Non-equilibrium Processing Research Articles

Understanding the solute segregation and redistribution behavior in rapidly solidified binary Ti-X alloys fabricated through non-equilibrium laser processing

Understanding the solute segregation and redistribution behavior in rapidly solidified binary Ti-X alloys fabricated through non-equilibrium laser processing

An energy and information analysis method of logic gates based on stochastic thermodynamics.

To reduce the energy consumption of logic gates in digital circuits, the size of transistors approaches the mesoscopic scale, e.g. sub-7 nanometers. However, existing energy consumption analysis methods exhibit various deviation for logic gates when the nonequilibrium information processing of mesoscopic scale transistors with ultra-low voltages is analyzed. Based on the stochastic thermodynamics theory, an information energy ratio method is proposed for the energy consumption estimation of XOR gates composed of mesoscopic scale transistors. The proposed method provides a new insight to quantify the transformation between the information capacity and energy consumption for XOR gates and extending to other logic gates. Utilizing the proposed analysis method, the supply voltage of the parity check circuit can be optimized by numerical simulations without expensive and complex practical measurements. The information energy ratio is the first analytical method to quantify the energy and information transformation of logic gates at the mesoscopic scale.

Kinetics-controlled reaction pathway and microstructure development of Ti3SiC2-TiC composite processed through reactive spark plasma sintering

Reactive spark plasma sintering of ternary Ti-Si-C system was performed using three different powder precursors systems 3Ti/Si/2C, 3Ti/SiC/C and 2Ti/TiC/Si, to explore the fundamental physics behind Ti3SiC2 MAX phase formation, its stability and microstructure development, and, finally linked with its hardening and contact induced damage tolerance. Phase evolution in Ti-Si-C system is a complex phenomenon, and, present experimental conditions never yield a phase pure Ti3SiC2 MAX phase, rather results in varying volume fractions of Ti3SiC2-(Tix,Si1-x)C solid solution due to non-equilibrium processing conditions exerted by SPS processing which restricts coherent site specific diffusional jumps and promotes the formation of (Ti, Si)C solid-solution instead of well reported non-stoichiometric TiCx. 3Ti/SiC/C precursor was the best candidate for processing composite with highest yields of Ti3SiC2. Phase evolution is guided by the free energy of formation of different phases and chemical affinity amongst the constituent elements rather than the equilibrium phase diagram of the Ti-Si-C system. Presence of free carbon, low temperature liquid phase and slow heating rate are the key requirements for forming phase pure Ti3SiC2, where excess free carbon reduces the stability of Ti3SiC2 via decarburization. Non-equilibrium processing conditions impart nano-precipitation of coherent hexagonal Ti3SiC2 precipitates within a cubic (Ti, Si)C matrix with a distinct orientation relation of (220)matrix ║(0004)precipitate and <114>matrix ║<2–1–10>precipitate that has never been reported, instead of growing highest density plane of hcp-on-fcc matrix. Coherency strain and fine interlocking microstructure of the as-processed composite experiences ≈36 % of enhancement in hardness followed by an improved contact damage for the as-processed composite.

Crafting Multifunctional Materials with Tailored Mechanical and Magnetic Properties by Solid-State Non-equilibrium Processing

Crafting Multifunctional Materials with Tailored Mechanical and Magnetic Properties by Solid-State Non-equilibrium Processing

Microstructure, multi-scale mechanical and tribological performance of HVAF sprayed AlCoCrFeNi high-entropy alloy coating

