Investigations of Shape Deformation Behaviors of the Ferromagnetic Ni-Mn-Ga Alloy/Porous Silicone Rubber Composite towards Actuator Applications.

Ferromagnetic shape memory alloys (FSMAs), which are potential candidates for future technologies (i.e., actuators in robots), have been paid much attention for their high work per volume and rapid response as external stimulation, such as a magnetic field, is imposed. Among all the FSMAs, the Ni-Mn-Ga-based alloys were considered promising materials due to their appropriate phase transformation temperatures and ferromagnetism. Nevertheless, their intrinsic embrittlement issue and sluggish twin motion due to the inhibition of grain boundaries restrict their practicability. This study took advantage of the single-crystal Ni-Mn-Ga cube/silicone rubber composite materials to solve the two aforementioned difficulties. The single-crystal Ni-Mn-Ga cube was prepared by using a high-temperature alloying procedure and a floating-zone (FZ) method, and the cubes were verified to be the near-{100}p Ni-Mn-Ga alloy. Various room temperature (RT) curing silicone rubbers were utilized as matrix materials. Furthermore, polystyrene foam particles (PFP) were used to provide pores, allowing a porous silicone rubber matrix. It was found that the elastic modulus of the silicone rubber was successfully reduced by introducing the PFP. Additionally, the magnetic field-induced martensite variant reorientation (MVR) was greatly enhanced by introducing a porous structure into the silicone rubber. The single-crystal Ni-Mn-Ga cube/porous silicone rubber composite materials are considered to be promising materials for applications in actuators.

Effects of 3d Transition Metal Substitutions on the Phase Stability and Mechanical Properties of Ti-5.5Al-11.8[Mo]eq Alloys.

The phase stability, mechanical properties, and functional properties of Ti-5.5Al-11.8[Mo]eq alloys are focused on in this study by substituting 3d transition metal elements (V, Cr, Co, and Ni) for Mo as ß-stabilizers to achieve similar ß phase stability and room temperature (RT) superelasticity. The ternary alloy systems with the equivalent chemical compositions of Ti-5.5Al-17.7V, Ti-5.5Al-9.5Cr, Ti-5.5Al-7.0Co, and Ti-5.5Al-9.5Ni (mass%) alloys were selected as the target materials based on the Mo equivalent formula, which has been applied for the Ti-5.5Al-11.8Mo alloy in the literature. The fundamental mechanical properties and functionalities of the selected alloys were examined. The ß phase was stabilized at RT in all alloys except for the Ti-Al-V alloy. Among all alloys, the Ti-Al-Ni alloy exhibited superelasticity in the cyclic loading-unloading tensile tests at RT. As a result, similar to the Ti-5.5Al-11.8Mo mother alloy, by utilizing the Mo equivalent formula to substitute 3d transition metal elements for Mo, a RT superelasticity was successfully imposed.

Framework of magnetostrain responsive Ni-Mn-Ga microparticles driving magnetic field induced out-of-plane actuation of laminate composite.

Ni-Mn-Ga single crystals (SC) exhibiting a giant magnetic field induced strain (MFIS), resulting from twin boundaries rearrangements, are excellent materials for novel actuators although enhanced brittleness and high costs are remaining the issues for applications. In polycrystalline state Ni-Mn-Ga alloys show small MFIS due to grain boundary constraints. By simple size reduction of the mentioned materials it is hardly possible to create quasi-two-dimensional MFIS actuators on the microscale with a pertinent out-of-plane performance. In pursuit of the trend for next generation materials and functions by design, in the present work we have developed a laminate composite as a prototype of microactuator with the out-of-plane stroke being driven by a framework of magnetostrain responsive Ni-Mn-Ga microparticles. The laminate consisted of the layer of crystallographically oriented Ni-Mn-Ga semi-free SC microparticles sandwiched between bonding polymer and Cu foils. Such design provided a particles isolation with a minimum constraint condition from the polymer. MFIS of the individual particles and the whole laminate composite was investigated by X-ray micro-CT 3D imaging. Both particles and laminate exhibited the same recoverable out-of-plane stroke produced by the particles´ MFIS of around 3% under 0.9 T. The developed microactuator design is promising for applications in the areas of micro-robotics, optical image stabilization in cameras, pumps for microfluidics etc.

