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At least 109 records · Page 6

Role of point defects in stress-induced martensite transformations in NiTi shape memory alloys: A molecular dynamics study

Shape-memory properties of equiatomic NiTi rely on the thermal- or stress-induced reversible martensitic phase transformation between the $\textit{B}$2 and $\textit{B}$19' phases. Irradiation defects suppress thermal-induced transformations, but their effects on stress-induced transformations are poorly understood. In this work, we use molecular dynamics to investigate the effect of vacancies, vacancy clusters, interstitials, and antisite defects on stress-induced transformations. All defects suppress the transformation, but vacancy clusters do so to the greatest extent, while antisite defects do so to the least extent. The responsible mechanisms are grain boundary pinning and chemical disordering.

36 MATERIALS SCIENCE↗

Acoustic emission analysis of cyclically loaded superelastic shape memory alloy fiber reinforced mortar beams

Superelastic shape memory alloys (SMAs) are metallic alloys that can recover their nonlinear deformations upon unloading. The use of SMAs in cementitious composites as fibers can enable crack recovery and re-centering capabilities. In this study, the crack recovery characteristics of SMA fiber reinforced mortar specimens subjected to flexural cyclic loading are studied through acoustic emission analysis. SMA fiber reinforced mortar specimens with fiber volume ratios of 0.3%, 0.5% and 1.0% are tested under cyclic flexural loads. Acoustic emissions (AE) signals are captured and analyzed to characterize the crack formation and crack width development at each cycle of loading. In addition, the crack width propagation of the specimens is monitored by Digital Image Correlation measurement system and is used as a basis in AE analyses. Results show that the SMA fiber reinforced mortars exhibit considerable re-centering and crack recovery characteristics at large deformation amplitudes.

36 MATERIALS SCIENCE↗

A Processable Shape Memory Polymer System for Biomedical Applications

Polyurethane shape memory polymers (SMPs) with tunable thermomechanical properties and advanced processing capabilities are synthesized, characterized, and implemented in the design of a microactuator medical device prototype. The ability to manipulate glass transition temperature ( T g ) and crosslink density in low-molecular weight aliphatic thermoplastic polyurethane SMPs is demonstrated using a synthetic approach that employs UV catalyzed thiol-ene “click” reactions to achieve postpolymerization crosslinking. Polyurethanes containing varying C=C functionalization are synthesized, solution blended with polythiol crosslinking agents and photoinitiator and subjected to UV irradiation, and the effects of number of synthetic parameters on crosslink density are reported. Thermomechanical properties are highly tunable, including glass transitions tailorable between 30 and 105 °C and rubbery moduli tailorable between 0.4 and 20 MPa. This new SMP system exhibits high toughness for many formulations, especially in the case of low crosslink density materials, for which toughness exceeds 90 MJ m –3 at select straining temperatures. To demonstrate the advanced processing capability and synthetic versatility of this new SMP system, a laser-actuated SMP microgripper device for minimally invasive delivery of endovascular devices is fabricated, shown to exhibit an average gripping force of 1.43 ± 0.37 N and successfully deployed in an in vitro experimental setup under simulated physiological conditions.

42 ENGINEERING↗

Shape-memory transformations of NiTi: Minimum-energy pathways between austenite, martensites, and kinetically limited intermediate states

NiTi is the most used shape-memory alloy, nonetheless, a lack of understanding remains regarding the associated structures and transitions, including their barriers. Using a generalized solid-state nudge elastic band (GSSNEB) method implemented via density-functional theory, we detail the structural transformations in NiTi relevant to shape memory: those between body-centered orthorhombic (BCO) groundstate and a newly identified stable austenite (“glassy” B2-like) structure, including energy barriers (hysteresis) and intermediate structures (observed as a kinetically limited R-phase), and between martensite variants (BCO orientations). All results are in good agreement with available experiment. We contrast the austenite results to those from the often-assumed, but unstable B2. Furthermore, these high- and low-temperature structures and structural transformations provide much needed atomic-scale detail for transitions responsible for NiTi shape-memory effects.