Thermal spray high-entropy alloy (HEA) coatings have demonstrated potential for improving the wear resistance of conventional materials used in extreme engineering environments. In the present work, an equiatomic AlCoCrFeNi HEA coating was manufactured using the high velocity air fuel (HVAF) process. The phase and microstructural transformations in gas-atomized (GA) powder during HVAF spraying were analyzed using SEM, EDS and EBSD techniques. The tribological properties of this HEA coating sliding against an Al2O3 ball at both room temperature (RT) and 600 °C were also evaluated. The GA powder was composed of Body Centred Cubic (BCC) + ordered BCC (B2) phases, which transformed to BCC + B2 + minor Face Centred Cubic (FCC) phases during the HVAF coating process, validating the thermodynamic phase prediction projected by the Scheil simulation for non-equilibrium processing conditions. The rapid solidification and high velocity impact-assisted deformation of GA powder resulted in significant grain refinement in the HVAF coating, which ultimately improved the mechanical properties at both micro and nanoscale levels. The wear resistance of the HEA coating at RT was severely impacted by the relatively brittle BCC/B2 phase structure, leading to susceptibility to abrasive wear and surface fatigue. The wear resistance at 600 °C was slightly lower at RT due to the formation of a brittle oxide layer on the worn surface, which induced surface fatigue and aggravated mass loss of the coating.

Strengthening synergies of various interlayers in NiTi toTi6Al4V dissimilar laser joints

A sound NiTi-Ti6Al4V dissimilar joint featuring NiTi's superelasticity is crucial for merging both material benefits in aerospace and biomedical fields. Yet, the solidification of excessive intermetallic compounds (IMCs) for dissimilar par, notably Ti2Ni, poses a considerable risk of severe brittleness. Altering the chemistry of the fusion zone (FZ) could prevent embrittlement and enhance the mechanical performance of the joints. In this regard, understanding the impact of filler materials on the solidification behavior is vital. This study unveils the synergistic impact of employing these diverse interlayers, characterized by varying melting points, metallurgical compatibilities, and reaction spontaneity, on solidification behavior, microstructure evolution, and mechanical properties and presents a viable approach to enhance the microstructure and performance of NiTi and Ti6Al4V joints. A notable improvement in properties was observed in the Pd-interlayered joint, where the strong reaction spontaneity in the Ti-Pd system facilitated the preferential solidification of the TiPd phase in the FZ. This significantly reduced the amount of detrimental Ti2Ni IMC, ultimately decreasing joint embrittlement. Mechanical testing data demonstrated a progression in performance in the following sequence: interlayer-free, Co-interlayered, Zr-interlayered, and Pd-interlayered. Using interlayer materials that form lower-energy compounds with Ti and offer good mechanical properties, such as TiPd in this study, is presented as an optimal approach to enhance joint mechanical properties. The present work advances the metallurgical knowledge associated with non-equilibrium processing of NiTi and Ti6Al4V alloys.

Scalable multilayered dielectric polymer film exhibiting significantly improved high-temperature energy density

Dielectric polymers, serving as crucial dielectric media in high-power-density energy storage devices, play a pivotal part in modern industries and electrical systems. However, the rapid degradation of breakdown strength and charge-discharge efficiency in elevated temperature environment imposes formidable limitations on the utilization of polymer dielectric under extreme conditions. Here, a series of polyetherimide/polysulfone alternating multilayer composite films are prepared using a non-equilibrium processing method, which effectively blocks the development of breakdown paths by the interface barriers in the multilayer structure. The deep trap sites within the interface capture the charge carriers excited at high temperatures, thus decreasing conduction loss and enhancing the efficiency and breakdown field strength of the dielectric polymer. Consequently, excellent capacitive performances including a high energy density of 5.4 J cm−3 with an efficiency exceeding 90% at 200 °C and cycle stability up to 106 cycles have been obtained. Furthermore, the multilayer polymer capacitors (MLPC) constructed from composite films also exhibit significant flexibility and thermal stability. This work provides valuable insights for the advancement of high-temperature energy storage polymers with commercial application value.

Transient Interfacial Pattern Formation in Block Copolymer Thin Films via Sequential Thermal and Solvent Immersion Annealing.

