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Shape memory polymers

New shape memory polymer compositions, methods for synthesizing new shape memory polymers, and apparatus comprising an actuator and a shape memory polymer wherein the shape memory polymer comprises at least a portion of the actuator. A shape memory polymer comprising a polymer composition which physically forms a network structure wherein the polymer composition has shape-memory behavior and can be formed into a permanent primary shape, re-formed into a stable secondary shape, and controllably actuated to recover the permanent primary shape. Polymers have optimal aliphatic network structures due to minimization of dangling chains by using monomers that are symmetrical and that have matching amine and hydroxl groups providing polymers and polymer foams with clarity, tight (narrow temperature range) single transitions, and high shape recovery and recovery force that are especially useful for implanting in the human body.

59 BASIC BIOLOGICAL SCIENCES↗

Shape memory polymers

New shape memory polymer compositions, methods for synthesizing new shape memory polymers, and apparatus comprising an actuator and a shape memory polymer wherein the shape memory polymer comprises at least a portion of the actuator. A shape memory polymer comprising a polymer composition which physically forms a network structure wherein the polymer composition has shape-memory behavior and can be formed into a permanent primary shape, re-formed into a stable secondary shape, and controllably actuated to recover the permanent primary shape. Polymers have optimal aliphatic network structures due to minimization of dangling chains by using monomers that are symmetrical and that have matching amine and hydroxl groups providing polymers and polymer foams with clarity, tight (narrow temperature range) single transitions, and high shape recovery and recovery force that are especially useful for implanting in the human body.

Wilson, Thomas S.↗

Characterization of the microstructures and the shape memory properties of the Fe-Mn-Si-Cr-Ni-C shape memory alloy after severe plastic deformation by differential speed rolling and subsequent annealing

Highlights: • The Fe-SMA was subjected to severe plastic deformation and then annealed. • Recovery strain increased with increasing grain size. • An optimum grain size existed for the largest recovery stress. • Grain reduction is useful for having a high recovery stress. - Abstract: The Fe-13.51Mn-4.82Si-8.32Cr-3.49Ni-0.15C shape memory alloy was subjected to severe plastic deformation by high-ratio differential speed rolling and subsequent annealing (between 873 and 1373 K) to find the factors that affect recovery stress and recovery strain. As the annealing temperature increased (i. e., as grain size increased), the recovery strain increased. This was attributed to decrease in the density of grain boundaries and the density of twins with increasing grain size. The recovery stress, however, showed a different behavior. It increased with annealing temperature up to 973 K, at which an ultrafine grain size near 1.6 μm was obtained, and then decreased with further increase in the temperature. The difference between the recovery strain and the plastic strain induced by recovery stress under constrained displacement during cooling was proposed to determine the amount of recovery stress. There was an optimum grain size for the largest difference between the recovery strain and the plastic strain. The current study shows that grain-size reduction is not good for having a high recovery strain but it is beneficial for having a high recovery stress in the Fe-Mn-Si shape memory alloys.

36 MATERIALS SCIENCE↗

Processing-induced strain glass states in a Ni 49.5 Ti 50.5 shape memory alloy

Shape memory alloys (SMAs) represent a revolutionary and innovative class of active materials which can provide potential solutions to many of today's engineering problems due to their compact form, high energy densities, and multifunctional capabilities. While many applications in the biomedical, aerospace, and automotive industries have already been investigated and realized for Nickel-Titanium (NiTi) based SMAs, the effects of restricting the ferroelastic transformation to nanosized domains is not well understood and the potential remains untapped. In binary NiTi, the martensitic transformation, which is characterized by long-range strain ordering (LRO), can be replaced with a strain glass transition, which consists of an LRO parent phase and a short-range strain ordered glassy phase. Such alloys have been named strain glass alloys (SGAs) due to the fact that they exhibit a glassy state which results from compositionally- or processing-induced strain. While SGAs do not exhibit a stress-free, temperature-induced macroscopic phase change, they still exhibit the strain recovery and actuation capabilities intrinsic to near equiatomic NiTi and other SMAs. It has been shown in the available literature that certain compositions, for example 51.5 at. % Nickel in binary NiTi, can create a strain glass; however, these compositionally-induced NiTi SGAs generally have transformation temperatures below 173 K and this will restrict their practical applications. In the present study, a new method for producing a strain glass phase in Ti-rich NiTi through sufficient plastic deformation via cold work is reported; the resulting SGA exhibits a temperature-induced ferroelastic recovery above room temperature. Additionally, the macroscopic actuation capabilities are improved when compared to both compositionally-induced SGAs and the base material due to the increased functional stresses of the SGA. To better understand the transition from an SMA to an SGA, Ni49.5Ti50.5 (at. %) rods were processed to several degrees of cold work and characterized via scanning and transmission electron microscopy, differential scanning calorimetry, thermomechanical testing, and synchrotron radiation x-ray diffraction. The experimental results indicate that twin size decreases with additional cold work and, around 45% thickness reduction, stress-free thermal cycling no longer results in a measurable phase transformation; however, mechanically-induced phase transformation is still possible, where fully recoverable strains in these SGAs were observed to be above 4.5% when loaded at room temperature and recovered at 150 °C.

