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At least 487 records · Page 27

First-order magnetic phase transition in P r 2 In with negligible thermomagnetic hysteresis

Magnetic first-order phase transitions are key for the emergence of functionalities of fundamental and applied significance, including magnetic shape memory as well as magnetostrictive and magnetocaloric effects. Such transitions are usually associated with thermomagnetic hysteresis. In this paper we report the observation of a firstorder transition in Pr 2 In from a paramagnetic to a ferromagnetic state at $T_C$ = 57K without a detectable thermomagnetic hysteresis, which is also accompanied by a large magnetocaloric effect. The peculiar electronic structure of Pr2In exhibiting a large density of states near the Fermi energy explains the highly responsive magnetic behavior of the material. The magnetic properties of Pr 2 In are reported, including observation of another (second-order) magnetic transition at 35 K.

36 MATERIALS SCIENCE↗

Precisely computing phonons via irreducible derivatives

Computing phonons from first principles is typically considered a solved problem, yet inadequacies in existing techniques continue to yield deficient results in systems with sensitive phonons. Here, in this study, we circumvent this issue using the lone irreducible derivative (LID) and bundled irreducible derivative (BID) approaches to computing phonons via finite displacements, where the former optimizes precision via energy derivatives and the latter provides the most efficient algorithm using force derivatives. A condition number optimized basis for BID is derived which guarantees the minimum amplification of error. Additionally, a hybrid LID-BID approach is formulated, in which select irreducible derivatives computed using LID replace BID results. We illustrate our approach on two prototypical systems with sensitive phonons: the shape memory alloy AuZn and metallic lithium. Comparing our resulting phonons in the aforementioned crystals to calculations in the literature reveals nontrivial inaccuracies. Our approaches can be fully automated, making them well suited for both niche systems of interest and high-throughput approaches.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Nanoscale magnetic phase competition throughout the Ni 50– x Co x Mn 40 Sn 10 phase diagram: Insights from small-angle neutron scattering

The Ni 2 MnSn-derived Ni 50– x Co x Mn 25+ y Sn 25– y alloys are premier examples of a class of off-stoichiometric Heusler alloys recently discovered to exhibit attractive magnetic properties in tandem with extraordinarily reversible martensitic phase transformations. Multiferroicity, magnetic phase competition and separation, field-induced martensitic transformations, magnetic shape memory behavior, and sizable magneto-, elasto-, and barocaloric effects result, generating substantial interest and application potential. In this work we expand on a prior small-angle neutron scattering (SANS) study at a single composition (Ni 44 Co 6 Mn 40 Sn 10 ) by exploring all three main regions of the recently established Ni 50–x Co x Mn 40 Sn 10 phase diagram, i.e., at the representative y = 15 composition. Wide temperature and scattering wave-vector range (20–500K, 0.004–0.2Å –1 ) SANS data on x = 2, 6, and 14 polycrystals provide a detailed picture of the evolution in magnetic order and inhomogeneity. Consistent with recent studies with a variety of techniques, phase separation into short-range coexisting ferromagnetic and antiferromagnetic regions is deduced below the martensitic transformation at x = 2 and 6, with average ferromagnetic cluster spacing of ~13 nm. Remarkably, at x = 14, where the martensitic transformation is suppressed and ferromagnetic austenite is stabilized to low temperatures, nanoscopic magnetic inhomogeneity nevertheless persists. Further, distinct ferromagnetic clusters (~36-nm average spacing) in a ferromagnetic matrix are observed at intermediate temperatures, homogenizing into a uniform long-range ordered ferromagnet only at low temperatures. This unusual ferromagnet cluster/ferromagnet matrix inhomogeneity, as well as x -dependent subtleties of the superparamagnetic freezing of ferromagnetic clusters, are discussed in light of 55 Mn nuclear magnetic resonance data, and the recent observation of annealing-induced core/shell nanoprecipitates. The origins of nanoscalemagnetic inhomogeneity are discussed in terms of statistical variations in local composition and structure, tendency to chemical phase separation, and other forms of disorder.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Control of ternary alloy composition during remote epitaxy on graphene