A variety of structures encountered in nature only arise in materials under highly nonequilibrium conditions, suggesting to us that the scope for creating new functional block copolymer (BCP) structures might be significantly enlarged by embracing complex processing histories that allow for the fabrication of structures quite unlike those created under "near-equilibrium" conditions. The present work examines the creation of polymer film structures in which highly nonequilibrium processing conditions allow for the creation of entirely new types of transient BCP morphologies achieved by transitioning between different ordered states. Most previous studies of BCP materials have emphasized ordering them from their disordered state obtained from a solution film casting process, followed by a slow thermal annealing (TA) process at elevated temperatures normally well above room temperature. We have previously shown that achieving the equilibrium TA state can be accelerated by a direct solvent immersion annealing (DIA) preordering step that creates nascent ordered microstructures, followed by TA. In the present work, we examine the reverse nonequilibrium sequential processing in which we first thermally anneal the BCP film to different levels of partial (lamellar) order and then subject it to DIA to swell the lamellae. This sequential processing rapidly leads to a swelling-induced wrinkle pattern that initially grows with immersion time and can be quenched by solvent evaporation into its corresponding glassy state morphology. The article demonstrates the formation of wrinkling "defect" patterns in entangled BCP films by this sequential annealing that does not form under ordinary TA conditions. At long DIA times, these highly "defective" film structures evolve in favor of the equilibrium morphology of parallel lamellae observed with DIA alone. In conjunction with our previous study of sequential DIA + TA, the present TA + DIA study demonstrates that switching the order of these processing methods for block copolymer films gives the same final state morphology in the limit of long time as any one method alone, but with drastically different intermediate transient state morphologies. These transient morphologies could have many applications.

Microgravity effects on nonequilibrium melt processing of neodymium titanate: thermophysical properties, atomic structure, glass formation and crystallization

The relationships between materials processing and structure can vary between terrestrial and reduced gravity environments. As one case study, we compare the nonequilibrium melt processing of a rare-earth titanate, nominally 83TiO2-17Nd2O3, and the structure of its glassy and crystalline products. Density and thermal expansion for the liquid, supercooled liquid, and glass are measured over 300–1850 °C using the Electrostatic Levitation Furnace (ELF) in microgravity, and two replicate density measurements were reproducible to within 0.4%. Cooling rates in ELF are 40–110 °C s−1 lower than those in a terrestrial aerodynamic levitator due to the absence of forced convection. X-ray/neutron total scattering and Raman spectroscopy indicate that glasses processed on Earth and in microgravity exhibit similar atomic structures, with only subtle differences that are consistent with compositional variations of ~2 mol. % Nd2O3. The glass atomic network contains a mixture of corner- and edge-sharing Ti-O polyhedra, and the fraction of edge-sharing arrangements decreases with increasing Nd2O3 content. X-ray tomography and electron microscopy of crystalline products reveal substantial differences in microstructure, grain size, and crystalline phases, which arise from differences in the melt processes.

Synthesis of functional ceramics by microwave non-equilibrium processing

Synthesis of functional ceramics by microwave non-equilibrium processing

Unimer suppression enables supersaturated homopolymer swollen micelles with long-term stability after glassy entrapment.

Micelle sizes are critical for a range of applications where the simple ability to adjust and lock in specific stable sizes has remained largely elusive. While micelle swelling agents are well-known, their dynamic re-equilibration in solution implies limited stability. Here, a non-equilibrium processing sequence is studied where supersaturated homopolymer swelling is combined with glassy-core ("persistent") micelles. This path-dependent process was found to sensitively depend on unimer concentration as revealed by DLS, SAXS, and TEM analysis. Here, lower-selectivity solvent combinations led to the formation of unimer-homopolymer aggregates and eventual precipitation, reminiscent of anomalous micellization. In contrast, higher-selectivity solvents enabled supersaturated homopolymer loadings favored by rapid homopolymer insertion. The demonstrated ∼40-130 nm core-size tuning exceeded prior equilibrium demonstrations and subsequent core-vitrification enabled size persistence beyond 6 months. Lastly, the linear change in micelle diameter with homopolymer addition was found to correlate with a plateau in the interfacial area per copolymer chain.

