Fabricating Novel Metallic Materials Under Thermodynamic Far-from-Equilibrium Conditions

doi:10.12068/j.issn.1005-3026.2025.20240202

Abstract

Abstract:

The preparation of traditional metallic materials is mostly carried out under near-thermodynamic equilibrium conditions， where the interplay of multiple coupled sub-processes within the material limits the formation of ideal microstructures. By precisely regulating the rapid evolution of system thermodynamic parameters across the spatiotemporal dimensions， the material systems can be driven far from thermodynamic equilibrium. This dynamic decoupling of sub-processes enables novel pathways for the evolution of material composition and structure， facilitating the realization of unique microstructures and compositions that transcend the predictions of equilibrium phase diagrams. Guided by this principle， researchers have successfully developed far-from-equilibrium preparation techniques， such as ultrafast heat treatment， Joule heating preparation， and carbothermal shock. These methods have led to the discovery of various novel metallic materials with excellent properties. Principles and strategies for far-from-equilibrium metal material fabrication， focusing on the methods of controlling thermodynamic conditions in spatiotemporal dimensions. Furthermore， it delves into the application prospects of these techniques in the development of new materials， not only deepening the understanding of the nature of non-equilibrium processes but also providing innovative design paradigms for surpassing the performance boundaries of conventional materials.

Key words: non-equilibrium state, thermodynamic far-from-equilibrium, dynamic pathway, ultra-fast synthesis, new materials

CLC Number:

TB 31

Song LI, Yi-hong YU, Gao-wu QIN. Fabricating Novel Metallic Materials Under Thermodynamic Far-from-Equilibrium Conditions[J]. Journal of Northeastern University(Natural Science), 2025, 46(8): 57-76.

Figures/Tables 15

Fig.1 Energy evolution during the structural transformation of materials

Fig.2 Flash heat treatment of high-entropy alloys achieves high-density nanoprecipitation strengthening, enhancing the material’s ductility and toughness[37-38]

Fig.3 Relationship between heating rate and microstructural characteristics of Q&P steel[44-45]

Fig.4 Tensile fracture morphology and evolution of 5052 aluminum alloy annealed with different heating rates[50]

Fig.5 Gibbs-Thomson conditions for near-equilibrium and far-from-equilibrium solid-liquid interfaces[59]

Fig.6 The structure and properties of dual phase nano layered high entropy alloy (HEAs) AlCoCrFeNi2.1 printed by laser powder bed melting (L-PBF) technology[51]

Fig.7 Hot-top direct chill casting of large-size 2024 aluminum alloy ingots assisted by a twin-cooling field[15]

Fig.8 Carbonthermal shock (CTS) synthesis process of HEA-NPs on carbon supports[14]

Fig.9 Schematic diagram of the in situ self-assembly process of aluminum nanoparticles[68]

Fig.10 Synthesis and characterization of high-entropy M-RuIrFeCoNiO2[70]

Fig.11 Strategy comparison for synthesizing MOF-derived ultrasmall metal NPs[78]

Fig.12 Preparation of far-from-equilibrium functional materials via high-temperature plasma electrolytic oxidation[81] and arc discharge[85] methods

Fig.13 Nanoporous hierarchical high-entropy alloys via an electrochemical method with ultrahigh overpotential[86]

Fig.14 Preparation of solid solution CuAg nanoalloys via an electrochemical method with ultrahigh overpotential[89]

Table 1 Representative material types and unified performance metrics across various far-from-equilibrium

技术类型	材料类型	性能指标类别	代表性评价指标
超快热处理（FJH，CTS等）	高熵合金、钢铁	力学性能	屈服强度（σ）、抗拉强度（UTS）、断后伸长率（EL）、强度与塑性积（UTS×EL）
超快热处理（FJH，CTS等）	高熵合金、钢铁	显微结构参数	晶粒尺寸分布、位错密度、析出物密度（/m³）、平均粒径、孪晶密度
空间温差调控（增材制造等）	铝合金、HEAs	组织均匀性	晶粒尺寸梯度、组织双峰程度、元素偏析因子、冷却速率、热流密度
焦耳热/放电等极端加热	功能氧化物、MOFs	电催化性能	起始过电位、Tafel斜率、电化学活性表面积（ECSA）、金属负载量、粒径分布
电化学合成（电沉积、脉冲）	HER/ORR/CO₂RR	催化效率	法拉第效率、电流密度（mA/cm²）、生成速率（μmol/cm²·s）

