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At least 91 records · Page 5

Shape Recovery with Concomitant Mechanical Strengthening of Amphiphilic Shape Memory Polymers in Warm Water

Maintaining adequate or enhancing mechanical properties of shape memory polymers (SMPs) after shape recovery in an aqueous environment are greatly desired for biomedical applications of SMPs as self-fitting tissue scaffolds or minimally invasive surgical implants. Here we report stable temporary shape fixing and facile shape recovery of biodegradable triblock amphiphilic SMPs containing a poly(ethylene glycol) (PEG) center block and flanking poly(lactic acid) or poly(lactic-co-glycolic acid) blocks in warm water, accompanied with concomitant enhanced mechanical strengths. Differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WXRD) and small-angle X-ray scattering (SAXS) analyses revealed that the unique stiffening of the amphiphilic SMPs upon hydration was due to hydration-driven microphase separation and PEG crystallization. We further demonstrated that the chemical composition of degradable blocks in these SMPs could be tailored to affect the persistence of hydration-induced stiffening upon subsequent dehydration. These properties combined open new horizons for these amphiphilic SMPs for smart weight-bearing in vivo applications (e.g. as self-fitting intervertebral discs). In conclusion, this study also provides a new material design strategy to strengthen polymers in aqueous environment in general.

36 MATERIALS SCIENCE↗

Ultra low density biodegradable shape memory polymer foams with tunable physical properties

Compositions and/or structures of degradable shape memory polymers (SMPs) ranging in form from neat/unfoamed to ultra low density materials of down to 0.005 g/cc density. These materials show controllable degradation rate, actuation temperature and breadth of transitions along with high modulus and excellent shape memory behavior. A method of m ly low density foams (up to 0.005 g/cc) via use of combined chemical and physical aking extreme blowing agents, where the physical blowing agents may be a single compound or mixtures of two or more compounds, and other related methods, including of using multiple co-blowing agents of successively higher boiling points in order to achieve a large range of densities for a fixed net chemical composition. Methods of optimization of the physical properties of the foams such as porosity, cell size and distribution, cell openness etc. of these materials, to further expand their uses and improve their performance.

36 MATERIALS SCIENCE↗

High Damping of Lightweight TiNi-Ti{sub 2}Ni Shape Memory Composites for Wide Temperature Range Usage

A bimodal porous TiNi-Ti{sub 2}Ni shape memory alloy composite (SMAC) with 59% porosity was fabricated by sintering Ti-46at.%Ni elemental powders with pore-forming agent. The porous TiNi-Ti{sub 2}Ni SMAC contains two irregular pores of about 400 and 120 μm. We investigated the microstructure and pore morphology correlated with the mechanical properties and damping capacities of the SMAC. Ti{sub 2}Ni intermetallic phases with size of 1-3 μm were homogeneously distributed in the TiNi matrix. The porous TiNi-Ti{sub 2}Ni SMAC exhibits exceptionally high inverse mechanical quality factor (Q{sup −1}) of ~0.25 at < 40 °C, which is among the highest value reported for porous/dense shape memory alloys or composites to best of our knowledge, and it shows very high compressive fracture strain of about 25%. Moreover, the fabricated porous SMAC at relatively low strain amplitude can exhibit considerable high Q{sup −1} of 0.06 ~ 0.11 for a wide range of temperature between − 90 and 200 °C, which is attributed to the stress concentration distribution provided by the bimodal structure of pores and the massive interfaces between pore/matrix and TiNi/Ti{sub 2}Ni. These porous SMACs can be an ideal candidate for using as a lightweight damping material in the energy-saving applications.

36 MATERIALS SCIENCE↗

Microstructure Anisotropy Effects on Fracture and Fatigue Mechanisms in Shape Memory Alloy Martensites

