A Comparative Biocompatibility Analysis of Ternary Nitinol Alloys

Nitinol alloys are rapidly being utilized as the material of choice in a variety of applications in the medical industry. It has been used for self-expanding stents, graft support systems, and various other devices for minimally invasive interventional and endoscopic procedures. However, the biocompatibility of this alloy remains a concern to many practitioners in the industry due to nickel sensitivity experienced by many patients. In recent times, several new Nitinol alloys have been introduced with the addition of a ternary element. Nevertheless, there is still a dearth of information concerning the biocompatibility and corrosion resistance of these alloys. This study compared the biocompatibility of two ternary Nitinol alloys prepared by powder metallurgy (PM) and arc melting (AM) and critically assessed the influence of the ternary element. ASTM F 2129-08 cyclic polarization in vitro corrosion tests were conducted to evaluate the corrosion resistance in phosphate buffered saline (PBS). The growth of endothelial cells on NiTi was examined using optical microscopy.     

冷喷涂制备多孔Ta涂层及生物相容性

目的 提高生物医用钛合金的生物相容性。方法 采用冷喷涂技术在其表面制备了内部多孔且表面粗糙的钽涂层,并对涂层的微观组织、弹性模量、表面粗糙度、孔隙率、相组成等进行表征;通过溶血率实验、动态凝血时间实验、血小板黏附实验和细胞增殖实验等评价其血液相容性。结果 涂层表面粗糙度为24.9μm,孔隙率为12.6%,弹性模量为147 GPa。喷涂后涂层相组成为Ta,涂层与基体的结合强度为24 MPa。TC4钛合金基体和钽涂层2种材料均具有优异的红细胞相容性且2种材料表面的动态凝血程度相似,表明在TC4钛合金表面制备钽涂层后,钽涂层不会影响凝血因子的活性。钽涂层具有更好的防止血小板黏附与变形的性能。在细胞增殖实验中,细胞在钽涂层表面的增殖能力略高于TC4钛合金。结论 多孔钽涂层的弹性模量相对钽块降低了22%。其生物活性高于TC4钛合金基体。     

Cytotoxicity of Ni from Surface-Treated Porous Nitinol (PNT) on Osteoblast Cells

The leaching of nickel from the surface of porous Nitinol (PNT) is mainly dependent on its surface characteristics, which can be controlled by appropriate surface treatments. In this investigation, PNT was subjected to two surface treatments, namely, water-boiling and dry-heating passivations. Phosphate buffer saline (PBS) solutions obtained from cyclic potentiodynamic polarization tests on PNT were employed to assess the cytotoxicity of Ni contained therein on osteoblast cells by Sulforhodamine B (SRB) assay. In addition, similar concentrations of Ni were added exogenously to cell culture media to determine cytotoxic effects on osteoblast cells. The morphologies of the untreated and the surface-treated PNTs were examined using SEM and AFM. Furthermore, growth of human osteoblast cells was observed on the PNT surfaces.     

The Effect of Material Removal on the Corrosion Resistance and Biocompatibility of Nitinol Laser-Cut and Wire-Form Products

Laser cutting and wire forming are two of the most commonly used processes in the manufacture of Nitinol medical devices. This study explores how varying the amount of material removed during the final surface treatment steps affects the corrosion resistance of Z-type stents that have either been laser-cut from tube or shape set from wire. All parts were subjected to a typical heat treatment process necessary to achieve an Austenite finish (A_f) temperature of 25 ± 5 °C, and were subsequently post-processed with an electrochemical passivation process. The total weight loss during post-processing was recorded and the process adjusted to create groups with less than 5%, less than 10%, and less than 25% amounts of weight loss. The parts were then crimped to 6 mm and allowed to expand back to their original diameter. The corrosion test results showed that on average both groups of Z-stents experienced an increase in the corrosion breakdown potential and a decrease in the standard deviation with increasing amounts of material removal. In addition, less material removal is required from the wire-form Z-stents as compared to the laser-cut Z-stents to achieve high corrosion resistance. Finally, 7 day nickel ion release tests performed on the wire-formed Z-stents showed a dramatic decrease from 0.0132 mg of nickel leached per day for the low weight loss group to approximately 0.001 mg/day for the medium and high weight loss groups.     

