Pd2 MnGa Metamagnetic Shape Memory Alloy with Small Energy Loss.

Metamagnetic shape memory alloys (MMSMAs) are attractive functional materials owing to their unique properties such as magnetostrain, magnetoresistance, and the magnetocaloric effect caused by magnetic-field-induced transitions. However, the energy loss during the martensitic transformation, that is, the dissipation energy, Edis , is sometimes large for these alloys, which limits their applications. In this paper, a new Pd2 MnGa Heusler-type MMSMA with an extremely small Edis and hysteresis is reported. The microstructures, crystal structures, magnetic properties, martensitic transformations, and magnetic-field-induced strain of aged Pd2 MnGa alloys are investigated. A martensitic transformation from L21 to 10M structures is seen at 127.4 K with a small thermal hysteresis of 1.3 K. The reverse martensitic transformation is induced by applying a magnetic field with a small Edis (= 0.3 J mol-1 only) and a small magnetic-field hysteresis (= 7 kOe) at 120 K. The low values of Edis and the hysteresis may be attributed to good lattice compatibility in the martensitic transformation. A large magnetic-field-induced strain of 0.26% is recorded, indicating the proposed MMSMA's potential as an actuator. The Pd2 MnGa alloy with low values of Edis and hysteresis may enable new possibilities for high-efficiency MMSMAs.

Non-Hookean large elastic deformation in bulk crystalline metals.

Crystalline metals can have large theoretical elastic strain limits. However, a macroscopic block of conventional crystalline metals practically suffers a very limited elastic deformation of <0.5% with a linear stress-strain relationship obeying Hooke's law. Here, we report on the experimental observation of a large tensile elastic deformation with an elastic strain of >4.3% in a Cu-based single crystalline alloy at its bulk scale at room temperature. The large macroscopic elastic strain that originates from the reversible lattice strain of a single phase is demonstrated by in situ microstructure and neutron diffraction observations. Furthermore, the elastic reversible deformation, which is nonhysteretic and quasilinear, is associated with a pronounced elastic softening phenomenon. The increase in the stress gives rise to a reduced Young's modulus, unlike the traditional Hooke's law behaviour. The experimental discovery of a non-Hookean large elastic deformation offers the potential for the development of bulk crystalline metals as high-performance mechanical springs or for new applications via "elastic strain engineering."

Flexible and Tough Superelastic Co-Cr Alloys for Biomedical Applications.

The demand for biomaterials has been increasing along with the increase in the population of elderly people worldwide. The mechanical properties and high wear resistance of metallic biomaterials make them well-suited for use as substitutes or as support for damaged hard tissues. However, unless these biomaterials also have a low Young's modulus similar to that of human bones, bone atrophy inevitably occurs. Because a low Young's modulus is typically associated with poor wear resistance, it is difficult to realize a low Young's modulus and high wear resistance simultaneously. Also, the superelastic property of shape-memory alloys makes them suitable for biomedical applications, like vascular stents and guide wires. However, due to the low recoverable strain of conventional biocompatible shape-memory alloys, the demand for a new alloy system is high. The novel body-centered-cubic cobalt-chromium-based alloys in this work provide a solution to both of these problems. The Young's modulus of <001>-oriented single-crystal cobalt-chromium-based alloys is 10-30 GPa, which is similar to that of human bone, and they also demonstrate high wear and corrosion resistance. They also exhibit superelasticity with a huge recoverable strain up to 17.0%. For these reasons, the novel cobalt-chromium-based alloys can be promising candidates for biomedical applications.

Iron-based superelastic alloys with near-constant critical stress temperature dependence.

Shape memory alloys recover their original shape after deformation, making them useful for a variety of specialized applications. Superelastic behavior begins at the critical stress, which tends to increase with increasing temperature for metal shape memory alloys. Temperature dependence is a common feature that often restricts the use of metal shape memory alloys in applications. We discovered an iron-based superelastic alloy system in which the critical stress can be optimized. Our Fe-Mn-Al-Cr-Ni alloys have a controllable temperature dependence that goes from positive to negative, depending on the chromium content. This phenomenon includes a temperature-invariant stress dependence. This behavior is highly desirable for a range of outer space-based and other applications that involve large temperature fluctuations.

Magnetoresistance and Thermal Transformation Arrest in Pd2Mn1.4Sn0.6 Heusler Alloys.

The magnetization, electric resistivity, and magnetoresistance properties of Pd 2 Mn 1 . 4 Sn 0 . 6 Heusler alloys were investigated. The Curie temperature of the parent phase, martensitic transformation temperatures, and magnetic field dependence of the martensitic transformation temperatures were determined. The magnetoresistance was investigated from 10 to 290 K, revealing both intrinsic and extrinsic magnetoresistance properties for this alloy. A maximum of about - 3 . 5 % of intrinsic magnetoresistance under 90 kOe and of about - 30 % of extrinsic magnetoresistance under 180 kOe were obtained. Moreover, the thermal transformation arrest phenomenon was confirmed in the Pd 2 Mn 1 . 4 Sn 0 . 6 alloy, and an abnormal heating-induced martensitic transformation (HIMT) behavior was observed.