Shape memory effect and aging behavior of Bi-added Ti-Cr alloys for biomedical applications.

For the further development of biocompatible metastable ß (bcc) Ti alloys, the purpose of this study is to evaluate the potential of bismuth (Bi) addition in terms of shape memory properties and phase stability. It was found that the shape memory effect appeared in Ti-5Cr-1.6Bi (mol%) alloy. However, permanent (unrecoverable) deformation due to dislocations or twinning was also introduced simultaneously from the early stage of deformation. Regarding the formation of isothermal ω phase and the resulting hardness change by aging, it was found that the hardness change was large and that the isothermal ω phase formed in Ti-5Cr-1.6Bi alloy, while age hardening was small and no isothermal ω phase formed in Ti-5Cr-6.1Bi alloy. These results indicate the suppression of not only athermal ω but also isothermal ω phase by Bi addition. However, considering the fact that the alloy becomes brittle when Bi addition is over 3 mol%, it can be concluded that 1-3 mol% Bi addition is worth for the improvement of shape memory effect, suppression of ω phase, X-ray imaging, magnetic resonance imaging, and biocompatibility in metastable ß Ti alloys.

Platinum Metallization of Polyethylene Terephthalate by Supercritical Carbon Dioxide Catalyzation and the Tensile Fracture Strength.

Polyethylene terephthalate (PET) is known to be highly inert, and this makes it difficult to be metallized. In addition, Pt electroless plating is rarely reported in the metallization of polymers. In this study, the metallization of biocompatible Pt metal is realized by supercritical CO2 (sc-CO2)-assisted electroless plating. The catalyst precursor used in the sc-CO2 catalyzation step is an organometallic compound, palladium (II) acetylacetonate (Pd(acac)2). The electrical resistance is evaluated, and a tape adhesion test is utilized to demonstrate intactness of the Pt layer on the PET film. The electrical resistance of the Pt/PET with 60 min of the Pt deposition time remains at a low level of 1.09 Ω after the adhesion test, revealing positive effects of the sc-CO2 catalyzation step. A tensile test is conducted to evaluate the mechanical strength of the Pt/PET. In-situ electrical resistances of the specimen are monitored during the tensile test. The fracture strength is determined from the stress value when the short circuit occurred. The fracture strength is 33.9 MPa for a specimen with 30 min of the Pt deposition time. As the Pt deposition time increases to 45 min and 60 min, the fracture strengths reach 52.3 MPa and 65.9 MPa, respectively. The promoted fracture strength and the decent electrical conductivity demonstrate the advantages toward biomedical devices.

Promoted mechanical properties and functionalities via Ta-tailored Ti-Au-Cr shape memory alloys towards biomedical applications.

In view of the urgent demands of shape memory alloys (SMAs) for biomedical applications due to the world population aging issue, the mechanical properties and functionalities of the biocompatible Ti-Au-Cr-based SMAs, which are tailored by Ta additions, have been developed in this study. The quaternary SMAs were successfully manufactured by physical metallurgy techniques and their mechanical properties and functionalities were examined. In the continuous tensile tests, it was found that the correlation between the yielding strength and phase stability followed a typical trend of mechanical behavior of SMAs, showing the lowest yielding strength at the metastable ß-parent phase. Functional mappings between the alloy strength and elongation revealed that compared to the Ta-free specimen, the ductility was promoted 50% while the strength remained intact through the 4 at.% introduction of Ta. Slight shape recovery was observed in the cyclic loading-unloading tensile tests during the unloading process and the highest shape recovery was found in the Ti-4 at.% Au-5 at.% Cr-4 at.% Ta specimen. This indicates that the 4 at.% Ta tailored Ti-Au-Cr SMAs could be a promising material for biomedical applications.