The chief scientific object was to investigate the fatigue and fracture mechanisms in NiTi shape memory alloys, in the presence of stress concentrating factors such as micro-pores and notches. In particular, the interactions between structure (factors related to the geometry of the specimen, such as holes, pores and notches) and microstructure (related to properties of the material such as grains, secondary phases, twins) in influencing the inelastic deformation, leading up to fracture in NiTi was examined. Primarily, there were two major thrusts. The first thrust focused on fracture behavior in Shape Memory Alloys where the high crystal symmetry cubic phase transformed into the low symmetry phase during deformation and propagation of cracks. This thrust revealed the interplay between size of micro-pores, size of grains and grain orientations in determining the resistance to crack growth, during cyclic tensile deformation of porous-like NiTi specimens. The role of secondary phases (impurities of Ti, often formed during fabrication) were also shown to induce local inelastic deformation gradients during tensile deformation and reduce overall extent of deformation. The second thrust focused on the fatigue and fracture behavior in the low crystal symmetry martensite phase. Unlike high symmetry phases, characterization of deformation in low symmetry phases such as martensitic NiTi has been challenging, due to a hierarchical microstructure spanning from nanoscale twins to the macroscale, a highly anisotropic microstructure stemming from the low crystal symmetry and a multitude of inelastic mechanisms for deformation. Thus, advanced X-ray techniques such as 3D high-energy diffraction microscopy and x-ray micro-Laue diffraction and spectroscopy were used in conjunction with traditional techniques such as SEM and TEM to understand the inelastic deformation in the martensite phase in NiTi, in the presence of notches. This thrust revealed a stark difference in deformation mechanisms based on the nature of stress: regions near the notch experience a highly triaxial stress while those far away experience a uniaxial stress. Additionally, while regions close to the notch were shown to deform locally by amorphization/nanocrystallization, ultimately leading to fracture, regions far away from the notch deformed in a more traditional manner, with detwinning and twin reorientation the primary mechanisms of deformation. More importantly, this thrust revealed that in the presence of structural factors such as notches, the traditional picture of reorientation (coalescence) of nanoscale martensite twins into increasingly larger domains with increased loading does not hold true, even up to fracture of the specimen. These conclusions will inform the modeling and understanding of deformation behavior of specimens, where structure and microstructure coexist and interact.

36 MATERIALS SCIENCE↗

Biobased Semi-Interpenetrating Polymer Networks of Poly(ε-caprolactone) and Epoxidized Soybean Oil with Nanoscale Morphology, Shape-Memory Effect, and Biocompatibility

Creating biobased polymer blends with outstanding properties, nanoscale morphology, shape-memory capability, and biocompatibility is very crucial and requires a fundamental understanding of the phase behavior, macromolecular structure, and biological compatibility of the polymer blends with living cells. It is very critical to understand the complex relationships among the polymer structure, morphology, and performance of multifunctional smart materials under conditions that they are likely to encounter during use, particularly in biomedical applications. Biobased semi-interpenetrating polymer networks of poly(ε-caprolactone) and epoxidized soybean oil with nanoscale morphology have been successfully synthesized via in situ cationic polymerization and compatibilization in a homogeneous solution. Varies analytical and characterization techniques, such as Fourier transform infrared spectroscopy, differential scanning calorimetry, dynamic mechanical analysis, transmission electron microscopy, X-ray scattering, cell toxicity, and shape-memory effects (SMEs), have been employed to understand the structure–properties relationship of these smart, biobased nanostructured polymer blends. The synthesized nano blends were nontoxic or biocompatible and supported attachment of human vein endothelial cells, showing their potential use in biomedical applications. The current versatile, low-cost strategy for synthesizing the nanoscale morphology of semi-interpenetrating polymer networks with SMEs and biocompatibility should be widely applicable for polymer systems. This study is also considered as a continuation to our efforts in the area of biobased polymers to develop innovative technologies to transform natural resources into smart multifunctional materials for a wide range of applications, including coatings, adhesives, and medical devices.

36 MATERIALS SCIENCE↗

Tuning the Mechanical Properties of Shape Memory Metallic Glass Composites with Brick and Mortar Designs

We use molecular dynamics simulations to characterize the tensile deformation and failure of shape memory alloy-bulk metallic glass composites (BMGCs). As the failure in BMGCs shifts from the MG matrix to the second phase different strategies are required to further improve their mechanical properties. Results show that a staggered brick BMGC displays enhanced ductility with mild strength loss following a homogeneously distributed plasticity. This demonstrates that judiciously designed BMGCs can effectively synergize the mechanical properties of metallic glasses and shape memory alloys by effectively distributing stress and preventing the generation of critical shear bands and premature failure while preserving strength.

36 MATERIALS SCIENCE↗

Designing shape-memory-like microstructures in intercalation materials

During the reversible insertion of ions, lattices in intercalation materials undergo structural transformations. These lattice transformations generate misfit strains and volume changes that, in turn, contribute to the structural decay of intercalation materials and limit their reversible cycling. In this paper, we draw on insights from shape-memory alloys, another class of phase transformation materials, that also undergo large lattice transformations but do so with negligible macroscopic volume changes and internal stresses. We develop a theoretical framework to predict structural transformations in intercalation compounds and identify crystallographic design rules necessary for forming shape-memory-like microstructures in intercalation materials. We use our approach to systematically screen open-source structural databases comprising $n$ > 5000 pairs of intercalation compounds. We identify candidate compounds, such as Li x Mn 2 O 4 (Spinel), Li x Ti 2 (PO 4 ) 3 (NASICON), that approximately satisfy the crystallographic design rules and can be precisely doped to form shape-memory-like microstructures. Throughout, we compare our analytical results with experimental measurements of intercalation compounds. We find a direct correlation between structural transformations, microstructures, and increased capacity retention in these materials. These results, more generally, show that crystallographic designing of intercalation materials could be a novel route to discovering compounds that do not decay with continuous usage.