Atomic ordering, magnetic properties, and electronic structure of Mn2CoGa Heusler alloy.

The magnetic properties and atomic arrangement of Mn2CoGa Heusler alloy were investigated experimentally and by theoretical calculations. The magnetic moment derived from spontaneous magnetization at 5 K was 2.06 µ B/f.u. and was close to the integer number of the expected value from theoretical calculation and the Slater-Pauling rule predicted by Galanakis et al. The Curie temperature and L21-B2 order-disorder phase transition temperature were 741 and 1047 K, respectively. Powder neutron diffraction experiment results suggested that the atomic arrangement prefers an L21b-type structure rather than that of Hg2CuTi, being consistent with our previous results of high-angle annular dark-field-scanning transmission electron microscopic observations. The magnetic moments obtained were in good agreement with the theoretical values in the model of the L21b-type structure. The density of states obtained by the first-principles calculation combined with the coherent potential approximation in Mn2CoGa with the L21b-type crystal structure maintained the half-metallic character, even though disordering by Mn and Co atoms was introduced.

Ultra-large single crystals by abnormal grain growth.

Producing a single crystal is expensive because of low mass productivity. Therefore, many metallic materials are being used in polycrystalline form, even though material properties are superior in a single crystal. Here we show that an extraordinarily large Cu-Al-Mn single crystal can be obtained by abnormal grain growth (AGG) induced by simple heat treatment with high mass productivity. In AGG, the sub-boundary energy introduced by cyclic heat treatment (CHT) is dominant in the driving pressure, and the grain boundary migration rate is accelerated by repeating the low-temperature CHT due to the increase of the sub-boundary energy. With such treatment, fabrication of single crystal bars 70 cm in length is achieved. This result ensures that the range of applications of shape memory alloys will spread beyond small-sized devices to large-scale components and may enable new applications of single crystals in other metallic and ceramics materials having similar microstructural features.Growing large single crystals cheaply and reliably for structural applications remains challenging. Here, the authors combine accelerated abnormal grain growth and cyclic heat treatments to grow a superelastic shape memory alloy single crystal to 70 cm.

HpDTC1, a Stress-Inducible Bifunctional Diterpene Cyclase Involved in Momilactone Biosynthesis, Functions in Chemical Defence in the Moss Hypnum plumaeforme.

Momilactones, which are diterpenoid phytoalexins with antimicrobial and allelopathic functions, have been found only in rice and the moss Hypnum plumaeforme. Although these two evolutionarily distinct plant species are thought to produce momilactones as a chemical defence, the momilactone biosynthetic pathway in H. plumaeforme has been unclear. Here, we identified a gene encoding syn-pimara-7,15-diene synthase (HpDTC1) responsible for the first step of momilactone biosynthesis in the moss. HpDTC1 is a bifunctional diterpene cyclase that catalyses a two-step cyclization reaction of geranylgeranyl diphosphate to syn-pimara-7,15-diene. HpDTC1 transcription was up-regulated in response to abiotic and biotic stress treatments. HpDTC1 promoter-GUS analysis in transgenic Physcomitrella patens showed similar transcriptional responses as H. plumaeforme to the stresses, suggesting that a common response system to stress exists in mosses. Jasmonic acid (JA), a potent signalling molecule for inducing plant defences, could not activate HpDTC1 expression. In contrast, 12-oxo-phytodienoic acid, an oxylipin precursor of JA in vascular plants, enhanced HpDTC1 expression and momilactone accumulation, implying that as-yet-unknown oxylipins could regulate momilactone biosynthesis in H. plumaeforme. These results demonstrate the existence of an evolutionarily conserved chemical defence system utilizing momilactones and suggest the molecular basis of the regulation for inductive production of momilactones in H. plumaeforme.

A jumping shape memory alloy under heat.

Shape memory alloys are typical temperature-sensitive metallic functional materials due to superelasticity and shape recovery characteristics. The conventional shape memory effect involves the formation and deformation of thermally induced martensite and its reverse transformation. The shape recovery process usually takes place over a temperature range, showing relatively low temperature-sensitivity. Here we report novel Cu-Al-Fe-Mn shape memory alloys. Their stress-strain and shape recovery behaviors are clearly different from the conventional shape memory alloys. In this study, although the Cu-12.2Al-4.3Fe-6.6Mn and Cu-12.9Al-3.8Fe-5.6Mn alloys possess predominantly L2(1) parent before deformation, the 2H martensite stress-induced from L2(1) parent could be retained after unloading. Furthermore, their shape recovery response is extremely temperature-sensitive, in which a giant residual strain of about 9% recovers instantly and completely during heating. At the same time, the phenomenon of the jumping of the sample occurs. It is originated from the instantaneous completion of the reverse transformation of the stabilized 2H martensite. This novel Cu-Al-Fe-Mn shape memory alloys have great potentials as new temperature-sensitive functional materials.

Morphological and chemical analysis of bainite in Cu-17Al-11Mn (at.%) alloys by using orthogonal FIB-SEM and double-EDS STEM.