36 MATERIALS SCIENCE↗

Shape Memory Characteristics of Ti(sub 49.5)Ni(sub 25)Pd(sub 25)Sc(sub 0.5) High-Temperature Shape Memory Alloy After Severe Plastic Deformation

A Ti(49.5)Ni25Pd25Sc(0.5) high-temperature shape memory alloy is thermomechanically processed to obtain enhanced shape-memory characteristics: in particular, dimensional stability upon repeated thermal cycles under constant loads. This is accomplished using severe plastic deformation via equal channel angular extrusion (ECAE) and post-processing annealing heat treatments. The results of the thermomechanical experiments reveal that the processed materials display enhanced shape memory response, exhibiting higher recoverable transformation and reduced irrecoverable strain levels upon thermal cycling compared with the unprocessed material. This improvement is attributed to the increased strength and resistance of the material against defect generation upon phase transformation as a result of the microstructural refinement due to the ECAE process, as supported by the electron microscopy observations.

Atli, K. C.↗

Stress transfer during different deformation stages in a nano-precipitate-strengthened Ni-Ti shape memory alloy

Understanding the role of fine coherent precipitates in the micromechanical behavior of precipitate-strengthened shape memory alloys (SMAs), which still remains a mystery heretofore, is of crucial importance to the design of advanced SMAs with optimal functional and mechanical properties. Here, we investigate the lattice strain evolution of, and the stress partition between the nanoscale Ni{sub 4}Ti{sub 3} precipitates and the matrix in a precipitate-strengthened Ni-Ti SMA during different deformation stages by in-situ synchrotron high-energy X-ray diffraction technique. We found that, during R-phase reorientation and stress-induced martensitic transformation, which both involve the shear deformation process, the lattice strain of the nanoscale precipitates drastically increases by a magnitude of 0.5%, which corresponds to an abrupt increase of ∼520 MPa in internal stress. This indicates that stress repartition occurs and most of the stress is transferred to the precipitates during the shear deformation of the matrix. It is further revealed that the nanoscale precipitates which only have a low volume fraction bear a considerable amount of applied stress during all deformation stages investigated, implying that the nanoscale precipitates play an important role in the deformation behavior of the precipitate-strengthened Ni-Ti SMAs.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Auxetic Thermo-Responsive Shape-Memory Polyurethane Aerogels

Shape memory polymer aerogels are stimuli-responsive aerogel materials that incorporate polymer aerogel characteristics such as flexibility at low density, and high porosity with shape-changing capabilities upon exposure to external stimuli. By designing the structure of these materials at meso- to macroscale, their shape memory response can be efficiently engineered to show an auxetic response such as a negative Poisson’s ratio, leading to an active and tunable metamaterial. We present a material technology based on a shape memory polyurethane aerogel derived from aliphatic triisocyanate and triethylene glycol, which demonstrates and remembers an auxetic shape change through a thermomechanical cycle first below, and then back again above the glass transition temperature of the polyurethane. Our auxetic shape memory polyurethane aerogels exhibit a significant auxetic response with a negative Poisson’s ratio of approximately -0.8 at 15% compressive strain. This technology is expected to impact multiple areas of interest in relation to commercial, aeronautic, and aerospace industries. Potential applications include minimally invasive medical technologies, soft robotics, and self-deployable structures and habitats. Structure-property relationships of the auxetic shape memory polymer aerogels will be discussed.

Sadeq Malakooti↗

A Machine Learning Approach to Predict Martensitic Transition Temperatures for Shape Memory Alloys

Shape memory alloys (SMAs) are a unique class of materials with several remarkable properties including shape recovery, superelasticity, etc. Especially important for many NASA applications is the ability to tune the martensitic phase transition temperature by varying the alloy composition. Nickel-titanium (NiTi) based alloys are the most widely studied of this class, with compositions involving ternary, quaternary, or higher additions being considered. Over the past several years, a significant database of SMA properties has been assembled by NASA researchers. Such a database is ideal for data science-based approaches including machine learning. We present results from a developed machine learning model capable of accurately predicting the transition temperature of SMAs across a wide range of compositions. Our model has the added benefit of interpretability and even provides confidence intervals for our predictions. This model will make rapid screening and design of new SMA materials possible. Predictions from the machine learning model can be validated by empirical and/or atomistic scale modeling.