References 90

[1]	Li Z W， Gan M Y， Wang Y， et al. Superior activity and durability of Co₃Mo correlated with interfacial microenvironment for hydrogen evolution［J］. Applied Catalysis B： Environmental and Energy， 2024， 358： 124395.
[2]	Yu Z R， Zhu L， Xu H X， et al. Selective enhancement of ethylene epoxidation via directing reaction pathways over Ag single-atom catalyst［J］. Industrial & Engineering Chemistry Research， 2024， 63（7）： 3044-3056.
[3]	Dai Y Z， Li H， Wang C H， et al. Manipulating local coordination of copper single atom catalyst enables efficient CO₂-to-CH₄ conversion［J］. Nature Communications， 2023， 14（1）： 3382.
[4]	武晓雷，朱运田.异构金属材料及其塑性变形与应变硬化［J］.金属学报，2022，58（11）：1349-1359.
	Wu Xiao-lei， Zhu Yun-tian. Heterostructured metallic materials： plastic deformation and strain hardening［J］. Acta Metallurgica Sinica， 2022， 58（11）： 1349-1359.
[5]	Zhu W， Gao X， Yao Y Y， et al. Nanostructured high entropy alloys as structural and functional materials［J］. ACS Nano， 2024， 18（20）： 12672-12706.
[6]	Mishra R S， Gupta S. Microstructural engineering through high enthalpy states： implications for far-from-equilibrium processing of structural alloys［J］. Frontiers in Metals and Alloys， 2023（2）： 1135481.
[7]	Yao G Y， Dong Q， Brozena A， et al. High-entropy nanoparticles： synthesis-structure-property relationships and data-driven discovery［J］. Science， 2022， 376（6589）： eabn3103.
[8]	Yu Y H， Qin Z P， Zhang X F， et al. Far-from-equilibrium processing opens kinetic paths for engineering novel materials by breaking thermodynamic limits［J］. ACS Materials Letters， 2024， 7（1）： 319-332.
[9]	Jiang R， Da Y M， Han X P， et al. Ultrafast synthesis for functional nanomaterials［J］. Cell Reports Physical Science， 2021， 2（1）： 100302.
[10]	Eddy L， Xu S C， Liu C H， et al. Electric field effects in flash joule heating synthesis［J］. Journal of the American Chemical Society， 2024， 146（23）： 16010-16019.
[11]	Skrabalak S E. Mashing up metals with carbothermal shock［J］. Science， 2018， 359（6383）： 1467.
[12]	Liang Z， Sasikumar K， Keblinski P. Liquid phase stability under an extreme temperature gradient［J］. Physical Review Letters， 2013， 111（22）： 225701.
[13]	Ramirez-Ledesma A L， Luna-Manuel J C， Lopez H F， et al. Defects induced through rapid solidification in a Co-20 Cr alloy［J］. Materials Science and Engineering： A， 2022， 844： 143161.
[14]	Yao Y G， Huang Z N， Xie P F， et al. Carbothermal shock synthesis of high-entropy-alloy nanoparticles［J］. Science， 2018， 359（6383）： 1489-1494.
[15]	Zhu C， Zhao Z H， Zhu Q F， et al. Hot-top direct chill casting assisted by a twin-cooling field： improving the ingot quality of a large-size 2024 Al alloy［J］. Journal of Materials Science & Technology， 2022， 112： 114-122.
[16]	Yang C， Ko B H， Hwang S， et al. Overcoming immiscibility toward bimetallic catalyst library［J］. Science Advances， 2020， 6（17）： eaaz6844.
[17]	Silvestroni L， Rueschhoff L M， Acord K A， et al. Synthesis of far-from-equilibrium materials for extreme environments［J］. MRS Bulletin， 2022， 47（11）： 1143-1153.
[18]	Jung C， Ihm Y， Cho D H， et al. Inducing thermodynamically blocked atomic ordering via strongly driven nonequilibrium kinetics［J］. Science Advances， 2021， 7（52）： eabj8552.
[19]	Düvel M， Merboldt M， Bange J P， et al. Far-from-equilibrium electron-phonon interactions in optically excited graphene［J］. Nano Letters， 2022， 22（12）： 4897-4904.