In this study, new microscopy techniques were developed for understanding the mechanism for the bainitic transformation in a Cu-17Al-11Mn (at%) alloy. An orthogonally arranged focused ion beam and a scanning electron microscope were employed to observe three-dimensional (3D) morphology of the bainite phase, in addition to compositional analysis by using a scanning transmission electron microscope equipped with a double-detector energy-dispersive X-ray spectrometer system. The 3D morphology of these samples was observed at different aging times and aging temperatures; the results obtained indicated that with increasing aging time and/or aging temperature, the bainite phase at the initial stage of formation exhibits a plate-like shape, which changes to a lenticular form. A habit plane was uniquely determined as ∼{9 3 2} by the combination of 3D image reconstruction and an electron back-scattered diffraction technique. The compositional analysis revealed the spatial distribution of the compositional variation between the bainite and matrix phases in the initial stages of the transformation. In the bainite phase, the Cu concentration was higher, while the concentrations of Al and Mn were lower than those in the surrounding matrix, indicative of the diffusion of the constituent elements with the growth of the bainite phase.

In situ heating SEM observation of the bainitic transformation process in Cu-17Al-11Mn (at.%) alloys.

To understand the bainitic transformation behavior in Cu-17Al-11Mn (at.%) alloys, dynamicin situobservation during heating was carried out in a scanning electron microscope (SEM). In this study, after optimizing the sample preparation method and observation conditions, we successfully observed the transformation process with sufficient resolution and contrast. From the observation results, bainite is first formed preferentially at the grain boundaries of the parent phase. Bainite is also formed inside the grains to relax the elastic strain generated by the initial bainite. Regarding the growth mode, in the early stage of the transformation, bainite grows along the longitudinal direction, and in the late stage, it grows along the lateral direction. The growth rate of the bainite was also evaluated by continuous observation of the same plate. Dynamicin situobservation of a martensitic transformation in the same alloy was also performed to compare the growth mode with that of bainite, and it was found that the behavior is considerably different between bainitic and the martensitic transformations.

Drastic change in density of states upon martensitic phase transition for metamagnetic shape memory alloy Ni2Mn(1+x)In(1-x).

We have unravelled the electronic structure of a class of metamagnetic shape memory alloy Ni2Mn1+x In1-x by combining bulk-sensitive hard x-ray photoelectron spectroscopy and first-principles density-functional calculations. A sharp drop in the Ni 3d e(g) density of states forming a pseudogap in the martensitic phase transition (MPT) for x = 0.36 has been observed near the Fermi level. As a feature of MPT, hysteretic behaviour of this drop has been confirmed in both cooling and warming. This pseudogap is responsible for the giant negative magnetoresistance. The experimental result is well reproduced by the first principle calculation. We have also clarified theoretically that the MPT is linked to a competition of ferromagnetic and anti-ferromagnetic coupling between ordinary and anti-site Mn atoms.

Abnormal grain growth induced by cyclic heat treatment.

In polycrystalline materials, grain growth occurs at elevated temperatures to reduce the total area of grain boundaries with high energy. The grain growth rate usually slows down with annealing time, making it hard to obtain grains larger than a millimeter in size. We report a crystal growth method that employs only a cyclic heat treatment to obtain a single crystal of more than several centimeters in a copper-based shape-memory alloy. This abnormal grain growth phenomenon results from the formation of a subgrain structure introduced through phase transformation. These findings provide a method of fabricating a single-crystal or large-grain structure important for shape-memory properties, magnetic properties, and creep properties, among others.

Mevalonate-dependent enzymatic synthesis of amorphadiene driven by an ATP-regeneration system using polyphosphate kinase.

Polyphosphate kinase (PPK), which can regenerate ATP from ADP, was utilized in the mevalonate-dependent enzymatic synthesis of amorphadiene. The activity of PPK, cloned from Escherichia coli, was determined by (31)P-NMR. The yield from the PPK-catalyzed synthesis was 25%, 2.5 times higher than that without PPK. The (31)P-NMR analysis of the final reaction mixture indicated no accumulation of intermediates.

A simple method to treat an ingrowing toenail with a shape-memory alloy device.

An ingrowing toenail has no definitive treatment. Previously, effective methods were complicated but easy ones had less effect. We show both an easy and an effective way with Cu-Al-Mn-based shape-memory alloys (SMAs). They have a characteristic shape which patients themselves can detach easily without any pain. But they also have enough corrective force. Cu-based SMAs cost much less than Ni-Ti-based alloys. Despite not being appropriate for all cases of ingrowing toenails, it is an easy, effective and less costly alternative.

Development of medical guide wire of Cu-Al-Mn-base superelastic alloy with functionally graded characteristics.

A new type of medical guide wire with functionally graded hardness from the tip to the end was developed with the use of Cu-Al-Mn-based alloys. The superelasticity (SE) of the Cu-Al-Mn-based alloys in the tip is drastically improved by controlling the grain size, whereas the end of the wire is hardened using bainitic transformation by aging at around 200-400 degrees C. Therefore, the tip of the guide wire shows a superelasticity and its end has high stiffness. This guide wire with functionally graded characteristics shows excellent pushability and torquability, superior to that of the Ni-Ti guide wire.