36 MATERIALS SCIENCE↗

Shape memory alloy engine for high efficiency low-temperature gradient thermal to electrical conversion

More than half of the energy generated worldwide is lost as unused thermal energy because of the lack of efficient methodology for harnessing the low-grade heat. In this paper, we demonstrate that shape-memory alloy can be an effective mechanism for recovering low-grade heat. Shape memory alloys exhibit thermally induced martensite to austenite phase transformation and super-elasticity (stress-induced martensitic transformation). Employing these two characteristics, we demonstrate a thermal engine for harnessing waste energy through all modes of heat transfer: convection, conduction, and radiation. In this work, we performed material and heat transfer analysis for achieving high frequency, sustainable and efficient operation of our engine. An optimized shape memory alloy engine generated 36 W per kilogram or 234 kW of electricity per cubic meter of active material. A continuous three-day operation of several SMA engines could generate 7.2 kWh of electricity when installed on a 500 m long hot pipe network. This generated power can potentially reduce the carbon footprint by 5.1 kg of CO 2 illustrating the promise of this technology for addressing climate change.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Ultra Low Density Shape Memory Polymer Foams With Tunable Physicochemical Properties for Treatment of intracranial Aneurysms

Shape memory polymers (SMPs) are a rapidly emerging class of smart materials that can be stored in a deformed temporary shape, and can actively return to their original shape upon application of an external stimulus such as heat, pH or light. This behavior is particularly advantageous for minimally invasive biomedical applications comprising embolic/regenerative scaffolds, as it enables a transcatheter delivery of the device to the target site. The focus of this work was to exploit this shape memory behavior of polyurethanes, and develop an efficient embolic SMP foam device for the treatment of intracranial aneurysms.In summary, this work reports a novel family of ultra low density polymer foams which can be delivered via a minimally invasive surgery to the aneurysm site, actuated in a controlled manner to efficiently embolize the aneurysm while promoting physiological fluid/blood flow through the reticulated/open porous structure, and eventually biodegrade leading to complete healing of the vasculature.

36 MATERIALS SCIENCE↗

Microstructural study and simulation of intrinsic two-way shape memory behavior of functionally graded Ni-rich/NiTiCu thin film

Highlights: • Ni-rich/Ti-rich bi-layer thin film was deposited on Si by using DC magnetron sputtering. • The bi-layer exhibits the gradient structure and mechanical properties through the thickness. • The bi-layer shows intrinsic two-way shape memory effect due to functionally graded structure. • The intrinsic two-way shape memory effect was confirmed by finite element simulation. - Abstract: In this research, the gradient structure and mechanical properties of an austenitic/martensitic (Ni{sub 50.8}Ti/Ni{sub 45}TiCu{sub 5} (at.%)) bi-layer thin film was investigated. The bi-layer was deposited on a Si substrate using DC magnetron sputtering. After crystallization of the film at 773 K for 60 min, the microstructure and mechanical properties of the bi-layer thin film were characterized using X-ray diffraction (XRD), transmission electron microscopy (STEM and HRTEM) and nanoindentation, respectively. The diffraction pattern illustrated that the crystallized bi-layer was combined of martensitic and austenitic layers while secondary ion mass spectroscopy (SIMS) and high resolution transmission electron microscopy analysis demonstrated the existence of a compositional gradient through the thickness and residual strain in the interface of the bi-layer, respectively. Furthermore, the compositional gradient in the bi-layer led to gradual variations in the structure, hardness and Young's modulus through the thickness of the bi-layer. The intrinsic two-way shape memory effect due to its functionally graded structure and the induced stress was confirmed by experimental test and finite element simulation.