[20]	Zhang Z M， Lu Z Y. Nonequilibrium theoretical framework and universal design principles of oscillation-driven catalysis［J］. Journal of Physical Chemistry Letters， 2023， 14（33）： 7541-7548.
[21]	Bianchini M， Wang J， Clément R J， et al. The interplay between thermodynamics and kinetics in the solid-state synthesis of layered oxides［J］. Nature Materials， 2020， 19（10）： 1088-1095.
[22]	Haugerud I S， Jaiswal P， Weber C A. Nonequilibrium wet-dry cycling acts as a catalyst for chemical reactions［J］. The Journal of Physical Chemistry B， 2024， 128（7）： 1724-1736.
[23]	Tong X， Zhang Y E， Shang B S， et al. Breaking the vitrification limitation of monatomic metals［J］. Nature Materials， 2024， 23（9）： 1193-1199.
[24]	Min Y， Kwak J， Soon A， et al. Nonstoichiometric nucleation and growth of multicomponent nanocrystals in solution［J］. Accounts of Chemical Research， 2014， 47（10）： 2887-2893.
[25]	Xing Z Y， Lu J， Ji X L. A brief review of metallothermic reduction reactions for materials preparation［J］. Small Methods， 2018， 2（12）： 1800062.
[26]	Maklar J， Windsor Y W， Nicholson C W， et al. Nonequilibrium charge-density-wave order beyond the thermal limit［J］. Nature Communications， 2021， 12： 2499.
[27]	Prigogine I， Stengers I. Order out of chaos： man’s new dialogue with nature ［M］. New York： Bantam Books， 1984.
[28]	Dong Q， Lele A D， Zhao X P， et al. Depolymerization of plastics by means of electrified spatiotemporal heating［J］. Nature， 2023， 616（7957）： 488-494.
[29]	Han Y C， Cao P Y， Tian Z Q. Controllable synthesis of solid catalysts by high-temperature pulse［J］. Accounts of Materials Research， 2023， 4（8）： 648-654.
[30]	Goldstein R， Eddir T， Buchner E， et al. Modeling of temperature gradients during short time dilatometry testing［J］. Journal of Materials Engineering and Performance， 2020， 29（6）： 3638-3660.
[31]	Chen A N， Wang W Y， Mao Z Y， et al. Multimaterial 3D and 4D bioprinting of heterogenous constructs for tissue engineering［J］. Advanced Materials， 2024， 36（34）： 2307686.
[32]	Zhu C， Gemeda H B， Duoss E B， et al. Toward multiscale， multimaterial 3D printing［J］. Advanced Materials， 2024， 36（34）： 2314204.
[33]	马恩，刘畅.如何使合金兼具高强度与高塑性［J］.金属学报，2025，61（5）：665-673.
	Ma En， Liu Chang. Achieving alloys with concurrent high strength and high ductility［J］. Acta Metallurgica Sinica， 2025， 61（5）： 665-673.
[34]	Li W D， Xie D， Li D Y， et al. Mechanical behavior of high-entropy alloys［J］. Progress in Materials Science， 2021， 118： 100777.
[35]	Miracle D B， Senkov O N. A critical review of high entropy alloys and related concepts［J］. Acta Materialia， 2017， 122： 448-511.
[36]	Wu Q F， He F， Li J J， et al. Phase-selective recrystallization makes eutectic high-entropy alloys ultra-ductile［J］. Nature Communications， 2022， 13（1）： 4697.
[37]	Wang N， Nutor R K， Li Y X， et al. Tuning mechanical properties of high entropy alloys by electro-pulsing method［J］. Journal of Alloys and Compounds， 2022， 902： 163684.
[38]	Liu L Y， Zhang Y， Rogozhkin S， et al. Enhanced ductility via high-density nanoprecipitates driven by chemical supersaturation in a flash-heated precipitation-strengthened high-entropy alloy［J］. Acta Materialia， 2024， 281： 120434.
[39]	Mishnev R， Borisova Y， Kniaziuk T， et al. Phase transformations during partitioning in a Q&P steel with blocky retained austenite［J］. Materials Science and Engineering： A， 2024， 915： 147184.