HVOF-Sprayed Nano TiO2-HA Coatings Exhibiting Enhanced Biocompatibility

Biomedical thermal spray coatings produced via high-velocity oxy-fuel (HVOF) from nanostructured titania (n-TiO₂) and 10 wt.% hydroxyapatite (HA) (n-TiO₂-10wt.%HA) powders have been engineered as possible future alternatives to HA coatings deposited via air plasma spray (APS). This approach was chosen due to (i) the stability of TiO₂ in the human body (i.e., no dissolution) and (ii) bond strength values on Ti-6Al-4V substrates more than two times higher than those of APS HA coatings. To explore the bioperformance of these novel materials and coatings, human mesenchymal stem cells (hMSCs) were cultured from 1 to 21 days on the surface of HVOF-sprayed n-TiO₂ and n-TiO₂-10 wt.%HA coatings. APS HA coatings and uncoated Ti-6Al-4V substrates were employed as controls. The profiles of the hMSCs were evaluated for (i) cellular proliferation, (ii) biochemical analysis of alkaline phosphatase (ALP) activity, (iii) cytoskeleton organization (fluorescent/confocal microscopy), and (iv) cell/substrate interaction via scanning electron microscopy (SEM). The biochemical analysis indicated that the hMSCs cultured on n-TiO₂-10 wt.%HA coatings exhibited superior levels of bioactivity than hMSCs cultured on APS HA and pure n-TiO₂ coatings. The cytoskeleton organization demonstrated a higher degree of cellular proliferation on the HVOF-sprayed n-TiO₂-10wt.%HA coatings when compared to the control coatings. These results are considered promising for engineering improved performance in the next generation of thermally sprayed biomedical coatings.     

锌锶共掺杂TiO_2多孔涂层的抗菌及生物相容性

为改善钛的抗菌性能和生物活性,采用微弧氧化(MAO)技术在纯钛表面制备了锌掺杂TiO_2涂层(M-Zn)、锶掺杂的TiO_2涂层(M-Sr)和锌锶共掺杂TiO_2涂层(M-Zn/Sr)。利用扫描电子显微镜(SEM)和X射线衍射仪(XRD)对制备的涂层的组织结构和成分进行分析;采用平板计数法研究了涂层的抗菌性能;利用细胞荧光染色和甲基噻唑基四唑(MTT)的方法探究了细胞在材料表面的生长状况。结果表明:形成的TiO_2涂层都是典型的多孔结构,主要由金红石和锐钛矿相组成,锌、锶的掺杂对涂层形貌影响不大。M-Zn/Sr涂层中锌、锶的原子数分数分别为7.9%和1.7%。M-Zn及M-Zn/Sr涂层大肠杆菌展现了良好的抗菌性能,抗菌率接近100%。M-Zn、M-Sr和M-Zn/Sr均能促进成骨细胞增殖,M-Zn/Sr涂层具有抗菌和细胞增殖的双重功能。     

Nitinol Strain Effects

Straining annealed Nitinol (TiNi) wire changes the characteristics of its subsequent phase transformation. It generates peaks in electrical resistance and an additional peak in the calorimetry curve. This work explores the relationship between the stress associated with this strain and the peaks formed during transformation. Straining the wire in the martensitic vs. austenitic condition can produce differences in the subsequent phase transformation. This phenomenon can be exploited for higher temperature transformations in one-time applications.     

Comparison of the Fatigue Performance of Commercially Produced Nitinol Samples versus Sputter-Deposited Nitinol

Self-expanding vascular implants are typically manufactured from Nitinol tubing, using laser cutting, shape setting, and electropolishing processes. The mechanical and fatigue behavior of those devices are affected by the raw material and its processing such as the melting process and subsequent warm and cold forming processes. Current trends focus on the use of raw material with fewer inclusions to improve the fatigue performance. Further device miniaturization and higher fatigue life requirements will drive the need toward smaller inclusions and new manufacturing methods. As published previously, the high-cycle fatigue region of medical devices from standard processed Nitinol is usually about 0.4-0.5% half-alternating strain. However, these results highly depend on the ingot and semi-finished materials, the applied manufacturing processes, the final dimensions of test samples, and applied test methods. Fabrication by sputter deposition is favorable, because it allows the manufacturing of micro-patterned Nitinol thin-film devices without small burrs, heat-affected zones, microcracks, or any contamination with carbides, as well as the fabrication of complex components e.g., 3D geometries. Today, however, there is limited data available on the fatigue behavior for real stent devices based on such sputter-deposited Nitinol. A detailed study (e.g., using metallographic methods, corrosion, tensile, and fatigue testing) was conducted for the first time in order to characterize the micro-patterned Nitinol thin-film material.     

Nitinol Surfaces for Implantation

Nitinol, a group of nearly equiatomic Ni-Ti alloys, steadily conquers new areas of application. Because of the need to keep a low profile of miniature implant devices, and considering the lack of compatibility between Nitinol superelasticity and the mechanical properties of traditional coatings, bare surfaces are of interest. In this article, an overview of our studies of bare Nitinol surfaces is presented, and the performance of coated surfaces is outlined. Together dense and porous Nitinol offer a wide array of surface topographies, suitable for attachment and migration of biological cells and tissue ingrowth. Native Nitinol surface oxides vary from amorphous to crystalline and exhibit semiconducting properties associated with better blood compatibility. Nitinol surfaces are analyzed with regard to high and lasting nickel release in vitro. Surface oxide thickness and Nitinol intermetallic particulates are discussed in relation to corrosion resistance and mechanical performance of the material.     