36 MATERIALS SCIENCE↗

Processable, tunable thio-ene crosslinked polyurethane shape memory polymers

An embodiment includes a platform shape memory polymer system. Such an embodiment exhibits a blend of tunable, high performance mechanical attributes in combination with advanced processing capabilities and good biocompatibility. A post-polymerization crosslinking synthetic approach is employed that combines polyurethane and thiol-ene synthetic processes. Other embodiments are described herein.

36 MATERIALS SCIENCE↗

Processable, tunable thiol-ene crosslinked polyurethane shape memory polymers

An embodiment includes a platform shape memory polymer system. Such an embodiment exhibits a blend of tunable, high performance mechanical attributes in combination with advanced processing capabilities and good biocompatibility. A post-polymerization crosslinking synthetic approach is employed that combines polyurethane and thiol-ene synthetic processes. Other embodiments are described herein.

Hearon, Keith↗

Phase diagram of magnetic shape memory alloy Ni 50 Mn $50–x$ In $x$ , 0 < $x$ , 25 from first principles, via spin cluster expansion and phonon vibrational entropies

The metamagnetic shape memory Heusler alloy Ni 50 Mn $50–x$ In $x$ exhibits a rich phase diagram featuring competing magnetic states, coupled magnetic–structural phase transitions, and strong compositional sensitivity. Existing first-principles approaches struggletocapturetheintertwinedchemical, magnetic, andvibrationaleffectsinthesealloys, necessitating a more integrated modeling framework. We develop a spin cluster expansion (spin-CE) framework augmented by a quasi-harmonic phonon model to capture both configurational (chemical and magnetic) and vibrational contributions to the free energy of Ni 50 Mn $50–x$ In $x$ over the full compositional range 0 ≤ x ≤25. The spin-CE includes both chemical clusters and composition-dependent Ising spin interactions, with parameters fit to a first-principles density functional theory (DFT) dataset. Using this approach, we predict the complete magnetostructural phase diagram and transformation temperatures of Ni 50 Mn $50–x$ In $x$ across the composition space. We find that vibrational entropy alone is insufficient to reproduce the martensitic transformation in the magnetic shape memory alloy regime, highlighting the essential role of magnetism. Incorporating both magnetic and vibrational contributions allows us to reproduce all experimentally known phases, including the disappearance of the stable martensite phase at a critical In concentration and the Curie temperature of the austenite phase. The method also captures the transition with increasing In in martensite from antiferromagnetic to ferromagnetic order and predicts re-entrant ferromagnetism, though the latter occurs at higher In content than reported experimentally. We discuss possible sources of this discrepancy and highlight the broader applicability of the method to other magnetostructurally complex materials, where it may offer mechanistic insight and predictive design capabilities.

Cluster expansion↗

Post polymerization cure shape memory polymers

This invention relates to chemical polymer compositions, methods of synthesis, and fabrication methods for devices regarding polymers capable of displaying shape memory behavior (SMPs) and which can first be polymerized to a linear or branched polymeric structure, having thermoplastic properties, subsequently processed into a device through processes typical of polymer melts, solutions, and dispersions and then crossed linked to a shape memory thermoset polymer retaining the processed shape.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Post polymerization cure shape memory polymers

This invention relates to chemical polymer compositions, methods of synthesis, and fabrication methods for devices regarding polymers capable of displaying shape memory behavior (SMPs) and which can first be polymerized to a linear or branched polymeric structure, having thermoplastic properties, subsequently processed into a device through processes typical of polymer melts, solutions, and dispersions and then crossed linked to a shape memory thermoset polymer retaining the processed shape.

Wilson, Thomas S.↗

Post polymerization cure shape memory polymers

This invention relates to chemical polymer compositions, methods of synthesis, and fabrication methods for devices regarding polymers capable of displaying shape memory behavior (SMPs) and which can first be polymerized to a linear or branched polymeric structure, having thermoplastic properties, subsequently processed into a device through processes typical of polymer melts, solutions, and dispersions and then crossed linked to a shape memory thermoset polymer retaining the processed shape.