36 MATERIALS SCIENCE↗

Investigations on the electronic, structural, magnetic properties related to shape-memory behavior in Ti{sub 2}CoX (X=Al, Ga, In)

Highlights: • The analysis of phase stability trend is studied for Ti{sub 2}CoX(X = Al, Ga, In). • Ti{sub 2}CoGa is more suitable as shape memory alloy. • Total magnetic moments disappear with a increase of c/a ratio for all systems. • Density of states at the Fermi level are also shown. - Abstract: Using the full-potential local orbital minimum-basis method, we have performed a systematic investigations on the electronic, structural, and magnetic properties related to shape memory applications for Ti{sub 2}CoX (X=Al, Ga, In) alloys. Our results confirm that these alloys are half-metallic ferromagnets with total magnetic moment of 2μ{sub B} per formula unit in austenite phase, and undergo a martensitic transformation at low temperatures. The relative stabilities of the martensitic phases differ considerably between Ti{sub 2}CoX (X=Al, Ga, In). Details of the electronic structures suggest that the differences in hybridizations between the magnetic components are responsible for trends of phase. Quantitative estimates for the energetics and the magnetizations indicate that Ti{sub 2}CoGa is a promising candidate for shape memory applications.

36 MATERIALS SCIENCE↗

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↗

Controlled Shape Memory Behavior of a Smectic Main-Chain Liquid Crystalline Elastomer

Here, we describe how a smectic main-chain liquid crystalline elastomer (LCE), with controlled shape memory behavior, is synthesized by polymerizing a biphenyl-based epoxy monomer with an aliphatic carboxylic acid curing agent. Microstructures of the LCEs, including their liquid crystallinity and cross-linking density, are modified by adjusting the stoichiometric ratio of the reactants to tailor the thermomechanical properties and shape memory behavior of the material. Thermal and liquid crystalline properties of the LCEs, characterized using differential scanning calorimetry and dynamic mechanical analysis, and structural analysis, performed using small-angle and wide-angle X-ray scattering, show that liquid crystallinity, cross-linking density, and network rigidity are strongly affected by the stoichiometry of the curing reaction. With appropriate structural modifications it is possible to tune the thermal, dynamic mechanical, and thermomechanical properties as well as the shape memory and thermal degradation behavior of LCEs.

36 MATERIALS SCIENCE↗

Effects of the interplay between atomic and magnetic order on the properties of metamagnetic Ni-Co-Mn-Ga shape memory alloys

Ni-Co-Mn-Ga ferromagnetic shape memory alloys show metamagnetic behavior for a range of Co contents. The temperatures of the structural and magnetic transitions depend strongly on composition and atomic order degree, in such a way that combined composition and thermal treatment allows obtaining martensitic transformation between any magnetic state of austenite and martensite. This work presents a detailed analysis of the effect of atomic order on Ni-Co-Mn-Ga alloys through the evolution of structural and magnetic transitions after quench from high temperatures and during post-quest ageing. It is found that the way in which the atomic order affects the martensitic transformation temperatures and entropy depends on the magnetic order of austenite and martensite. The results can be explained assuming that improvement of atomic order decreases the free energy of the structural phases according to their magnetic order. However, it is assumed in this work that changes in the slope—that is, the entropy—of the Gibbs free energy curves are also decisive to the stability of the two-phase system. The experimental transformation entropy values have been compared with a phenomenological model, based on a Bragg–Williams approximation, accounting for the magnetic contribution. The excellent agreement obtained corroborates the magnetic origin of changes in transformation entropy brought about by atomic ordering.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

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↗

Microstructure and transformation behavior of Ni{sub 24.7}Ti{sub 50.3}Pd{sub 25} high temperature shape-memory alloy with Sc micro-addition