稀土CeO2增强型多孔钛的制备与性能

孔隙率对多孔钛的成骨性能影响较大,高的孔隙率更有利于骨组织的长入。但随着孔隙率的升高,其力学性能必然会急剧下降。因此,如何在保证多孔钛高孔隙率的前提下提高其力学性能,成为当前势必解决的难题。本研究采用浆料发泡法,通过在钛粉中加入不同含量的氧化铈,制备出高孔隙率的多孔钛。结果表明,多孔钛孔隙呈三维网络状,孔隙率为71.6%～73.5%,孔径主要分布在100～700μm,且孔壁上分布着微米级的微孔。当氧化铈的加入量为0.2%(质量分数,下同)时,多孔钛表现出最优的生物力学相容性,其杨氏模量为2.08GPa,抗压强度为60.19MPa。     

Morphology Engineering of Porous Media for Enhanced Solar Fuel and Power Production

The favorable and adjustable transport properties of porous media make them suitable components in reactors used for solar energy conversion and storage processes. The directed engineering of the porous media’s morphology can significantly improve the performance of these reactors. We used a multiscale approach to characterize the changes in performance of exemplary solar fuel processing and solar power production reactors incorporating porous media as multifunctional components. The method applied uses imaging-based direct numerical simulations and digital image processing in combination with volume averaging theory to characterize the transport in porous media. Two samples with varying morphology (fibrous vs. foam) and varying size range (mm vs. μm scale), each with porosity between 0.46 and 0.84, were characterized. The obtained effective transport properties were used in continuum-scale models to quantify the performance of reactors incorporating multifunctional porous media for solar fuel processing by photoelectrochemical water splitting or power production by solar thermal processes.     

Nitinol surface finishing by magnetoelectropolishing

Abstract

A new advanced technology is proposed to obtain bare metal surfaces for peripheral stents, endodontic files and another medical devices. The effect of an externally applied magnetic field during electropolishing (magnetoelectropolishing) of Nitinol on its surface properties was investigated. The results are compared with standard electropolished Nitinol in the same electrolyte under the same process conditions. To evaluate surface properties, the following techniques were used: SEM and EDX, AFM, contact angle measurement, Auger electron spectroscopy, electrochemical impedance spectroscopy and fatigue resistance testing. All of the above analyses showed significant differences between magnetoelectropolished and conventional electropolished Nitinol surfaces. The two most prominent differences, which are likely to have the most profound implications on increased use of this intermetallic material in medical application are improved wettability and fatigue resistance.     

Analysis of New Nitinol Ingot Qualities

New ingot qualities, processed by optimized vacuum arc remelting (VAR), optimized vacuum induction melting followed by VAR and VAR followed by electron beam remelting, were compared with standard quality. Finished components as well as diamond-shaped samples representing a typical dimension of self-expanding stents were produced using Nitinol tubing drawn from the new ingot qualities. Metallographic longitudinal sections were prepared and analyzed to determine inclusion size and distributions of the various ingot qualities. Radial force and uniaxial tensile tests were used to determine the mechanical properties of fully processed material and tubing, respectively. Transformation temperatures of tubing as delivered from supplier and processed stents were measured by differential scanning calorimetry and deformation-and-free-recovery testing. Finally, fatigue tests were performed on diamond-shaped samples to evaluate the strain-life characteristics of the new ingot qualities. Results of this study are compared to ADMEDES historical data from standard Nitinol materials to gain an assessment of the new improved ingot qualities with regard to the production of Nitinol vascular implants. The latest developments in Nitinol ingot quality are highlighted and the results of the comparison from technical point of view are shown.     

稀土LaF3增强型梯度结构多孔钛及其力学性能

采用粉末冶金法制备外层高孔隙率/内层低孔隙率的梯度结构多孔钛,以解决单层多孔钛孔隙率高强度低的问题。梯度双层多孔钛内层孔隙率约为30%,外层孔隙率可达65%以上,孔径范围在100~255μm之间,内/外层孔径和孔隙率呈梯度分布,其抗压强度和弹性模量分别为117.50~143.55MPa和1.95~3.08GPa。在梯度多孔钛外层添加稀土氟化镧进一步提高了其力学性能。当添加量为0.05%(质量分数)时,其抗压强度和弹性模量最高,可达到213.76MPa和3.38GPa。     