Understanding the sticking coefficient σ, i.e., the probability of an adatom sticking to a surface, is essential for controlling the stoichiometry during epitaxial film growth. However, σ on monolayer graphene-covered surfaces and its impact on remote epitaxy are not understood. Here, using molecular-beam epitaxial growth of the magnetic shape memory alloy Ni 2 MnGa, we show that the sticking coefficients for metals on graphene-covered MgO (001) are less than one and are temperature and element dependent, as revealed by ion backscattering spectrometry and energy-dispersive x-ray spectroscopy. This lies in stark contrast with most transition metals sticking on semiconductor and oxide substrates, for which σ is near unity at typical growth temperatures (T < 800°C). By initiating growth below 400°C, where the sticking coefficients are closer to unity and wetting on the graphene surface is improved, we demonstrate the epitaxy of Ni 2 MnGa films with controlled stoichiometry that can be exfoliated to produce freestanding membranes. Straining these membranes tunes the magnetic coercive field. Finally, our results provide a route to synthesize membranes with complex stoichiometries whose properties can be manipulated via strain.

36 MATERIALS SCIENCE↗

An in situ neutron diffraction study of anomalous superelasticity in a strain glass Ni 43 Fe 18 Ga 27 Co 12 alloy

Superelastic behavior is traditionally related to the martensitic transition with a collective transformation scenario in some shape memory alloys. A kind of quasi-linear superelasticity accompanied by a finite avalanche or confined martensitic transformation was recently found in some alloy systems with strain glass state. Here, an in situ neutron diffraction technique was used to study the deformation behavior in an Ni 43 Fe 18 Ga 27 Co 12 alloy with strain glass state in order to reveal the new intrinsic physical nature of the quasi-linear superelasticity. A significant modulus softening prior to the stress-induced martensitic transformation was observed during compression in the studied alloy, which is similar to the characteristics exhibited in the tweed precursor phenomena prior to temperature-induced martensitic transformation. Moreover, the diffraction peak broadening was further shown during the elastic stage of deformation for both single-crystal and polycrystalline samples, which mainly stems from the short-range fluctuation in the strain field inside each grain based on Williamson–Hall analysis. The authors believe that there exists a spatial heterogeneity in the modulus of the confined martensitic transformation alloy.

Zhang, Q. H.↗

Derived crystal structure of martensitic materials by solid–solid phase transformation

A mathematical description of crystal structure is proposed consisting of two parts: the underlying translational periodicity and the distinct atomic positions up to the symmetry operations in the unit cell, consistent with the International Tables for Crystallography. By the Cauchy–Born hypothesis, such a description can be integrated with the theory of continuum mechanics to calculate a derived crystal structure produced by solid–solid phase transformation. In addition, the expressions for the orientation relationship between the parent lattice and the derived lattice are generalized. Additionally, the derived structure rationalizes the lattice parameters and the general equivalent atomic positions that assist the indexing process of X-ray diffraction analysis for low-symmetry martensitic materials undergoing phase transformation. The analysis is demonstrated in a CuAlMn shape memory alloy. From its austenite phase (L2 1 face-centered cubic structure), it is identified that the derived martensitic structure has orthorhombic symmetry Pmmn with the derived lattice parameters a d = 4.36491, b d = 5.40865 and c d = 4.2402 Å, by which the complicated X-ray Laue diffraction pattern can be well indexed, and the orientation relationship can be verified.

