Sustainability through Alloy Design: Challenges and Opportunities

This introduction paper is based on the paper "Sustainability through Alloy Design: Challenges and Opportunities" published by "Elsevier".

1. Overview:

• Title: Sustainability through Alloy Design: Challenges and Opportunities
• Author: Jaclyn L. Cann, Anthony De Luca, David C. Dunand, David Dye, Daniel B. Miracle, Hyun Seok Oh, Elsa A. Olivetti, Tresa M. Pollock, Warren J. Poole, Rui Yang, C. Cem Tasan
• Year of publication: 2020
• Journal/academic society of publication: Elsevier
• Keywords: Steel, Aluminum, Titanium, Magnesium, Superalloys, Shape memory alloys, High entropy alloys, Metallurgy, Sustainability

2. Abstract:

Exciting metallurgical breakthroughs of the last decades, and the development and wide range availability of new and more capable experimental and theoretical tools for metals research, demonstrate that we are witnessing the dawn of a new age in metals design. Historically, the discovery of new metallic materials has enabled the vast majority of the key engineering advances in human history.
Current engineering challenges create an urgent need for new metallic materials, to further our technological advances in multiple industries that are key to our existence. Yet, present data on metals processing clearly demonstrate the significant environmental impact of the metallurgical industry on our planet’s future. There are numerous reports in which this impact and corresponding processing solutions are discussed. On the other hand, design of new metallic materials with improved property combinations can help address key environmental challenges in various ways. To this end, the goal of this review is to discuss the most urgent sustainability challenges that can be addressed with alloy design, to help orchestrate the increasing interest in metallurgical research to focus on these most critical challenges.

3. Introduction:

The global use of metals is increasing [1], leading to a greater environmental burden from production and highlighting the urgency of addressing metals sustainability [2]. This requires a life cycle perspective, considering impacts from ore extraction, metal processing, product use, and end-of-life [3]. Alloy design can contribute significantly, for example, by enabling higher operating temperatures for increased thermodynamic efficiency, reducing mass in moving parts (like vehicles, offsetting higher production burdens with use-phase fuel savings [4–7]), or creating products with higher functionality for alternative energy generation.

While overall metal use grows, consumption of some toxic metals (Cd, Pb) has declined or stabilized [8], though their supply might persist as by-products [9]. Metals production, particularly primary production (using 7-8% of global energy), significantly impacts the environment through energy consumption, greenhouse gas emissions (e.g., CO2 in steel and Mg production), mining impacts (health, landscape, waste, water use), and potential release during use (corrosion) [10]. Steel has the largest impact by volume. High-impact metals per kilogram include trace elements (Sc, Re, Ge), while Fe, Al, and Cu contribute most to global warming potential annually [11].

Increasing elemental diversity in alloys (e.g., superalloys) improves properties but complicates end-of-life recovery and recycling [12, 13]. Recycling is limited by thermodynamics, element compatibility (Table 1), and infrastructure [14], posing challenges for compositionally complex alloys (CCAs) [15]. Resource availability and materials criticality are also concerns, especially for elements concentrated in politically unstable regions (Figure 1) or mined as byproducts [16–20].

Opportunities for increased sustainability exist in improving manufacturing efficiency (reducing yield losses, e.g., 25% in steel, 40% in Al - Figure 2) [21, 22], potentially through additive manufacturing [23]. However, the largest opportunity may lie in designing alloys for lifetime extension through improved durability, reliability, repairability, and reuse, particularly for ubiquitous materials like steel [24]. This review focuses on highlighting critical challenges and promising opportunities for promoting sustainability through alloy design across various alloy systems, considering environmental, political, and economic factors.

4. Summary of the study:

Background of the research topic:

The increasing demand for metals, coupled with the significant environmental footprint of their production and use (7-8% of global energy consumption, emissions, resource depletion), creates an urgent need for sustainable solutions within the metallurgical industry. Alloy design, influencing material properties and performance throughout the life cycle, represents a critical pathway to address these sustainability challenges.

Status of previous research:

Extensive research exists on improving sustainability through process modifications (e.g., production efficiency [26, 27], recycling [28, 29], CO2 reduction [26, 30], alternative production [26, 34]). Life cycle assessment methodologies [3] are established for evaluating environmental impacts. Specific alloy development efforts within various metal families have targeted improved properties like strength, temperature resistance, and durability. Research has also highlighted challenges related to recycling complex alloys [13, 14, Table 1], resource criticality [16, 17, Figure 1], and the trade-offs between production impacts and use-phase benefits (e.g., lightweighting [7]). Computational tools (DFT, CALPHAD, ICME) are increasingly used in alloy development.

