with a unique crystal structure can be formed.
  • This new intermetallic phase will contribute to enhanced mechanical properties, leading to a magnesium alloy with an excellent balance of strength, ductility, and cost-effectiveness.
  • The ALaM440 alloy, designed with a controlled Al/La ratio to promote the formation of this new intermetallic phase, will outperform existing die casting magnesium alloys and approach or surpass the performance of A380 aluminum alloy in specific applications.

4. Research Methodology:

• Research Design:
  • Alloy Design: A new alloy design concept based on strictly controlling intermetallic phase components by modifying alloy compositions was employed. Specifically, the Mg-Al-La system was investigated by meticulously controlling the Al/La ratio.
  • Experimental Investigation: The research involved fabrication of alloys, microstructural characterization, mechanical property evaluation, and computational simulations.
• Data Collection Method:
  • Alloy Fabrication: Alloys were prepared using both gravity die casting and high-pressure die casting (HPDC). Pure magnesium, aluminum, Mg-20 wt% La, and Mg-2 wt% Mn master alloys were used. HPDC samples were produced using a 380-ton Frech cold chamber HPDC machine. Alloy compositions were determined using inductively coupled plasma atomic emission spectrum (ICP-AES).
  • Microstructural Characterization:
    • X-ray Diffraction (XRD): Used to identify intermetallic phases. Carried out using a Siemens diffractometer.
    • Scanning Electron Microscopy (SEM): Used to characterize morphologies and distributions of intermetallic phases. Performed with a JEOL 7001 FEG SEM.
    • Transmission Electron Microscopy (TEM): Used for detailed structural analysis of intermetallic phases, including bright-field TEM (BF-TEM), selected area electron diffraction (SAED), energy-dispersive X-ray spectrometer (EDS) analysis, and high-angle annular dark field scanning transmission electron microscopy (HAADF STEM). TEM was performed using FEI Tecnai G2 F20 and FEI Titan³TM G2 60-300 microscopes.
• Analysis Method:
  • Phase Identification and Crystal Structure Determination: XRD patterns and SAED patterns were used to identify intermetallic phases. Crystal structure of the new intermetallic phase was determined through SAED pattern analysis and refined using Density Functional Theory (DFT) calculations and HAADF STEM imaging.
  • Mechanical Property Evaluation: Yield strength, elongation to failure, and creep strength were evaluated and compared with existing Mg alloys and A380 aluminum alloy. Data for mechanical properties of other alloys were sourced from cited literature.
  • Diffraction Pattern Simulation: Single Crystal (CrystalMaker Software Ltd) software was used to simulate diffraction patterns to aid in phase identification.
  • HAADF STEM Image Simulation: QSTEM software package was used for structural modeling and HAADF STEM image simulation to validate the determined crystal structure.
  • Density Functional Theory (DFT) Calculation: DFT simulations using VASP 5.2.2 were performed to optimize the crystal structure of the new intermetallic phase and calculate its formation energy.
• Research Subjects and Scope:
  • The primary focus was on the Mg-Al-La-Mn alloy system.
  • A specific alloy, ALaM440 (Mg-3.5Al-4.2La-0.3Mn wt.%), was designed and extensively characterized.
  • Comparative analysis included commercially available die casting Mg alloys (AE44, AE46, AZ91, AM60, AS41, AS31, AAS21, AX52, AX53, AJ52, AJ62, MRI153A, AXJ530, MRI153M, MRI230D, ACM522, ALaCe44, Mg-RE) and A380 aluminum alloy.