(Invited) Gravitational Level Effects on Electrochemical Interfacial Phenomena

Electrochemical copper refining technology invented in Niagara area made a great progress over more than 100 years through better understanding of natural convection phenomena. Ionic mass-transfer rate enhanced by natural convection developing along 1m high vertical electrode surfaces has been unconsciously utilized by trial-and-error method. As the local electrolyte composition is partly stratified in an electrolytic cell (roughly 5m long x 1.3m wide x 1.3m depth). The industrial electrolytic tank house is composed of about 1000 cells through which the electrolyte is continuously supplied. Thus, the electrolyte circulation is a key technology in industrial copper refining processes as well as appropriate selection of effective additive and stable sedimentation of anode slime containing precious metals on the electrolytic tank bottom.On the other hand, Cu nanowire arrays were electrodeposited potentiostatically with PC filter template in two kinds of electrolytic cell configurations: cathode over anode (C/A) and anode over cathode (A/C). The effect of gravitational level on the coupling phenomena between the morphological variation and the ionic mass transfer rate in nanosized pores(a mesoscopic scale of a fewμm high and 30nm in diameter) was also found. Hitherto, the coupling phenomena accompanied with the electrochemical interfacial reactions confined in such a mesoscopic space has not been studies in spite of the great technological interest for the production of micro- or meso-scale fabrication techniques encountered in microelectronics and energy conversion & storage technology field. The initial stage including nucleation and growth process during electrochemical phase transformation reactions must be at first focused to profoundly comprehend the present subject in order to reasonably design such an advanced device technology.Fundamental aspects in electrochemical processes in microgravity environments have not been frequently reported. However, Artemis projects may provide the large opportunities on the energy storage and power generation, as well as materials processing. The effects of gravitational level and magnetic field gradient on the electrochemical interfacial phenomena should be understood. The drop tower facility surely offers the appropriate & “unique” experimental opportunities to propose such research program in the future space engineering fields. Electrocrystallization of metals is selected as a good subject for starting direction of research. Its reaction mechanism is relatively simple, the deposition rate can be easily varied by changing the current density or potential, and a smooth copper film is deposited so long as it is not too thick.By the way, the damascene process has been introduced to copper wiring process in ULSI field by IBM almost 25 years ago. It is important to control the nucleation and crystal growth in the initial stages of electrodeposition process. For this purpose, many effects of additive have been intensively examined. However, few quantitative examinations have been reported on the coupling phenomena of ionic mass transfer and nucleation and crystal growth. In the present work, we introduce various gravitational levels as new parameters into the nonequilibrium electrochemical processing in order to create or tailor the unique physical properties in nano space field. It is fruitful in terms of physicochemical hydrodynamics that the experiments are done under various gravitational levels. In fact, it has been confirmed that the gravitational levels as well as the magnetic field introduce the intensified effects from that under 1 G normal environment. Here is a report to analyze the effect of gravitational level on the initial stages of Cu electrodeposition on TaN or TiN substrate.

Synergetic effect of microfluidic flow and ultrasonication on chains pre-ordering in conjugated polymer solution

Multi-physical fields solution processing strategy provides a universal and facile way to prepare various conjugated polymer (CP) films and high-performance devices, whereas the hierarchical structures evolution and crystallization of the polymer chains are elusive particularly under the far-from-equilibrium state in solution. In this work, we employed a combined microfluidic flow and ultrasonication strategy (FU) for CP solution processing and found a pronounced synergetic effect of these fields in promoting the pre-ordering of chains in solution. This conformation order and anisotropy of the solution were revealed by using UV–Vis absorption, polarized optical microscopy (POM) and cryogenic transmission electron microscopy (Cryo-TEM) characterizations. A non-classical nucleation model for the conjugated polymer crystallization in the procedure of non-equilibrium solution processing was confirmed. The roles of microfluidic flow and ultrasonication on the chain aggregation and crystallization were addressed with the aim of a multi-physical simulation based on pressure acoustics streaming, fluid heat transfer and thermoviscous boundary layer impedance. Compared to pristine solutions, the FU strategy showed improved solution anisotropy and crystallization kinetics, substantially giving rise to a larger crystallinity in films and much increased mobilities for the organic field-effect transistor (OFET) devices by more than an order of magnitude. With an appropriate balance between the solvation and interchain interactions, the FU processing strategy is universal for regulation of chains conformation and aggregation in conjugated polymer solution.