Purpose of the study:

This review aims to identify and discuss the most significant sustainability challenges that can be effectively addressed through strategic alloy design. It surveys key opportunities across seven major alloy systems (steels, aluminum, titanium, magnesium, superalloys, shape memory alloys, high entropy/complex concentrated alloys) to guide future metallurgical research towards maximizing positive environmental impact. The focus is specifically on the role of alloy design, rather than processing improvements alone, in achieving sustainability goals.

Core study:

The review examines sustainability challenges and alloy design solutions for seven classes of metallic materials:

1. Steels:
   • Challenges: Largest production volume, significant environmental impact [21, 25], balancing strength/ductility, damage susceptibility in AHSS, recycling limitations (Cu contamination [67]), lifetime limitations (wear, fatigue, hydrogen embrittlement [HE]).
   • Solutions: Designing steels that "do more, with less, for longer."
     • Do more: Advanced High Strength Steels (AHSS - DP [36], TRIP [37], TWIP [38], 3rd Gen [41-43]) for improved strength-ductility, requiring better understanding of damage mechanisms [44-64].
     • With less: Promoting reuse/reforming [65, 66], lightweighting via density reduction (e.g., Al-alloyed TRIPlex steels [74, 75, Figure 3]) or modulus reduction (composites [77]).
     • For longer: Enhancing wear resistance (nano-bainite [78, 79], TWIP [84]), fatigue resistance (nanolaminated structures [80]), and HE resistance (austenite nano-films [95, 96], hcp ε-martensite designs [81, 98, 99]).
2. Aluminum alloys:
   • Challenges: High energy intensity of primary production [107], limited load-bearing capacity at elevated temperatures (>220°C) [104].
   • Solutions: Developing creep-resistant alloys for higher temperature applications (lightweighting in transport [103], power transmission [105], heat exchangers [106]). Key strategy: Precipitation strengthening with thermally stable, coarsening-resistant L12 nanoprecipitates (e.g., Al3Sc [108-120], Al3Zr [121-126], Al3Er [127, 128]). Design involves ternary/quaternary additions (Zr, Er, REEs) creating core-shell structures [114, 130-138, Figure 4], micro-alloying/inoculants (Si, Zn, Ge, Sn, Sb) [139-145], replacing expensive Sc [146-151], adding refractory elements (Ti, Hf, V, Nb, Ta) [152-156], and dual precipitation with α-Al(Fe,Mn)Si phases [165-173, Figure 5]. Recycling offers significant energy savings (92%) [107].
3. Titanium alloys:
   • Challenges: Energy-intensive extraction (Kroll process [180]), high cost, difficult certification for new alloys (aerospace dominance).
   • Solutions: Cost reduction via cheaper alloying elements (Fe for V [183, 184]), increased scrap usage [182], near-net-shape processing (AM [23]). Improving existing alloys:
     • (α+β) alloys: Enhancing strength/toughness balance through hierarchical microstructures [185] by controlling α precipitation from β using metastable phases (ω [189, 191-193], α″ martensite [190, 196, Figure 6], O′ [197], O″ [198]). Stress-induced α″ enables superelasticity [199-202].
     • Near α alloys: Mitigating cold dwell fatigue [186] by understanding and controlling microtexture and slip anisotropy (role of Mo, load shedding [203-210, Figure 7]).
     • γ-TiAl alloys: Increasing operating temperature (>750°C [188]) by controlling detrimental metastable phases (β/B2, ω, O phase [211-217]) formed at service temperatures, potentially via alloying (Zr, Mo) and strain engineering.
4. Magnesium alloys:
   • Challenges: Low density but high CO2 emissions in production (Pidgeon process [218, 223, Figure 8]), poor corrosion resistance [224], relative immaturity as structural material, complex behavior due to HCP structure.
   • Solutions: Holistic life cycle view is critical. Alloy design informed by ICME [235]: using CALPHAD [225, 226] and diffusion data [227], understanding solidification [229-232], controlling texture during wrought processing [234], activating slip for ductility via alloying (REs, Y, Ca, Mn, Zn, Al [236-242, Figure 9, Figure 10]), understanding deformation/recrystallization mechanisms [243-258], and precipitation hardening [259-262].
5. Superalloys:
   • Challenges: Reaching temperature limits of Ni-base alloys in high-pressure turbines [263, 264, Figure 11], reliance on expensive/critical elements (Re).
   • Solutions: Developing higher melting point materials (SiC-SiC [266], refractory alloys [267-269], Co-base γ-γ' alloys [270-273]). For Co-base alloys (precipitating L12 Co3(Al,W) [270, Figure 12]): navigating large compositional space using computational tools (DFT for stacking fault energy [287, Figure 13a], CALPHAD [302-305]), understanding unique deformation mechanisms (SISF/SESF shearing [281, 282, 285, 286]), developing W-free [292-301] and Re-free compositions, ensuring oxidation resistance and coating compatibility [311-315]. Continued development of constitutive/degradation models is needed [316].
6. Shape Memory Alloys (SMAs):
   • Challenges: Limited functional lifetime (fatigue) hinders applications in actuation (e.g., aerospace [317]) and potentially high-efficiency elastocaloric cooling/heat pumps [318-322, Figure A1].
   • Solutions:
     • NiTi: Improving functional fatigue life (>10^7 cycles [332]) by understanding defect generation [331] and tailoring transformation strain/hysteresis via alloying (cofactor conditions [332-336]) and introducing nanoscale precipitates [334].
     • CuZnAl: Exploring as a cheaper, lower-stress alternative [329, 337-341]; requires understanding its phase transformations (B2 -> 18R [342], γ phase [343, 346]) and stabilization strategies [345, 347]. Resource availability favors CuZnAl [346].
7. High Entropy Alloys (HEAs) and Complex Concentrated Alloys (CCAs):
   • Challenges: Moving beyond traditional single-base alloy design [348]; vast compositional space [349, 350]; constraints from cost, price volatility, resource availability (HHI Index [15, Figure 14]), and recyclability [15, Table 1]; need for fundamental understanding beyond configurational entropy [351, 363].
   • Solutions: Rational element selection based on sustainability criteria [15]. Developing design rules based on physics (e.g., lattice distortion [363], solid-solution strengthening [360, 361, 364], ductility criteria [362]). Employing multi-mechanism design: introducing intermetallic precipitates (high entropy superalloys [365]) or short-range order (SRO) [366-368]. Utilizing high-throughput experimental [369-373] and computational methods. Expanding the design space by integrating concepts from functional materials research [375-377, Figure 15].