36 MATERIALS SCIENCE↗

A Subspace-Inclusive Sampling Method for the Computational Design of Compositionally Graded Alloys

Abstract Compositionally graded alloys, a subclass of functionally graded materials (FGMs), utilize localized variations in composition with a single metal part to achieve higher performance than traditional single material parts. In previous work [Kirk, T., Galvan, E., Malak, R., and Arroyave, R., 2018, “Computational Design of Gradient Paths in Additively Manufactured Functionally Graded Materials,” J. Mech. Des., 140, p. 111410. 10.1115/1.4040816], the authors presented a computational design methodology that avoids common issues which limit a gradient alloy’s feasibility, such as deleterious phases, and optimizes for performance objectives. However, the previous methodology only samples the interior of a composition space, meaning designed gradients must include all elements in the space throughout the gradient. Because even small amounts of additional alloying elements can introduce new deleterious phases, this characteristic often neglects potentially simpler solutions to otherwise unsolvable problems and, consequently, discourages the addition of new elements to the state space. The present work improves upon the previous methodology by introducing a sampling method that includes subspaces with fewer elements in the design search. The new method samples within an artificially expanded form of the state space and projects samples outside the true region to the nearest true subspace. This method is evaluated first by observing the sample distribution in each subspace of a 3D, 4D, and 5D state space. Next, a parametric study in a synthetic 3D problem compares the performance of the new sampling scheme to the previous methodology. Lastly, the updated methodology is applied to design a gradient from stainless steel to equiatomic NiTi that has practical uses such as embedded shape memory actuation and for which the previous methodology fails to find a feasible path.

Engineering↗

Hybrid magnon-phonon localization enhances function near ferroic glassy states

Ferroic materials on the verge of forming ferroic glasses exhibit heightened functionality that is often attributed to competing long- and short-range correlations. However, the physics underlying these enhancements is not well understood. The Ni 45 Co 5 Mn 36.6 In 13.4 Heusler alloy is on the edge of forming both spin and strain glasses and exhibits magnetic field–induced shape memory and large magnetocaloric effects, making it a candidate for multicaloric cooling applications. We show using neutron scattering that localized magnon-phonon hybrid modes, which are inherently spread across reciprocal space, act as a bridge between phonons and magnons and result in substantial magnetic field–induced shifts in the phonons, triple the caloric response, and alter phase stability. We attribute these modes to the localization of phonons and magnons by antiphase boundaries coupled to magnetic domains. Because the interplay between short- and long-range correlations is common near ferroic glassy states, our work provides general insights on how glassiness enhances function.

36 MATERIALS SCIENCE↗

Accessing pluripotent materials through tempering of dynamic covalent polymer networks

Pluripotency, which is defined as a system not fixed as to its developmental potentialities, is typically associated with biology and stem cells. Here, inspired by this concept, we report synthetic polymers that act as a single “pluripotent” feedstock and can be differentiated into a range of materials that exhibit different mechanical properties, from hard and brittle to soft and extensible. To achieve this, we have exploited dynamic covalent networks that contain labile, dynamic thia-Michael bonds, whose extent of bonding can be thermally modulated and retained through tempering, akin to the process used in metallurgy. In addition, we show that the shape memory behavior of these materials can be tailored through tempering and that these materials can be patterned to spatially control mechanical properties.

36 MATERIALS SCIENCE↗

Recyclable Cellulose Fiber Reinforced Vitrimer Composite

Vitrimer is an innovative class of polymeric materials which demonstrates traditional thermoset-like mechanical and chemical resilience while still being able to flow on demand like a traditional thermoplastic through covalently adaptive dynamic linkages. Herein, high-performance cellulose fiber reinforced vitrimer composites are developed using an epoxy-based vitrimer and natural cellulose paper. The reinforced vitrimer composite was fabricated by impregnating the porous structure of cellulose paper with two curable monomers, followed by in-situ polymerization of the monomers inside the fibrous scaffold. The introduction of hydroxyl group present on the cellulosic framework assisted in a faster topological rearrangement of the crosslinked matrix through transesterification exchange reaction, thus imparting various sought-after properties like shape recovery and recyclability via simple thermal reprocessing. Moreover, the reinforced vitrimer composite exhibits superior tensile properties as high as 90 MPa with 15-25 volume% vitrimer loading due to the interfacial adhesion via ester exchange reaction between the epoxy matrix and functionalities on the cellulosic fibers. Noteworthily, the key ingredients of the resulting composite (i.e., epoxy-based vitrimer and cellulose fibers) can be comfortably recycled without using aggressive chemical treatment, enabling composite to be easily recycled or disposed of at the end of service life and assist in reducing the subsequent manufacturing cost. This study would shed light on the development of a recyclable polymer composite with exceptional mechanical properties while simultaneously demonstrating self-healing and shape memory capabilities.