Effect of Mn on eutectic phase equilibria in Al-rich Al-Ce-Ni alloys

Microstructural analysis of additively manufactured (AM) Al-Ce-Ni-Mn alloys has identified phases not predicted from existing ternary liquidus projections in the Al-Ce-Ni system. Because the rapid cooling rate of AM is orders of magnitude above that of traditional casting, it is unclear if these additional phases arose from the non-equilibrium processing conditions of AM, a drastic shift in phase stability in the system due to the addition of 1 wt% Mn, or some combination of these two influences. The phases and microstructure of cast samples of Al-Ce-Ni and Al-Ce-Ni-Mn alloys were characterized for several annealing conditions which revealed the equilibrium phases at different temperatures. Phase analysis confirmed that minute levels of Mn substituted for Ni in the system drastically shifts the liquidus projection in the Al-rich corner of the ternary phase diagram such that the eutectic Al3Ni phase is suppressed in favor of the Al23Ni6(Ce,Mn)4 phase. Further addition of Mn promotes the formation of Al20Mn2Ce and Al10Mn2Ce phases. The phase analysis data was then used to improve the CALPHAD modeling of the liquidus projection and isothermal sections for the Al-rich Al-Ce-Ni-Mn quaternary system. Thermodynamic modeling and experimental analysis on phases in the AM sample of Al-Ce-Ni with Mn confirmed that the phases present are consistent with Mn-containing Al-Ce-Ni cast samples. This investigation demonstrates the potential for using secondary alloying elements to drastically alter phase stability and microstructure in alloy systems.

Role of Kinetics and Thermodynamics in Controlling the Crystal Structure of Nickel Nanoparticles Formed on Reduced Graphene Oxide: Implications for Energy Storage and Conversion Applications

Ultrafast heating has emerged recently to speed up the synthesis processes of nanoparticles and control their morphology. However, it is not clear how the heating rate affects the formation of metal nanoparticles, particularly those formed on substrates. Here, we explored the formation of nickel (Ni) nanoparticles on graphene oxide (GO) substrates under slow (20 °C/min) and ultrafast (103 °C/s) heating rates. The experiments were performed in situ on heating microchip devices using an aberration-corrected transmission electron microscope. Interestingly, the GO structure was the most effective in controlling the stability of nanoparticles when ultrafast heating was employed, leading to a hexagonally close-packed Ni phase (hcp-Ni) because of less lattice mismatch with the graphitic substrate. On the contrary, fcc-Ni nanoparticles formed under a slow heating process where no strong correlation with the GO crystal structure was observed. Additionally, ultrafast heating resulted in smaller-size nanoparticles which could be ascribed to rapid reduction, nucleation rate, and higher diffusion barrier of hcp-Ni crystals on rGO. Nevertheless, the stability of the crystal structure of the nickel nanoparticles remains unaffected by their size. These results indicate the crucial role of the substrate on crystal structure during the nonequilibrium processing of materials and the competing effects of thermodynamics versus kinetics in creating novel phases of materials for energy storage and conversion applications.

Evaporation behavior of liquid microdroplets in atmospheric-pressure nonequilibrium plasma

In recent years, atmospheric-pressure nonequilibrium plasma processing using microdroplets has attracted significant attention. To improve the controllability of this process, an understanding of the evaporation behavior of droplets in plasma is highly desirable. In this study, we examine the evaporation behavior of well-controlled inkjet droplets in atmospheric-pressure nonequilibrium argon plasma through both experiments and modeling. A comparison of the droplet evaporation model based on energy balance considering gas temperature, electron and ion collisions, and recombination reactions with experimental evaporation behavior suggests that droplet evaporation is enhanced in high-density plasma environments with electron and ion densities exceeding 1019 m−3 when compared with that in non-ionized gaseous environments at a gas temperature below 1000 K.

Dynamic interfaces for contact-time control of colloidal interactions.