5. Research Methodology

Research Design:

This study employs a comprehensive literature review methodology. It synthesizes existing knowledge and research findings from a wide range of published scientific papers, reports, and databases.

Data Collection and Analysis Methods:

The authors collected data from published literature concerning the sustainability aspects of metals production and use, including environmental impacts (energy consumption, emissions, resource depletion), life cycle assessments, recycling challenges, and resource availability. They analyzed research focused on alloy design strategies within seven major alloy systems (steels, Al, Ti, Mg, superalloys, SMAs, HEAs/CCAs). The analysis involved identifying key sustainability challenges specific to each alloy system and reviewing alloy design approaches proposed or implemented to address these challenges. The findings were synthesized to highlight promising opportunities and guide future research directions.

Research Topics and Scope:

The research focuses on the intersection of materials science, specifically alloy design, and sustainability. The scope covers:

• General sustainability challenges in the metals sector: life cycle impacts, energy and resource consumption, emissions, recycling, material criticality.
• Specific challenges and alloy design opportunities within seven major structural and functional alloy systems:
  • Steels
  • Aluminum alloys
  • Titanium alloys
  • Magnesium alloys
  • Superalloys
  • Shape memory alloys
  • High entropy alloys (HEAs) and complex concentrated alloys (CCAs)
• The role of alloy composition, microstructure, processing, and properties in influencing sustainability outcomes (e.g., lightweighting, efficiency, durability, recyclability).
• The application of computational and high-throughput methods in sustainable alloy design.