Rohewal, Sargun Singh↗

Caloric effects in ferroic materials

The fundamentals and applications of ferroic materials$-$ferromagnetic, ferroelectric, and ferroelastic$-$are common subjects discussed in just about every graduate course related to functional materials. Looking beyond today’s traditional uses, such as in permanent magnets, capacitors, and shape-memory alloys, there are worthwhile and interesting questions common to the caloric properties of these ferroic materials. Can ferroic materials be used in a cooling cycle? Why are these materials susceptible to external fields? Which combination of properties is required to make some of them suitable for efficient cooling and heat pumping? We address these questions in this introduction to ferroic cooling, which comprises magnetocaloric, electrocaloric, elastocaloric and barocaloric approaches and combinations thereof (i.e., multicalorics). These are addressed in greater detail in the articles in this issue.

36 MATERIALS SCIENCE↗

Overcoming fatigue through compression for advanced elastocaloric cooling

Elastocaloric materials exhibit extraordinary cooling potential, but the repetition of cyclic mechanical loadings during long-term operation of cooling systems requires the refrigerant material to have long fatigue life. Here, this paper reviews the fundamental cause of fatigue from aspects of initiation and propagation of fatigue cracks in shape-memory alloys (SMAs) that are used as elastocaloric materials, and highlights recent advances in using compression to overcome fatigue by curtailing the generation of surfaces associated with crack propagation. Compression is identified as a key means to extend fatigue lifetime in engineering design of elastocaloric cooling drive mechanisms. We summarize the state-of-the-art performance of different SMAs as elastocaloric materials and discuss the influence of low cyclic strains and high resistance to transformation. We present integration of compression-based material assemblies into a cooling system prototype and optimization of the system efficiency using work recovery and related measures.

36 MATERIALS SCIENCE↗

A review of materials used in tomographic volumetric additive manufacturing

Abstract Volumetric additive manufacturing is a novel fabrication method allowing rapid, freeform, layer-less 3D printing. Analogous to computer tomography (CT), the method projects dynamic light patterns into a rotating vat of photosensitive resin. These light patterns build up a three-dimensional energy dose within the photosensitive resin, solidifying the volume of the desired object within seconds. Departing from established sequential fabrication methods like stereolithography or digital light printing, volumetric additive manufacturing offers new opportunities for the materials that can be used for printing. These include viscous acrylates and elastomers, epoxies (and orthogonal epoxy-acrylate formulations with spatially controlled stiffness) formulations, tunable stiffness thiol-enes and shape memory foams, polymer derived ceramics, silica-nanocomposite based glass, and gelatin-based hydrogels for cell-laden biofabrication. Here we review these materials, highlight the challenges to adapt them to volumetric additive manufacturing, and discuss the perspectives they present. Graphical abstract

36 MATERIALS SCIENCE↗

Crystallographic variant mapping using precession electron diffraction data

In this work, we developed three methods to map crystallographic variants of samples at the nanoscale by analyzing precession electron diffraction data using a high-temperature shape memory alloy and a VO2 thin film on sapphire as the model systems. The three methods are (I) a user-selecting-reference pattern approach, (II) an algorithm-selecting-reference-pattern approach, and (III) a k-means approach. In the first two approaches, Euclidean distance, Cosine, and Structural Similarity (SSIM) algorithms were assessed for the diffraction pattern similarity quantification. We demonstrated that the Euclidean distance and SSIM methods outperform the Cosine algorithm. We further revealed that the random noise in the diffraction data can dramatically affect similarity quantification. Denoising processes could improve the crystallographic mapping quality. With the three methods mentioned above, we were able to map the crystallographic variants in different materials systems, thus enabling fast variant number quantification and clear variant distribution visualization. The advantages and disadvantages of each approach are also discussed. We expect these methods to benefit researchers who work on martensitic materials, in which the variant information is critical to understand their properties and functionalities.