5. Main Research Results:

• Key Research Results:
  • Development of ALaM440 Alloy: A new die casting magnesium alloy, ALaM440 (Mg-3.5Al-4.2La-0.3Mn), was successfully developed by strictly controlling the Al/La ratio to optimize the intermetallic phase.
  • Identification of a New Intermetallic Phase (η-Al₃La): A new acicular intermetallic phase, designated as η-Al₃La, was identified in the ALaM440 alloy. This phase exhibits a monoclinic crystal structure.
  • Crystal Structure of η-Al₃La: The crystal structure of η-Al₃La was determined through SAED pattern analysis, DFT calculations, and HAADF STEM imaging. The unit cell parameters are a = 0.4437 nm, b = 0.4508 nm, c = 0.9772 nm, and β = 103.5°.
  • Superior Mechanical Performance: The ALaM440 alloy demonstrates a more excellent strength-ductility balance and cost performance than commercial/experimental HPDC Mg alloys and A380 aluminum alloy.
  • Coherent η-Al₃La/Mg Interface: TEM observations revealed a coherent interface between the η-Al₃La phase and the Mg matrix, with a specific orientation relationship: (011)η//(1122)Mg, [100]η deviated by 5.7-10.4° from [1010]Mg.
  • Planar Faults in η-Al₃La: Planar faults, identified as orientation twins (monolayer orientation twins - MOTs), were observed within the η-Al₃La phase.
• Statistical/Qualitative Analysis Results:
  • XRD Analysis: XRD pattern of ALaM440 alloy showed significant inconformity between experimental peak positions and theoretical diffraction peak positions for Al₁₁La₃ or Al₂La, suggesting a different intermetallic phase. (Fig. 2b)
  • EDS Analysis: Statistic EDS analysis indicated a stoichiometry of approximately Al₃La for the acicular phase in ALaM440 alloy. (Fig. 2c)
  • Mechanical Properties:
    • Yield Strength and Elongation: "However, the ALaM440 alloy developed in this work exhibits the most excellent strength-ductility balance compared with the previously studied HPDC Mg and A380 alloys." (Fig. 7a)
    • Ultimate Tensile Strength: "…although having slightly lower strength than the HPDC A380 alloy, the ALaM440 alloy exhibits the highest ultimate tensile strength at room temperature in all commercial and experimental HPDC Mg alloys…"
    • Creep Performance: "In thermal environments over 150°C, the ALaM440 alloy developed in this work along with the AXJ530 (Mg-5Al-3Ca-0.07Sr, wt.%) alloy exhibit excellent cost creep-performance in HPDC Mg alloys." (Fig. 7b)
    • Cost Performance: "However, the ALaM440 alloy owns lower cost, higher strength and ductility balance, and better castability [43] than the AXJ530 alloy. Therefore, the ALaM440 alloy is the most potential Mg alloy to be used for automotive powertrain components." (Fig. 7b)
• Data Interpretation:
  • The formation of the new intermetallic phase η-Al₃La, achieved by controlling the Al/La ratio, is crucial for the enhanced mechanical properties of the ALaM440 alloy.
  • The coherent interface between η-Al₃La and the Mg matrix facilitates stress transfer and contributes to strengthening.
  • The fine distribution of η-Al₃La particles and the layered Mg matrix in eutectic areas promote both high strength and ductility.
  • The presence of planar faults (MOTs) within the η-Al₃La phase may also play a role in the alloy's deformation behavior.
• Figure Name List:
  • Fig. 1. The components of intermetallic phases examined using XRD and TEM in the Mg-4La-xAl (x = 0-8, wt.%) alloys fabricated by gravity die casting.
  • Fig. 2. (a) Backscatter SEM image of the studied ALaM440 alloy, (b) the corresponding XRD pattern (the known Al₂La and Al₁₁La₃ were indicated by green and red lines, respectively), (c) the statistical diagram of the atomic ratio of Al/La for the new intermetallic phase, (d-g) the corresponding SAED patterns on various zone axes for this new phase, and (h-j) HAADF STEM images of the η-Al₃La phase taken along the zone axes indicated by (d-f) respectively.
  • Fig. 3. Unit cell configuration of the DFT optimized η-Al₃La phase.
  • Fig. 4. (the first and third rows) The simulated electron diffraction patterns along various zone axes, (the second and fourth rows) the corresponding experimental SAED patterns, (the fifth row) models viewed from [100], [010] and [110], respectively, with the colors of the balls being consistent with those in Fig. 3, (the sixth row) simulated HAADF STEM images using the above models, and (the last row) HAADF STEM images taken from [100], [010] and [110], respectively.
  • Fig. 5. (a) and (b) SAED patterns along [100] and [010] zone axes, respectively, and the corresponding (c and d) magnified SAED patterns and (e and f) atomic resolution HAADF STEM images.
  • Fig. 6. HAADF STEM images with various distributions for MOTs (marked by red arrows) and orientation twin (marked by orange arrows) in η-Al₃La phase.
  • Fig. 7. (a) Yield strength and elongation to failure of various HPDC Mg systems along with the A380 alloy [5,19,21,40-47]. Overall, die casting Mg alloys display an inverse relationship between yield strength and elongation, as indicated by the area between two blue dash lines. (b) The creep strength (the stress to produce 0.1% creep strain at 100 h) and the cost of the traditional die casting Mg alloys relative to that of A380 alloy [3,5,40,41,50,51].
  • Fig. 8. (a) and (b) BF-TEM images of the EAs, (c) SAED pattern from a fine η-Al₃La phase and (d) the interface between η-Al₃La and Mg matrix.
  • Fig. 9. High magnified TEM images showing the formation of faults on (a) {102}η, (b) (011) and (c) (110) planes, respectively.