[40]	Speer J， Matlock D K， de Cooman B C， et al. Carbon partitioning into austenite after martensite transformation［J］. Acta Materialia， 2003， 51（9）： 2611-2622.
[41]	Toji Y， Miyamoto G， Raabe D. Carbon partitioning during quenching and partitioning heat treatment accompanied by carbide precipitation［J］. Acta Materialia， 2015， 86： 137-147.
[42]	Papaefthymiou S， Banis A， Bouzouni M， et al. Effect of ultra-fast heat treatment on the subsequent formation of mixed martensitic/bainitic microstructure with carbides in a CrMo medium carbon steel［J］. Metals， 2019， 9（3）： 312.
[43]	Valdes-Tabernero M A， Vercruysse F， Sabirov I， et al. Effect of ultrafast heating on the properties of the microconstituents in a low-carbon steel［J］. Metallurgical and Materials Transactions A： Physical Metallurgy and Materials Science， 2018， 49（8）： 3145-3150.
[44]	de Knijf D， Puype A， Föjer C， et al. The influence of ultra-fast annealing prior to quenching and partitioning on the microstructure and mechanical properties［J］. Materials Science and Engineering： A， 2015， 627： 182-190.
[45]	Tan X D， Lu W J， Rao X. Effect of ultra-fast heating on microstructure and mechanical properties of cold-rolled low-carbon low-alloy Q&P steels with different austenitizing temperature［J］. Materials Characterization， 2022， 191： 112086.
[46]	Bertolo V， Vilasi L， Jiang Q， et al. Grain refinement by rapid cyclic heating and its effect on cleavage fracture behaviour of an S690 high strength steel［J］. Journal of Materials Research and Technology， 2023， 23： 1919-1933.
[47]	Yuan Q， Ren J， Mo J， et al. Effects of rapid heating on the phase transformation and grain refinement of a low-carbon mciroalloyed steel［J］. Journal of Materials Research and Technology， 2023， 23： 3756-3771.
[48]	Wen P Y， Hu B， Han J S， et al. A strong and ductile medium Mn steel manufactured via ultrafast heating process［J］. Journal of Materials Science & Technology， 2022， 97： 54-68.
[49]	Li Z H， Zhang J H， Xiao T X， et al. Regulating microstructure and improving precipitation hardening response of fine-grained Mg-RE-Ag hot-extruded alloy by extreme short-time heat treatment［J］. Materials Science and Engineering： A， 2024， 892： 146059.
[50]	Wen W Y， Zhao Y J， Deng Y J， et al. “Soft-hard” microstructure evolution and its relevance to high strength-plasticity and low plastic anisotropy of Al-Mg alloys based on ultra-fast heating［J］. Materials Science and Engineering： A， 2024， 893： 146154.
[51]	Ren J， Zhang Y， Zhao D X， et al. Strong yet ductile nanolamellar high-entropy alloys by additive manufacturing［J］. Nature， 2022， 608（7921）： 62-68.
[52]	Liu Q， Chu S J， Zhang X， et al. Laser shock processing of titanium alloys： a critical review on the microstructure evolution and enhanced engineering performance［J］. Journal of Materials Science & Technology， 2025， 209： 262-291.
[53]	DePond P J， Fuller J C， Khairallah S A， et al. Laser-metal interaction dynamics during additive manufacturing resolved by detection of thermally-induced electron emission［J］. Communications Materials， 2020（1）： 92.
[54]	Kermani M， Dong J， Biesuz M， et al. Ultrafast high-temperature sintering （UHS） of fine grained α-Al₂O₃ ［J］. Journal of the European Ceramic Society， 2021， 41（13）： 6626-6633.
[55]	Karma A， Tourret D. Atomistic to continuum modeling of solidification microstructures［J］. Current Opinion in Solid State and Materials Science， 2016， 20（1）： 25-36.