Understanding pairwise interactions between colloidal particles out of equilibrium has a profound impact on dynamical processes such as colloidal self assembly. However, traditional colloidal interactions are effectively quasi-static on colloidal timescales and cannot be modulated out of equilibrium. A mechanism to dynamically tune the interactions during colloidal contacts can provide new avenues for self assembly and material design. In this work, we develop a framework based on polymer-coated colloids and demonstrate that in-plane surface mobility and mechanical relaxation of polymers at colloidal contact interfaces enable an effective, dynamic interaction. Combining analytical theory, simulations, and optical tweezer experiments, we demonstrate precise control of dynamic pair interactions over a range of pico-Newton forces and seconds timescales. Our model helps further the general understanding of out-of-equilibrium colloidal assemblies while providing extensive design freedom via interface modulation and nonequilibrium processing.

Coacervate or precipitate? Formation of non-equilibrium microstructures in coacervate emulsions.

Non-equilibrium processing of aqueous polyelectrolyte complex (PEC) coacervates is critical to many applications. In particular, many coacervate-forming systems are known to become trapped in out-of-equilibrium states (e.g., precipitation). The mechanism and conditions under which these states form, and whether they age, is not clearly understood. Here, we elucidate the influence of processing on the PEC coarsening mechanism as it varies with flow during mixing for a model system of poly(allylamine hydrochloride) and poly(acrylic acid sodium salt) in water. We demonstrate that flow conditions can be used to toggle the formation of rough, precipitate-like aggregates of micron-scale PEC structures. These structures form at compositions with viscous-dominant equilibrium rheology, and observations of their formation via optical microscopy suggest that they comprise colloidal aggregates of PEC coacervate droplets. We further show that these aggregates exhibit micron-scale coarsening, with a mixing time-dependent characteristic aging time scale. The results show that the formation of precipitate-like structures is not solely determined by composition, but is instead highly sensitive to mass transport and colloidal instability effects. Our observations suggest that the details of mixing flow can provide non-equilibrium structural control of a broad range of PEC coacervate materials orthogonally to structure-property inspired polymeric design. We anticipate that these findings will open the door for future studies on the control of non-equilibrium PEC formation and structure.

Towards an alloy design strategy by tuning liquid local ordering: What solidification of an Al-alloy designed for laser powder bed fusion teaches us

High-strength aluminium alloys from the 2XXX, 6XXX, and 7XXX series suffer from severe hot cracking issues during 3D printing. Thus, there is a need to design new alloys with an improved hot cracking resistance while taking advantage of the non-equilibrium processing conditions of laser powder bed fusion to achieve optimized properties. Here, we report the successful fabrication of a new Al-Mn-Ni-Cu-Zr alloy designed for L-PBF. The as-built microstructure was characterized at different scales using synchrotron X-ray nano-tomography and microscopy with a special focus on automated crystallographic orientation mapping (ACOM) in transmission electron microscopy. Based on this multiscale microstructural investigation, we identify various mechanisms involving the presence of a locally ordered liquid during solidification under conditions typical of additive manufacturing. This local liquid ordering is often defined as Icosahedral Short Range Order (ISRO). The multiple consequences of ISRO in the liquid on the hierarchical microstructure inherited from additive manufacturing are discussed. ISRO enables refinement of the grain size thus improving the processability via an increase of the hot cracking resistance, producing equiaxed grains and twinned dendrites contributing to randomizing the crystallographic texture, and possibly extending supersaturated solid solutions through a cage effect. It is concluded that promoting ISRO should be considered a promising pathway to design alloys for additive manufacturing with good processability and optimized properties.

Strengthening Analysis of Ni-Sn Alloy Layer by Double Alloying Method Combined with First-Principles Calculation.

Surface modification improves the performance of materials in practical applications. In this paper, mechanical alloying pretreatment is adopted. Advanced non-equilibrium processing of a high-current pulse electron beam is then used to obtain an Sn-rich Ni-Sn alloy layer, characterized by a higher surface hardness than the initial pure nickel layer. In addition, the atomic structure of the Sn-doped nickel substrate in the alloy layer is simulated, and the improvement of the alloy layer is analyzed based on the first principle. Mechanical alloying and electron beam irradiation form fine and even nanocrystals on the surface of the nickel. Sn doping is also important for enlarging the lattice and increasing the stress.