Shreyas Honrao↗

Direct in situ measurement of coupled magnetostructural evolution in a ferromagnetic shape memory alloy and its theoretical modeling

Ferromagnetic shape memory alloys (FSMAs) have shown great potential as active components in next generation smart devices due to their exceptionally large magnetic-field-induced strains and fast response times. During application of magnetic fields in FSMAs, as is common in several magnetoelastic smart materials, there occurs simultaneous rotation of magnetic moments and reorientation of twin variants, resolving which, although critical for design of new materials and devices, has been difficult to achieve quantitatively with current characterization methods. At the same time, theoretical modeling of these phenomena also faced limitations due to uncertainties in values of physical properties such as magnetocrystalline anisotropy energy (MCA), especially for off-stoichiometric FSMA compositions. Here, in situ polarized neutron diffraction is used to measure directly the extents of both magnetic moments rotation and crystallographic twin-reorientation in an FSMA single crystal during the application of magnetic fields. Additionally, high-resolution neutron scattering measurements and first-principles calculations based on fully relativistic density functional theory are used to determine accurately the MCA for the compositionally disordered alloy of Ni 2 Mn 1.14 Ga 0.86 . The results from these state-of-the-art experiments and calculations are self-consistently described within a phenomenological framework, which provides quantitative insights into the energetics of magnetostructural coupling in FSMAs. Furthermore, based on the current model, the energy for magnetoelastic twin boundaries propagation for the studied alloy is estimated to be ~150 kJ/m 3 .

36 MATERIALS SCIENCE↗

Volumetric additive manufacturing of shape memory polymers

Shape memory polymers (SMPs) capable of recovering from a deformed state through heating were 3D printed using volumetric additive manufacturing, which enabled the layerless, single-step fabrication of self-standing tripod and actuating gripper structures.

36 MATERIALS SCIENCE↗

Extraction and Analysis of the Properties of Shape Memory Alloys

Shape Memory Alloys (SMA) are materials of high industrial importance, increasingly used for the aerospace applications. Use of SMA allows to simplify flight systems and reduce the total weight. Through the literature-based data mining, we extracted the computed SMA properties from the high-impact journals. We plotted the selected pairs of properties, found and parametrized correlations.

Jason Ernesto Diaz↗

Influence of Microstructural Features on Austenite-Martensite Interfaces in NiTi Shape Memory Alloys

Shape memory alloys (SMAs) exhibit several unique thermomechanical properties due to a reversible martensitic phase transformation. A key aspect of this transformation is the austenite-martensite interface. Here we present a molecular dynamics (MD) simulation methodology to study the atomic-scale features of austenite-martensite interface migration under near-equilibrium conditions. In single crystals, the interfaces migrate rapidly with only a small thermodynamic driving force. In polycrystals, however, interface migration is significantly impeded due to the change in orientation relationship at grain boundaries and the stored elastic energy resulting from microstructural constraints. This behavior can be linked to several mechanisms associated with transformation width and hysteresis in SMAs, properties of great importance for applications involving actuation. Additionally, we will present preliminary MD simulation results on the influence of precipitates on the formation and migration of austenite-martensite interfaces.

Gabriel Plummer↗

Influence of Microstructural Features on Austenite-Martensite Interfaces in NiTi Shape Memory Alloys

Shape memory alloys (SMAs) exhibit several unique thermomechanical properties due to a reversible martensitic phase transformation. A key aspect of this transformation is the austenite-martensite interface. Here we present a molecular dynamics (MD) simulation methodology to study the atomic-scale features of austenite-martensite interface migration under near-equilibrium conditions. In single crystals, the interfaces migrate rapidly with only a small thermodynamic driving force. In polycrystals, however, interface migration is significantly impeded due to the change in orientation relationship at grain boundaries and the stored elastic energy resulting from microstructural constraints. This behavior can be linked to several mechanisms associated with transformation width and hysteresis in SMAs, properties of great importance for applications involving actuation. Additionally, we will present preliminary MD simulation results on the influence of precipitates on the formation and migration of austenite-martensite interfaces.

Gabriel Plummer↗

Ruggedness Evaluation of ASTM International Standard Test Methods for Shape Memory Materials: E3097 Standard Test Method for Mechanical Uniaxial Constant Force Thermal Cycling of Shape Memory Alloys

This paper evaluates the ruggedness testing of the newly released ASTM International E3097 Standard Test Method for Mechanical Uniaxial Constant Force Thermal Cycling of Shape Memory Alloys. The ruggedness experiment was designed with eight runs in two replicates, consisting of seven factors of strain rate (ė), heating and cooling rates (Ṫ(heat) and Ṫ(cool), respectively), upper and lower cycle temperatures (UCT and LCT, respectively), hold time (thold), and minimum load (Fmin) imparted on the samples. The results indicate that the hold time factor had no effect on any result variable. The minimum load factor, alternatively, had the greatest effect on several result variables, with the greatest influence on the strains at martensite start and finish (strain variation ~0.1 percent), and the strains at the upper and lower cycle temperatures (strain variation of 0.14 percent). The UCT was found to have a large effect on the austenite and martensite finish tangent line and data intersect, denoted by Af* and Mf*, by ~17 and 4 °C, respectively. The testing methodology, analysis techniques, and resulting conclusions on the ruggedness of the test methods are presented.

shape memory alloy↗