[56]	Tourret D， Liu H， LLorca J. Phase-field modeling of microstructure evolution： recent applications， perspectives and challenges［J］. Progress in Materials Science， 2022， 123： 100810.
[57]	Ji K H， Dorari E， Clarke A J， et al. Microstructural pattern formation during far-from-equilibrium alloy solidification［J］. Physical Review Letters， 2023， 130（2）： 026203.
[58]	Kavousi S， Novak B R， Hoyt J， et al. Interface kinetics of rapid solidification of binary alloys by atomistic simulations： application to Ti-Ni alloys［J］. Computational Materials Science， 2020， 184： 109854.
[59]	Li Y， Wang L， Wang Z J， et al. A phase-field model bridging near-equilibrium and far-from-equilibrium alloy solidification［J］. Acta Materialia， 2025， 284： 120596.
[60]	Haapalehto M， Pinomaa T， Wang L， et al. An atomistic simulation study of rapid solidification kinetics and crystal defects in dilute Al-Cu alloys［J］. Computational Materials Science， 2022， 209： 111356.
[61]	Antillon E A， Hareland C A， Voorhees P W. Solute trapping and solute drag during non-equilibrium solidification of Fe-Cr alloys［J］. Acta Materialia， 2023， 248： 118769.
[62]	Zhu C， Zhao Z H， Zhu Q F， et al. Floating grain formation and macrosegregation in a 2024 Al alloy prepared by hot-top DC casting with a 2024 Al alloy insert［J］. Metallurgical and Materials Transactions A， 2021， 52（8）： 3342-3352.
[63]	Zhu C， Zhao Z H， Wang G S， et al. Effect of 2024 Al alloy insert on the grain refinement of a 2024 Al alloy prepared via insert mold casting［J］. Metals， 2019， 9（10）： 1126.
[64]	Zhu C， Zhao Z H， Zhu Q F， et al. Structures and macrosegregation of a 2024 aluminum alloy fabricated by direct chill casting with double cooling field［J］. China Foundry， 2022， 19（1）： 1-8.
[65]	Liu Y L， Chen H， Xu C J， et al. Control of catalytic activity of nano-Au through tailoring the Fermi level of support［J］. Small， 2019， 15（34）： 1901789.
[66]	Li C Y， Wang Z J， Liu M D， et al. Ultrafast self-heating synthesis of robust heterogeneous nanocarbides for high current density hydrogen evolution reaction［J］. Nature Communications， 2022， 13（1）： 3338.
[67]	Ahn J， Park S， Oh D H， et al. Rapid joule heating synthesis of oxide-socketed high-entropy alloy nanoparticles as CO₂ conversion catalysts［J］. ACS Nano， 2023， 17（13）： 12188-12199.
[68]	Chen Y N， Egan G C， Wan J Y， et al. Ultra-fast self-assembly and stabilization of reactive nanoparticles in reduced graphene oxide films［J］. Nature Communications， 2016， 7： 12332.
[69]	Dou S M， Xu J， Zhang D F， et al. Ultrarapid nanomanufacturing of high-quality bimetallic anode library toward stable potassium-ion storage［J］. Angewandte Chemie International Edition， 2023， 62（26）： e202303600.
[70]	Hu C， Yue K， Han J， et al. Misoriented high-entropy iridium ruthenium oxide for acidic water splitting［J］. Science Advances， 2023， 9（37）： eadf9144.
[71]	Dou X W， Hasa I， Saurel D， et al. Hard carbons for sodium-ion batteries： structure， analysis， sustainability， and electrochemistry［J］. Materials Today， 2019， 23： 87-104.
[72]	Luong D X， Bets K V.， Algozeeb W A， et al. Gram-scale bottom-up flash graphene synthesis［J］. Nature， 2020， 577（7792）： 647-651.
[73]	Stanford M G， Bets K V， Luong D X， et al. Flash graphene morphologies［J］. ACS Nano， 2020， 14（10）： 13691-13699.