Achievement of Room Temperature Superelasticity in Ti-Mo-Al Alloy System via Manipulation of ω Phase Stability.

The achievement of room-temperature (RT) superelasticity in a Ti-Mo-Al ternary alloy system through the addition of a relatively high concentration of Al to manipulate the phase stability of the ω phase is realized in this study. The composition of the Ti-6 mol% Mo (Ti-11.34 mass% Mo) alloy was designated as the starting alloy, while 5 mol% Al (=2.71 mass% Al) and 10 mol% Al (=5.54 mass% Al) were introduced to promote their superelastic behavior. Among the alloys, Ti-6 mol% Mo-10 mol% Al alloy, which was investigated for the very first time in this work, performed the best in terms of superelasticity. On the other hand, Ti-6 mol% Mo and Ti-6 mol% Mo-5 mol% Al alloys exhibited a shape memory effect upon heating. It is worth mentioning that in the transmission electron microscopy observation, ω phase, which appeared along with ß-parent phase, was significantly suppressed as Al concentration was elevated up to 10 mol%. Therefore, the conventional difficulties of the inhibited RT superelasticity were successfully revealed by regulating the number density of the ω phase below a threshold.

Investigations of Effects of Intermetallic Compound on the Mechanical Properties and Shape Memory Effect of Ti-Au-Ta Biomaterials.

Owing to the world population aging, biomedical materials, such as shape memory alloys (SMAs) have attracted much attention. The biocompatible Ti-Au-Ta SMAs, which also possess high X-ray contrast for the applications like guidewire utilized in surgery, were studied in this work. The alloys were successfully prepared by physical metallurgy techniques and the phase constituents, microstructures, chemical compositions, shape memory effect (SME), and superelasticity (SE) of the Ti-Au-Ta SMAs were also examined. The functionalities, such as SME, were revealed by the introduction of the third element Ta; in addition, obvious improvements of the alloy performances of the ternary Ti-Au-Ta alloys were confirmed while compared with that of the binary Ti-Au alloy. The Ti3Au intermetallic compound was both found crystallographically and metallographically in the Ti-4 at.% Au-30 at.% Ta alloy. The strength of the alloy was promoted by the precipitates of the Ti3Au intermetallic compound. The effects of the Ti3Au precipitates on the mechanical properties, SME, and SE were also investigated in this work. Slight shape recovery was found in the Ti-4 at.% Au-20 at.% Ta alloy during unloading of an externally applied stress.

Enhancement of mechanical properties and shape memory effect of Ti-Cr-based alloys via Au and Cu modifications.

The requirements for biomedical materials have been raised greatly due to the rapidly aging global population. Shape memory alloys (SMAs) are indeed promising materials for biomedical applications due to their controllable shape deformation via the manipulation of temperature and/or stress. This study investigated the enhancement of the fundamental mechanical properties and the shape memory effect (SME) in the Ti-Cr-based alloys via the modification of Au and Cu. The quaternary Ti-Cr-Au-Cu alloys were successfully manufactured by physical metallurgy methods and their phase constitutions, mechanical properties, SME, and superelastic (SE) behaviors have been investigated in this study. Cold-workability, which was enhanced by the introduction of the Au element, was elaborated by the phase constitutions of the alloys. The ß-parent phase was stabilized to around body temperature by the introduction of the ß-stabilizers of Cr, Au, and Cu, and the functionalities of the specimens were revealed at the operating temperature. Perfect SME at the shape recovery rate of 100% was practiced by the substitution of Au by Cu and the mechanical properties, such as strength and ductility, were also enhanced. Functional mappings of the fundamental mechanical properties, which could be a helpful tool for the investigations of the quaternary Ti-Cr-Au-Cu alloys, were constructed in this work.