Crystallographic variant mapping↗

Progress Report 2011: Understanding compound phase transitions in Heusler alloy giant magnetocaloric materials

Our goal is to gain insight into the fundamental physics that is responsible for magnetocaloric effects (MCE) and related properties at the atomic level. We are currently conducting a systematic study on the effects of atomic substitutions in Ni2MnGa-based alloys, and also exploring related full- and half-Heusler alloys, for example Ni-Mn-X (X=In, Sn, Sb), that exhibit a wide variety of interesting and potentially useful physical phenomena. It is already known that the magnetocaloric effect in the Heusler alloys is fundamentally connected to other interesting phenomena such as shape-memory properties. And the large magnetic entropy change in Ni2Mn0.75Cu0.25Ga has been attributed to the coupling of the first-order, martensitic transition with the second-order ferromagnetic paramagnetic (FM-PM) transition. Our research to this point has focused on understanding the fundamental physics at the origin of these complex, compound phase transitions, and the novel properties that emerge. We synthesize the materials using a variety of techniques, and explore their material properties through structural, magnetic, transport, and thermo-magnetic measurements.

36 MATERIALS SCIENCE↗

Additive Manufacturing of a y0-Tetragonal Uranium-Niobium Alloy

The ability to process near-net shape structures is of particular interest in applications using rare or expensive materials. Laser powder bed fusion additive manufacturing can meet this challenge, yet also introduces significant processing and materials challenges toward achieving structural integrity. Broadly addressed aspects affecting powder bed fusion structures include surface roughness, residual stresses, and porosity. Here, we focus on materials-specific challenges—namely, the influence of multiple pass reheating during processing and post-processing homogenization on phase transformations and the role of impurities and oxides on grain morphology and mechanical behavior—with a view of adopting laser powder bed fusion processing for the shape memory alloy, uranium-6 wt.% niobium. Our observations to date on the factors influencing material behavior and post-processing requirements and recommendations for process improvement are discussed herein.

36 MATERIALS SCIENCE↗

In Situ High Energy X-ray Diffraction Characterization of Phase Transformations and Mechanical Behaviors in Rapidly Solidified Titanium and Stainless Steel Alloys [Thesis]

Advanced manufacturing techniques like additive manufacturing (AM) have poised themselves to revolutionize metal manufacturing. A wide range of AM techniques are capable of manufacturing metal components with unique, complex geometries and hastening the scientific-engineering-development cycle. Metal AM relies on a layer-by-layer rapid manufacturing process to build components from the substrate up. Rapid solidification is a large departure from traditional metal manufacturing due to its complex physics. Characterization of rapid solidification is difficult, stemming from the small volumes used in AM and the fast dynamics of the process. High energy X-ray diffraction (HEXRD) is a solution to the characterization problems of rapidly solidified alloys and AM. HEXRD can probe small volumes at fast rates and provides a wide range of thermomechanical and kinetic information. This thesis presents the application of HEXRD to rapidly solidified titanium and stainless steel alloys through a series of case studies. In the first two studies, HEXRD is applied to rapidly solidified titanium and stainless steel welds. The materials are characterized for their temperature history, phase changes, kinetics, and microstructural evolution. In the next case study, HEXRD is applied to characterize phase changes in elastocaloric NiTi shape memory alloys (SMAs) under thermomechanical load. HEXRD, in conjunction with other tools, is used to explain the superior performance of the additively manufactured SMAs. In the final two case studies, HEXRD is used to measure the mechanical response of AM parts with complex geometries; namely, the octet truss lattice. Diffraction reveals a wide range of materials information about the AM microstructure including unexpected phases, texture, and mechanical response to loading. The mechanical results from HEXRD and then compared with theoretical predictions about the performance of octet truss lattices. Summarily, HEXRD is a diverse tool that is poised to address the complex characterization problems of many aspects of the additive manufacturing process.

36 MATERIALS SCIENCE↗