Fracture of Polymer-Coated Nitinol During Gamma Sterilization

After gamma sterilization of a packaged medical device, fractures were discovered in the superelastic nitinol wire used as part of the assembly. The nitinol wire was encased in fluorinated ethylene propylene (FEP) shrink tube. The only fractures occurred where the encased wire was held under strain during gamma sterilization. A study was conducted to determine the susceptibility of nitinol to this type of failure. The variables studied included wire diameter, wire surface finish, wire oxide layer, quantity of wires encased, type of tubing, and strain level during gamma sterilization. The greatest susceptibility to fracture occurred to single wire samples with a light oxide layer held under high strain in FEP shrink tube. Gamma sterilization experiments were conducted to isolate and confirm this failure mechanism. Scanning electron microscopy was used to analyze the fractured samples. Chemical analysis was performed in an attempt to detect trace elements to determine the root cause of the failures. Stress corrosion cracking caused by the liberation of fluorine due to the degradation of the polymer during gamma sterilization is suspected.     

Nitinol for Prosthetic and Orthotic Applications

As global populations age, conditions such as stroke and diabetes require individuals to use rehabilitation technology for many years to come due to chronic musculoskeletal, sensory, and other physical impairments. One in four males currently aged 45 will experience a stroke within 40 years and will often require access to prolonged rehabilitation. In addition, worldwide, one individual loses a limb every 30 s due to the complications of diabetes. As a result, innovative ideas are required to devise more effective prosthetic and orthotic devices to enhance quality of life. While Nitinol has already found much favor within the biomedical industry, one area, which has not yet exploited its unique properties, is in the field of physical rehabilitation, ranging from prosthetic and orthotic devices to assistive technology such as wheelchairs. Improved intervention capabilities based on materials such as Nitinol have the potential to vastly improve patients?? quality of life and in the case of orthoses, may even reduce the severity of the condition over time. It is hoped that this study will spark discussion and interest for the materials community in a field which has yet to be fully exploited.     

Stress Effects on Nitinol Phase Transformations

Nitinol alloys are based on the intermetallic compound TiNi.¹ They are noted for their shape memory capability, resulting from a martensite to austenite transformation. Residual stresses from prior cold work can have a major effect on the transformation as shown by measurements of linear contraction, electrical resistance, and calorimetry response following incremental annealing treatments of a cold wrought rod. It is postulated that the retention of an intermediate rhombohedral structure during the transition to martensite is a function of stresses. Precipitation ofthe excess nickel in solution can also generate stresses. Stress reliefofa severely cold wrought rod by annealing at temperatures of 300 to 400°C enables strain recoveries of more than 2.5%. The purpose this investigation was to: verify and explain the large irreversible “stage 1” contraction reported by Buehler et al.,² explain the directional dependence of the reversible “stage 2” dimensional changes; explore how a cold drawn alloy recovers the ability to undergo the phase transformation as a function of its annealing; delineate the effect of stresses on the transition; and provide understanding and guidance on techniques for the thermal processing of nickel-rich Nitinol alloys for use in heat-actuated devices.     

Design Considerations for Nitinol Bone Staples

The use of Nitinol in orthopedic staples has a long, successful history beginning with their first commercial introduction in the early 1980s. Nitinol bone staples are generally inserted through a process of being chilled, opened, and inserted into predrilled holes. Upon insertion, they recover their preprogrammed shape either through springing back after removal of a constraint (using superelasticity) or thermal triggering (using thermal shape memory). In general, Nitinol bone staples fall into one of three categories: (1) those which are superelastic at room temperature, (2) those which recover their shape upon heating to body temperature, or (3) those which recover their shape upon heating above body temperature with the application of an external heat source. These three different design approaches—room temperature superelastic, body temperature activated, and heat activated—each have different performance characteristics. A version of the heat activated staple that uses a controlled heat source appears to have the best combination of clinical forces and procedural control.     

Irradiation-Assisted Stress-Corrosion Cracking of Nitinol During eBeam Sterilization

Medical device fractures during gamma and electron beam (eBeam) sterilization have been reported. Two common factors in these device fractures were a constraining force and the presence of fluorinated ethylene propylene (FEP). This study investigated the effects of eBeam sterilization on constrained light-oxide nitinol wires in FEP. The goal was to recreate these fractures and determine their root cause. Superelastic nitinol wires were placed inside FEP tubes and constrained with nominal outer fiber strains of 10, 15, and 20%. These samples were then subjected to a range of eBeam sterilization doses up to 400 kGy and compared with unconstrained wires also subjected to sterilization. Fractures were observed at doses of >100 kGy. Analysis of the fracture surfaces indicated that the samples failed due to irradiation-assisted stress-corrosion cracking (IASCC). This same effect was also observed to occur with PTFE at 400 kGy. These results suggest that nitinol is susceptible to IASCC when in the presence of a constraining stress, fluorinated polymers, and irradiation.