Mechanical Properties Enhancement of the Au-Cu-Al Alloys via Phase Constitution Manipulation.

To enhance the mechanical properties (e.g., strength and elongation) of the face-centered cubic (fcc) α-phase in the Au-Cu-Al system, this study focused on the introduction of the martensite phase (doubled B19 (DB19) crystal structure of Au2CuAl) via the manipulation of alloy compositions. Fundamental evaluations, such as microstructure observations, phase identifications, thermal analysis, tensile behavior examinations, and reflectance analysis, have been conducted. The presence of fcc annealing twins was observed in both the optical microscope (OM) and the scanning electron microscope (SEM) images. Both strength and elongation of the alloys were greatly promoted while the DB19 martensite phase was introduced into the alloys. Amongst all the prepared specimens, the 47Au41Cu12Al and the 44Au44Cu12Al alloys performed the optimized mechanical properties. The enhancement of strength and ductility in these two alloys was achieved while the stress plateau was observed during the tensile deformation. A plot of the ultimate tensile strength (UTS) against fracture strain was constructed to illustrate the effects of the introduction of the DB19 martensite phase on the mechanical properties of the alloys. Regardless of the manipulation of the alloy compositions and the introduction of the DB19 martensite phase, the reflectance stayed almost identical to pure Au.

Evaluation of the Shape Memory Effect by Micro-Compression Testing of Single Crystalline Ti-27Nb Ni-Free Alloy.

In this work, micro-compression tests are performed at various temperatures with Ti-27Nb (at.%) single crystalline pillars to investigate anisotropic deformation behavior, including the shape memory effect. In non-tapered single-crystal pillars with loading directions parallel to [001], [011], and [111], transformation strain and stress show orientation dependence. [001]-oriented micropillars with aspect ratios of 2 and 1.5 demonstrate temperature-dependent transformation stress during micro-compression at various temperatures. Although more stress is required to induce martensite transformation in the pillar with the lower aspect ratio, the temperature dependence of ~1.8 MPa/K observed in both pillars is in good agreement with that of bulk Ti-27Nb.

Brillouin characterization of slimmed polymer optical fibers for strain sensing with extremely wide dynamic range.

To date, most distributed Brillouin sensors for structural health monitoring have employed glass optical fibers as sensing fibers, but they are inherently fragile and cannot withstand strains of >3%. This means that the maximal detectable strain of glass-fiber-based Brillouin sensors was ~3%, which is far from being sufficient for monitoring the possible distortion caused by big earthquakes. To extend this strain dynamic range, polymer optical fibers (POFs) have been used as sensing fibers. As POFs can generally withstand even ~100% strain, at first, Brillouin scattering in POFs was expected to be useful in measuring such large strain. However, the maximal detectable strain using Brillouin scattering in POFs was found to be merely ~5%, because of a Brillouin-frequency-shift hopping phenomenon accompanied by a slimming effect peculiar to polymer materials. This conventional record of the strain dynamic range (5%) was still far from being sufficient. Here, we have thought of an idea that the strain dynamic range can be further extended by employing a POF with its whole length slimmed in advance and by avoiding the Brillouin-frequency-shift hopping. The experimental results reveal that, by applying 3.0% strain to a slimmed POF beforehand, we can achieve a >25% strain dynamic range, which is >5 times the conventional value and will greatly extend the application fields of fiber-optic Brillouin sensing.

Plastic deformation behaviour of single-crystalline martensite of Ti-Nb shape memory alloy.