Wilson, Thomas S.↗

Large thermal hysteresis in a single-phase NiTiNb shape memory alloy

Large thermal hysteresis ($T$ hys ) is favorable in shape memory alloys (SMAs) because it renders wide service and storage temperature range of the SMA-made parts. In this letter, we show that large intrinsic $T$ hys up to 100 K is achieved in a low Nb content (2 at.%), β-Nb-free and single-phase NiTiNb SMA fabricated by casting, forging, wire-drawing and annealing. Such a large $T$ hys is comparable to that of the widely used dual-phase NiTiNb SMAs in which high Nb content and β-Nb are required. By exploiting the grain-size-dependence of $T$ hys in our single-phase NiTiNb SMA and that in an equiatomic NiTi SMA, we attribute the large $T$ hys to the enhanced kinetic resistance of transformation by the small grains. In conclusion, the connection between the $T$ hys and the kinetic resistance is demonstrated by a modified dislocation-based kinetic model.

36 MATERIALS SCIENCE↗

Multiferroic and Related Hysteretic Behavior in Ferromagnetic Shape Memory Alloys

In this work, we combine a Ginzburg–Landau model for a ferroelastic transition with the theory of micromagnetism to study the magnetostructural behavior leading to multicaloric effects in ferromagnetic shape memory alloys. We analyze the ferroelastic transition under different conditions of temperature, stress and magnetic field and establish the corresponding phase diagram. On the one hand, our results show that the proper combination of both fields may be used to reduce the transition hysteresis and thus improve the reversibility of the related elastocaloric effects, superelasticity and stress-mediated magnetocaloric effects. On the other hand, the stress-free magnetic field-driven and thermally driven magnetostructural evolution provides physical insight into the low-temperature field-induced domain reorientation, from which we derive strategies to modify the operational temperature ranges and thus the corresponding (magnetic) shape-memory effect.

36 MATERIALS SCIENCE↗

Active interlocking metasurfaces enabled by shape memory alloys

Interlocking metasurfaces (ILMs) are a newly developed joining technology that relies on arrays of interlocking features that transmit force and constrain motion between adjoining bodies in one or more directions. This study explores harnessing the shape memory effect (SME) in Nickel-Titanium shape memory alloys (NiTi SMAs) in structures fabricated using additive manufacturing (AM) to advance the development of active ILMs by creating unit cells that open or close at specific temperatures. The study encompasses designing and fabricating two distinct interlocking array configurations using near-equiatomic NiTi powder and the laser powder bed fusion (L-PBF) AM technique, following a previously developed AM process optimization framework to manufacture defect-free parts. To guide the design process, finite element analysis (FEA) was employed to predict strain values during engage-disengage cycles. The martensitic transformation characteristics of the ILMs were characterized. Thermomechanical testing revealed that the ILMs demonstrate high locking force once engaged, coupled with complete shape recovery and good cyclic stability. Digital image correlation (DIC) was also employed to validate the FEA predictions during the engage-disengage cycles. The results indicate that NiTi SMA-based ILMs can be designed and fabricated into complex shapes using L-PBF. By leveraging the SME, the functionality of an ILM can be improved upon. The combination of computational modeling, additive manufacturing, and thermomechanical and physical property characterization provides a framework for designing future ILMs out of active materials.

Additive manufacturing↗

Effect of Ni-Content on the Transformation Temperatures in NiTi-20 at. % Zr High Temperature Shape Memory Alloys

The effect of Ni-content on phase transformation behavior of NiTi-20 at. % Zr high temperature shape memory alloy (HTSMA) is investigated over a small composition range, i.e., 49.8, 50.0 and 50.2 at. % Ni, by differential scanning calorimetry (DSC), high-energy synchrotron radiation X-ray diffraction (SR-XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). All samples show a monoclinic B19' martensitic structure at room temperature. It is shown that even with these small variations in Ni-content, the alloy shows vastly different transformation temperatures and responds in a drastically different manner to aging treatments at 550 and 600 °C. Lastly, a discussion on H-phase composition with respect to bulk composition is presented.

36 MATERIALS SCIENCE↗

High-energy synchrotron X-ray diffraction measurements of simple bending of pseudoelastic NiTi shape memory alloy wires

Many technological applications of austenitic shape memory alloys (SMAs) involve cyclical mechanical loading and unloading in order to take advantage of pseudoelasticity. In this paper, we investigated the effect of mechanical bending of pseudoelastic NiTi SMA wires using high-energy synchrotron radiation X-ray diffraction (SR-XRD). Differential scanning calorimetry was performed to identify the phase transformation temperatures. Scanning electron microscopy images show that micro-cracks in compressive regions of the wire propagate with increasing bend angle, while tensile regions tend not to exhibit crack propagation. SR-XRD patterns were analyzed to study the phase transformation and investigate micromechanical properties. By observing the various diffraction peaks such as the austenite (200) and the martensite ( ${\bar 1}12$ ), ( ${\bar 1}03$ ), ( ${\bar 1}11$ ), and (101) planes, intensities and residual strain values exhibit strong anisotropy, depending upon whether the sample is in compression or tension during bending.

Zhang, Baozhuo↗