6. Conclusion and Discussion:

• Summary of Main Results:
  • This research successfully developed a new die casting magnesium alloy, ALaM440, by employing an alloy design concept based on controlling intermetallic phase components.
  • By meticulously controlling the Al/La ratio in the Mg-Al-La system, a new acicular intermetallic phase, η-Al₃La, was formed as the dominant intermetallic phase.
  • The crystal structure of η-Al₃La was determined to be monoclinic with specific lattice parameters.
  • The ALaM440 alloy exhibits a superior combination of strength, ductility, and cost-effectiveness compared to existing HPDC Mg alloys and even A380 aluminum alloy.
  • The enhanced mechanical properties are attributed to the fine distribution of η-Al₃La particles, the coherent η-Al₃La/Mg interface, and the layered Mg matrix structure in eutectic areas.
• Academic Significance of the Research:
  • The study introduces a novel alloy design concept centered on controlling intermetallic phase components to optimize the properties of magnesium alloys.
  • It reports the discovery and detailed characterization of a new intermetallic phase, η-Al₃La, in the Mg-Al-La system, expanding the fundamental knowledge of intermetallic phases in magnesium alloys.
  • The research provides valuable insights into the relationship between intermetallic phase structure, interface characteristics, and the resulting mechanical properties of magnesium alloys.
• Practical Implications:
  • The ALaM440 alloy demonstrates significant potential as a high-performance, cost-effective alternative to both magnesium and aluminum alloys, particularly in automotive powertrain components.
  • Its excellent strength-ductility balance and creep resistance, coupled with its lower cost compared to AXJ530 alloy and comparable performance to A380 aluminum alloy, make it a promising candidate for industrial applications.
  • The alloy design concept and the understanding of intermetallic phase control can be extended to develop other high-performance magnesium alloys for various applications.
• Limitations of the Research:
  • While the paper demonstrates excellent performance in laboratory settings, further research is needed to assess the alloy's performance in real-world automotive powertrain applications and under various service conditions.
  • The study primarily focuses on room temperature and elevated temperature mechanical properties. Further investigation into other critical properties such as fatigue behavior, corrosion resistance, and long-term stability is warranted.
  • The research is mainly focused on the fundamental understanding of the alloy system and phase characterization. Further studies on optimizing the casting process and industrial scale-up production of ALaM440 alloy are necessary for practical implementation.

7. Future Follow-up Research:

• Directions for Follow-up Research:
  • Further optimization of the ALaM440 alloy composition and processing parameters to maximize its mechanical performance and reduce production costs.
  • Comprehensive evaluation of the ALaM440 alloy's performance in simulated and actual automotive powertrain component applications, including fatigue testing, impact testing, and long-term durability assessments.
  • Investigation of the corrosion behavior and surface treatment options for ALaM440 alloy to ensure its long-term reliability in automotive environments.
  • Exploration of the industrial scalability and cost-effective manufacturing processes for ALaM440 alloy, including optimizing die casting parameters and exploring alternative production routes.
• Areas Requiring Further Exploration:
  • Detailed investigation of the planar faults (MOTs) within the η-Al₃La phase and their influence on the alloy's deformation mechanisms and mechanical properties.
  • Further study of the η-Al₃La/Mg interface characteristics and their role in stress transfer and overall alloy performance.
  • Exploration of the potential for further enhancing the creep resistance and high-temperature performance of ALaM440 alloy through minor alloying additions or microstructural modifications.
  • Comparative life cycle assessment of ALaM440 alloy against existing magnesium and aluminum alloys to fully evaluate its environmental and economic benefits in automotive applications.

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9. Copyright:

• This material is Fanzhi Meng et al.'s paper: Based on Developing a die casting magnesium alloy with excellent mechanical performance by controlling intermetallic phase.
• Paper Source: https://doi.org/10.1016/j.jallcom.2019.04.346

This material was summarized based on the above paper, and unauthorized use for commercial purposes is prohibited.
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