ß-Ti alloys have attracted considerable attention as new biomedical shape memory alloys. Given the critical importance of the plastic deformation in the martensite phase for the shape memory effect and superelasticity, we investigated here the plastic deformation behaviour of a single crystal of α″ (orthorhombic) martensite of Ti-27 mol%Nb shape memory alloy obtained by the stress-induced martensitic transformation of a single crystal of the parent ß phase. Four operative plastic deformation modes were observed, including two dislocation slips and two twinnings. To the best of our knowledge, two of these plastic deformation modes (one dislocation slip and one twinning) were discovered for the first time in this study. The identified slip and twinning systems in the martensite phase have corresponding slip and twinning systems in the parent ß phase with which they share many similarities. Therefore, we believe that the plastic deformation of the α″ martensite is inherited from that of the parent ß phase.

In vitro evaluation of biocompatibility of Ti-Mo-Sn-Zr superelastic alloy.

Shape memory alloys (SMAs) including superelastic alloys have unique properties such as shape memory and superelasticity, thus they are recognized as very useful biomaterials. These properties are very advantageous for medical use, and actually the SMA wires have been widely used in medical field. However, biocompatibility of nickel-titanium (Ni-Ti) alloy, which is the only practical SMA at present, has been questioned because of its high nickel content. The aim of this study was to evaluate the biocompatibility of a newly developed Ni-free Ti-based SMA for medical use. The newly developed SMA made of Ti-Mo-Sn-Zr system was processed into a disk of 15.1 mm in diameter. Pure titanium of the same shape was prepared as control. All the disk surfaces were polished using emery papers, #120, #400, and #600. Scanning electron microscopy and a 3D optics profiler were used to evaluate the surface of the materials. In vitro evaluations included colony examination for evaluation of the cell cytotoxicity, DNA quantification for the cell proliferation, Alamar blue assay for metabolic activity, FDA staining for the live cell imaging, and cell cycle analysis, using Chinese hamster fibroblastic V-79 cells and mouse osteoblastic MC3T3-E1 cells. In colony examination and DNA quantification, there was no significant difference between the Ti-Mo-Sn-Zr and the pure titanium. In FDA staining, cultured cells on the Ti-Mo-Sn-Zr alloy showed the same biocompatibility as those on the pure titanium. The present results suggest that the newly developed Ti-Mo-Sn-Zr alloy showed the high biocompatibility comparable to pure titanium and can be used as efficient biomaterial for medical use.

Novel Ti-base superelastic alloys with large recovery strain and excellent biocompatibility.

In this study, a new Ti-Zr-Nb-Sn alloy system was developed as Ni-free biomedical superelastic alloys with a large recovery strain and excellent biocompatibility. Ti-18Zr-(9-16)Nb-(0-4)Sn alloys were prepared by an Ar arc melting method and the effect of composition on the crystal structure and superelastic properties was investigated. A large superelastic recovery strain of 6.0% was observed in Ti-18Zr-12.5Nb-2Sn, Ti-18Zr-11Nb-3Sn, and Ti-18Zr-9.5Nb-4Sn alloys subjected to cold-rolling and solution treatment. XRD results showed that the large recovery strain of Sn-added alloys is due to a combination effect of a large transformation strain and a strong recrystallization texture. The Ti-18Zr-11Nb-3Sn alloy exhibited excellent cyclic stability with an extremely narrow stress hysteresis about 20MPa. Cytocompatibility was also examined using three types of cell lines, murine fibroblast L929, human osteosarcoma SaOS-2, and human umbilical vein endothelial cell HUVEC and the results showed that the Ti-18Zr-11Nb-3Sn alloy exhibited larger cell covering ratios when compared with those of the Ti-50.5Ni alloy for all kinds of cells.

Superelastic properties of biomedical (Ti-Zr)-Mo-Sn alloys.