NiTiPd shape-memory alloys (SMAs) are potential functional materials for use as solid-state actuators in the temperature range 100–250 °C. The present study investigates the effect of 1.0 at.% Sc micro-addition to Ni{sub 24.7}Ti{sub 50.3}Pd{sub 25} alloy, Sc replacing either Ti or Ni. Results show that all the three alloys studied have stable transformation behavior on stress-free thermal cycling and hence, are suitable for cyclic actuation applications. However, the addition of Sc to NiTiPd alloy leads to decrease of transformation temperatures, the magnitude of decrease being greater for the alloy with Sc replacing Ni. The martensite finish (M{sub f}) temperature of 181 °C for the NiTiPd alloy decreased to 139 °C for Sc replacing Ti and 83 °C for Sc replacing Ni. Also, the indentation modulus of NiTiPdSc (Sc replacing Ni) alloy is found to be significantly low compared to the other alloys. Analysis indicates that the observed differences in the alloy properties are related to the solubility of Sc in the NiTiPd matrix. While the quaternary NiTiPdSc alloy, Sc replacing Ti, has a single phase microstructure, the alloy with Sc replacing Ni shows the presence of Sc-rich and TiPd-type second phases in the microstructure. TEM examination revealed that the TiPd-type phase has a distinct rod-like morphology (30–50 nm) arranged in a grid-like structure. The transformation and indentation behavior of the alloys is elucidated using thermodynamic calculations of frictional energy and an electronic structure based analysis. - Highlights: • TEM of Ni{sub 23.7}Ti{sub 50.3}Pd{sub 25}Sc{sub 1} showed distinct grid of TiPd-type phase nanorods < 50 nm. • Stress-free thermal cycling of all the three alloys showed stable transformation behavior. • Ni{sub 24.7}Ti{sub 49.3}Pd{sub 25}Sc{sub 1} and Ni{sub 23.7}Ti{sub 50.3}Pd{sub 25}Sc{sub 1} showed single and multiphase structures. • Sc micro-addition (1 at.%) to Ni{sub 24.7}Ti{sub 50.3}Pd{sub 25} alloy decreased TTs significantly. • Ni{sub 23.7}Ti{sub 50.3}Pd{sub 25}Sc{sub 1} exhibited lower modulus of 67 GPa to 85 GPa of Ni{sub 24.7}Ti{sub 50.3}Pd{sub 25}.

36 MATERIALS SCIENCE↗

Thermomechanical behavior and microstructural evolution of a Ni(Pd)-rich Ni 24.3 Ti 49.7 Pd 26 high temperature shape memory alloy

We investigated the effect of thermomechanical cycling on a slightly Ni(Pd)-rich Ni 24.3 Ti 49.7 Pd 26 (near stochiometric Ni–Ti basis with Pd replacing Ni) high temperature shape memory alloy. Furthermore, aged tensile specimens (400 °C/24 h/furnace cooled) were subjected to constant-stress thermal cycling in conjunction with microstructural assessment via in situ neutron diffraction and transmission electron microscopy (TEM), before and after testing. It was shown that in spite of the slightly Ni(Pd)-rich composition and heat treatment used to precipitation harden the alloy, the material exhibited dimensional instabilities with residual strain accumulation reaching 1.5% over 10 thermomechanical cycles. This was attributed to insufficient strengthening of the material (insufficient volume fraction of precipitate phase) to prevent plasticity from occurring concomitant with the martensitic transformation. In situ neutron diffraction revealed the presence of retained martensite while cycling under 300 MPa stress, which was also confirmed by transmission electron microscopy of post-cycled samples. Neutron diffraction analysis of the post-thermally-cycled samples under no-load revealed residual lattice strains in the martensite and austenite phases, remnant texture in the martensite phase, and peak broadening of the austenite phase. The texture we developed in the martensite phase was composed mainly of those martensitic tensile variants observed during thermomechanical cycling. Presence of a high density of dislocations, deformation twins, and retained martensite was revealed in the austenite state via in-situ TEM in the post-cycled material, providing an explanation for the observed peak broadening in the neutron diffraction spectra. Despite the dimensional instabilities, this alloy exhibited a biased transformation strain on the order of 3% and a two-way shape memory effect (TWSME) strain of ~2%, at relatively high actuation temperatures.

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↗