6. Key Results:

Key Results:

The review highlights that alloy design is a powerful tool for addressing sustainability challenges in metallurgy, offering diverse opportunities summarized in Table 2. Key strategies identified across various alloy systems include:

• Improving material efficiency: Designing alloys with enhanced combinations of properties (e.g., strength and ductility in AHSS, (α+β) Ti alloys, HEAs/CCAs) allows for reduced material usage ("doing more with less").
• Extending functional lifetime: Developing alloys with superior resistance to wear, fatigue, hydrogen embrittlement (steels, Ti), cold dwell fatigue (Ti), and improving functional stability (SMAs) reduces the need for replacement. Designing for reuse and recycling (steels, HEAs/CCAs) also contributes.
• Enhancing energy efficiency: Creating alloys stable at higher temperatures (Al alloys, γ-TiAl, superalloys) enables more efficient engines and energy systems. Developing materials for novel efficient technologies like elastocaloric heat pumps (SMAs) offers new pathways.
• Sustainable compositions: Strategically selecting alloying elements to replace scarce, costly, or environmentally problematic ones (e.g., Sc in Al, Re in superalloys, W in Co-base alloys) and designing alloys compatible with existing recycling streams or enabling new ones are crucial.
• Enabling tools: Computational materials science (ICME, DFT, CALPHAD) and high-throughput experimental techniques are essential for navigating complex alloy design spaces and accelerating the development of sustainable materials.
• Life Cycle Perspective: A consistent theme is the necessity of considering the entire life cycle – from extraction to end-of-life – when evaluating the sustainability benefits of alloy design choices.

Figure Name List:

• Table 1. Recoverability of alloying elements during extractive metallurgical processes. Green indicates that an element can be recovered in a single stage recovery process. Yellow indicates that an element is likely lost in a single stage recovery process (requiring subsequent post-recovery) without detriment to the carrier metal. Red indicates that an element cannot be economically recovered and are potentially detrimental to the carrier metal. Reproduced from [15].
• Figure 1. Geographic concentration for relevant materials. Concentrated supply chains are more vulnerable to disruption from socio-political upheaval, weather, and manufacturing bottlenecks.
• Figure 2. Energy Sankey diagram for the primary steel supply chain. Reproduced from [31].
• Figure 3. Ultimate tensile strength (MPa) versus elongation of high manganese TWIP or TRIPlex steels. Reproduced from [74].
• Figure 4. (a,b,c) LEAP tomography dataset obtained from an Al-0.08Zr-0.014Sc-0.008Er-0.10Si (at.%) alloy (further described in Refs. [150,151] over-aged for 21 day at 375°C, with Al atoms omitted for clarity; (b) and (c) display only the Zr and Sc atoms, respectively. (d) Associated proximity histogram showing (Al,Si)3(Zr,Sc,Er) concentration profile with a representative nano-precipitate in inset.
• Figure 5. STEM HAADF micrographs obtained from a Mo- and Mn-modified Al-Zr-Sc-Er-Si alloy aged 11 days at 400°C [172]. The α-AlMnSi precipitates exhibit an orientation relationship with the matrix, displaying both coherent and semi-coherent interfaces. The α-AlMnSi and L12 Al3M coexist and contribute jointly to strengthening.
• Figure 6. Lattice correspondence between the orthorhombic martensite α″ and the β phase with body centered cubic structure. Reproduced from [384].
• Figure 7. Illustration of the Stroh model [385] for planar slip in two neighbouring hexagonal grains. Reproduced from [186].
• Figure 8. Savings of greenhouse gas emissions during use stage for different magnesium scenarios. Reproduced from [223]
• Figure 9. Activation energy for cross-slip and ductility index χ for binary and higher-order Mg alloys. (A) Average solute contribution to energy difference ∆EII−I(c) between the pyramidal I and II (c+a) screw dislocations for various REs. Al, Zn, Zr, Ca, Mn, and Ag, immediately showing which solutes will be effective in enhancing ductility. (B) Predicted pyramidal II-I cross-slip activation energy barrier including solute fluctuations and ductility index χ for binary Mg alloys as a function of solute concentration c for the same solutes. χ > 1 indicates favorable conditions for ductility. RE solutes achieve χ > 1 at very low concentrations; Zr and Ca are also highly effective, and Mn is moderately effective. Zn and Ag (almost identical) have χ < 0 and do not reach favorable conditions for ductility. (C) Mg-Al-X-X’ with varying Al concentrations and (D) Mg-Zn-X-X’ with varying Zn concentrations. In (c), Al-Ca, Al-Mn, and Al-Ca-Mn reach the favorable ductility condition χ > 1 over some ranges of Al concentrations, and binary Mg-Al approaches χ = 0 at 1 to 3 at % Al. In (D), Zn-Ce, Zn-Mn, Zn-Mn-Ce, Zn-Zr, and Zn-Gd reach the favorable ductility condition χ > 1 at low Zn concentrations, and χ decreases as the Zn concentration increases. In (C) and (D), predictions are shown for Al and Zn concentrations above their very dilute limits; 0.1% wt Ca and 0.2% wt Ce can be in the very dilute limits. Attainable solute concentrations are limited by solubility and precipitation, factors not assessed here. The individual labels indicate solute weight percentage to make contact with standard alloy nomenclature. Reproduced from [241]
• Figure 10. Computed values of the yttrium-similarity index, YSI for the 2850 solute pairs computed in this study and visualized in the form of a symmetric matrix (a) with yellow indicating a high similarity and blue a low one. Solute pairs that have a high index (YSI > 0.95) are shown in the upper triangular part in (b). Applying a cost and solubility filter only a single pair, Al-Ca, remains (c). Reproduced from [242].
• Figure 11. Aircraft engine schematic (GE 90) along with constituent materials by weight. Adapted from Schafrik et. al. [265].
• Figure 12. (a) Microstructure of a Co-Al-W based alloy (45.9Co-9.8Al-6.3W-6.4Cr-2.4Ta-29.2Ni, at%), (b) compared to the microstructure of a commercial Ni-base alloy (René N5) and (c) TEM weak beam image of superlattice intrinsic stacking faults that form in the L12 precipitates during deformation of Co-base alloys at elevated temperatures.
• Figure 13. (a) The superlattice stacking fault energy (defined as the normalized difference between the energy of the L12 and DO19 structures) for Co3(Al, W) compared to Ni3Al, calculated with 32 atom supercells using density functional theory [287] and (b) the effect of solute addition to the Co3X and the scaling of the solvus with the SISF.
• Figure 14. (a) Alloy price in ($/mol) versus number of elements in alloy. (b) Price volatility versus number of elements in alloy. (c) Herfindahl-Hirschman Index (HHI) for various elements. Reproduced from [15].
• Figure 15. Diagrams illustrating the crystal structures of (a) the constituent elements at 600°C that make up the Cantor alloy, CoCrFeMnNi, and (b) oxide phases that have been mixed in equal proportions to produce a high entropy rocksalt (B1) structure [377] with oxygen (gray) atoms on one sublattice and a mixture of the metallic ions on the other sublattice. Three different types of cubic crystals produce an FCC solid solution in (a), and a mixture of cubic, monoclinic and hexagonal phases produce a cubic rocksalt structure in (b).
• Table 2. Summary table of sustainability challenges and key opportunities for each alloy system.
• Figure A1. Tusek’s regenerator. Elastocaloric material is held between grips. Starting in the austenite, the regenerator is loaded (a), causing the martensite transformation and heating of the superelastic material. (b) Fluid is pumped through the hot side heat exchanger HHEX, rejecting heat. (c) The regenerator is compressed into the austenite, cooling it, before finally at (d) the hot fluid is cooled and passed through the cold heat exchanger (CHEX). Redrawn from [380].