A new class of Ti-50Zr base biomedical superelastic alloys was developed in this study. The (Ti-Zr)-Mo-Sn alloys exhibited a shape memory effect and superelastic property by adjusting Mo and Sn contents. The (Ti-Zr)-1.5Mo-3Sn alloy revealed the most stable superelasticity among (Ti-Zr)-(1-2)Mo-(2-4)Sn alloys. The superelastic recovery strain showed a strong dependence on heat treatment temperature after cold working in the (Ti-Zr)-1.5Mo-3Sn alloy. The superelastic recovery strain increased as the heat treatment temperature increased although the critical stress for slip decreased. The (Ti-Zr)-1.5Mo-3Sn alloy heat treated at 1073K exhibited excellent superelastic properties with a large recovery strain as large as 7% which is due to the strong {001}ß<110>ß recrystallization texture.

New internalized distraction device for craniofacial plastic surgery using Ni-free, Ti-based shape memory alloy.

This study was undertaken to examine effects and biocompatibility of a new internalized distraction device made from newly developed Ti-Nb-Al shape memory alloy (SMA). Crania of Wistar rats were expanded using a U-shaped wire of this SMA set on each cranium in an experimental group. At 2 or 4 weeks after operation, the rats were killed; width measurements and three-dimensional observations of crania were conducted using soft x-ray and microfocus x-ray computed tomography photography. After photography, histologic sections were made and stained with hematoxylin and eosin. No pathologic change in the experimental duration was observed macroscopically or histologically. Significantly increased size was found for the rat crania in the experimental group compared with the control group. Results demonstrated the feasibility and biocompatibility of internalized distraction osteogenesis using Ni-free, Ti-based SMA in craniofacial plastic surgery for craniofacial deformities.

Orthodontic buccal tooth movement by nickel-free titanium-based shape memory and superelastic alloy wire.

OBJECTIVE: To examine the mechanical properties and the usefulness of titanium-niobium-aluminum (Ti-Nb-Al) wire in orthodontic tooth movement as compared with nickel-titanium (Ni-Ti) wire. MATERIALS AND METHODS: The load deflection of expansion springs was gauged with an original jig. The gradient of the superelastic region was measured during the unloading process. Expansion springs comprising the two types of alloy wires were applied to upper first molars of rats. The distance between the first molars was measured with micrometer calipers. RESULTS: The force magnitude of the Ti-Nb-Al expansion spring was lower than that of the Ni-Ti expansion spring over the entire deflection range. The initial force magnitude and the gradient in the superelastic region of the Ti-Nb-Al expansion springs were half those of the Ni-Ti expansion springs. Thus, Ti-Nb-Al expansion springs generated lighter and more continuous force. Tooth movement in the Ni-Ti group proceeded in a stepwise fashion. On the other hand, tooth movement in the Ti-Nb-Al group showed relatively smooth and continuous progression. At 17 days after insertion of expansion springs, there were no significant differences between the Ti-Nb-Al and Ni-Ti groups in the amount of tooth movement. CONCLUSIONS: These results indicate that Ti-Nb-Al wire has excellent mechanical properties for smooth, continuous tooth movement and suggest that Ti-Nb-Al wire may be used as a practical nickel-free shape memory and superelastic alloy wire for orthodontic treatment as a substitute for Ni-Ti wire.

[Gamma knife radiosurgery for spontaneous carotid-cavernous sinus fistula (CCF)].

Gamma knife radiosurgery was carried out for spontaneous CCF (carotid-cavernous sinus fistula) in 8 patients (1 male and 7 females), and its results were reported. The ages ranged from 48 to 74 years with a mean of 60.6 years. As initial treatment before radiosurgery, embolization was carried out except in one patient, and radiotherapy was used in two patients. Six patients were in the category of Barrow's type D, and two patients were in the category of Barrow's type B. As it contained the fistula, the lateral wall of the cavernous sinus was irradiated with 8-14.5 Gy (mean 10.8 Gy). As a result, complete obliteration of CCF was confirmed by DSA in seven of the eight patients between 6 and 18 months after radiosurgery. There were no side effects observed during a follow-up period of 8 to 116 months. Although the main treatment for spontaneous CCF is intravascular surgery at present, gamma knife radiosurgery is a useful adjuvant treatment for the residual CCF after embolization.