[74]	Liu J J， You Y W， Huang L， et al. Precisely tunable instantaneous carbon rearrangement enables low-working-potential hard carbon toward sodium-ion batteries with enhanced energy density［J］. Advanced Materials， 2024， 36（44）： 2407369.
[75]	Au H， Alptekin H， Jensen A C S， et al. A revised mechanistic model for sodium insertion in hard carbons［J］. Energy & Environmental Science， 2020， 13（10）： 3469-3479.
[76]	Chen D Q， Zhang W， Luo K Y， et al. Hard carbon for sodium storage： mechanism and optimization strategies toward commercialization［J］. Energy & Environmental Science， 2021， 14（4）： 2244-2262.
[77]	Han Y C， Yi J， Pang B B， et al. Graphene-confined ultrafast radiant heating for high-loading subnanometer metal cluster catalysts［J］. National Science Review， 2023， 10（6）： nwad081.
[78]	Han Y C， Liu M L， Sun L， et al. A general strategy for overcoming the trade-off between ultrasmall size and high loading of MOF-derived metal nanoparticles by millisecond pyrolysis［J］. Nano Energy， 2022， 97： 107125.
[79]	Xie H， Hong M， Hitz E M， et al. High-temperature pulse method for nanoparticle redispersion［J］. Journal of the American Chemical Society， 2020， 142（41）： 17364-17371.
[80]	Ntomprougkidis V， Martin J， Nominé A， et al. Sequential run of the PEO process with various pulsed bipolar current waveforms［J］. Surface and Coatings Technology， 2019， 374： 713-724.
[81]	Cao X Q， Zhou J， Zhai Z P， et al. Synchronous growth of porous MgO and half-embedded nano-Ru on a Mg plate： a monolithic catalyst for fast hydrogen production［J］. ACS Sustainable Chemistry & Engineering， 2021， 9（9）： 3616-3623.
[82]	Cao X Q， Zhou J， Li S， et al. Ultra-stable metal nano-catalyst synthesis strategy： a perspective［J］. Rare Metals， 2020， 39（2）： 113-130.
[83]	Cao X Q， Zhou J， Wang H N， et al. Abnormal thermal stability of sub-10 nm Au nanoparticles and their high catalytic activity［J］. Journal of Materials Chemistry A， 2019， 7（18）： 10980-10987.
[84]	Li Y X， Liao Y J， Ji L Z， et al. Quinary high-entropy-alloy@graphite nanocapsules with tunable interfacial impedance matching for optimizing microwave absorption［J］. Small， 2022， 18（4）： 2107265.
[85]	Li Y X， Liao Y J， Zhang P J， et al. High-entropy-alloy nanoparticles with enhanced interband transitions for efficient photothermal conversion［J］. Angewandte Chemie：International Edition， 2021， 60（52）： 27113-27118.
[86]	Wang Y N， Yang H， Zhang Z， et al. Far-from-equilibrium electrosynthesis ramifies high-entropy alloy for alkaline hydrogen evolution［J］. Journal of Materials Science & Technology， 2023， 166： 234-240.
[87]	Wu C Y， Hsiao Y C， Chen Y， et al. A catalyst family of high-entropy alloy atomic layers with square atomic arrangements comprising iron-and platinum-group metals［J］. Science Advances， 2024， 10（30）： eadl3693.
[88]	Mattarozzi L， Cattarin S， Comisso N， et al. Electrodeposition of metastable Ag-Rh alloys and study of their hydrogen storage ability in comparison with Pd［J］. Electrochimica Acta， 2018， 271： 370-378.
[89]	Yu Y H， Wang D， Hong Y M， et al. Bulk-immiscible CuAg alloy nanorods prepared by phase transition from oxides for electrochemical CO₂ reduction［J］. Chemical Communications， 2022， 58（79）： 11163-11166.
[90]	Wang Y F， Hall A S. Pulsed electrodeposition of metastable Pd₃₁Bi₁₂ nanoparticles for oxygen reduction electrocatalysis［J］. ACS Energy Letters， 2020， 5（1）： 17-22.