7. Conclusion:

This review has highlighted the most promising opportunities for using alloy design as a sustainable tool across seven different alloy systems, summarized in Table 2. These opportunities range from reducing material quantities via property improvements and extending functional lifetimes, to increasing stability at high temperatures for enhanced efficiency. Achieving these goals requires both environmentally-conscious selection of alloying elements and the use of computationally-informed material design strategies.

Common themes emerge, such as the simultaneous improvement of strength and ductility (e.g., in steels, Ti alloys, HEAs) to use less material, and increasing alloy lifetime through enhanced durability or enabling reuse/recycling. Energy efficiency gains are pursued through lightweighting (Mg, Al, steels) and developing materials for high-temperature applications (Al, γ-TiAl, superalloys) or novel cycles (SMAs). Sustainability considerations must permeate alloy design, from element selection (e.g., replacing Sc in Al, Re/W in superalloys) to designing for recyclability.

Theory and computational approaches (ICME, DFT, CALPHAD, phase-field, finite element, statistical methods) are indispensable for navigating the complex design spaces and accelerating progress. The increasing environmental burden from metal production [21, 12, 378] necessitates deliberate, informed decisions in alloy design. By focusing on the identified challenges and opportunities through conscientious alloy design, the metallurgical community can address urgent environmental issues and forge a sustainable path forward.

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