The use of titanium bone fixation plates is considered the standard of care for skeletal reconstructive surgery. Highly stiff titanium bone fixation plates provide immobilization immediately after the surgery. However, after the bone healing stage, they may cause stress shielding and lead to bone resorption and failure of the surgery. Stiffness-modulated or stiffness-matched Nitinol bone fixation plates that are fabricated via additive manufacturing (AM) have been recently introduced by our group as a long-lasting solution for minimizing the stress shielding and the follow-on bone resorption. Up to this point, we have modeled the performance of Nitinol bone fixation plates in mandibular reconstruction surgery and investigated the possibility of fabricating these implants. In this study, for the first time the realistic design of stiffness-modulated Nitinol bone fixation plates is presented. Plates with different levels of stiffness were fabricated, mechanically tested, and used for verifying the design approach. Followed by the design verification, to achieve superelastic bone fixation plates we proposed the use of Ni-rich Nitinol powder for the AM process and updated the models based on that. Superelastic Nitinol bone fixation plates with the extreme level of porosity were fabricated, and a chemical polishing procedure used to remove the un-melted powder was developed using SEM analysis. Thermomechanical evaluation of the polished bone fixation plates verified the desired superelasticity based on finite element (FE) simulations, and the chemical analysis showed good agreement with the ASTM standard.
In this study, the effect of the addition of Hf on the oxidation behavior of NiTi alloy, which was processed using additive manufacturing and casting, is studied. Thermogravimetric analyses (TGA) were performed at the temperature of 500, 800, and 900 °C to assess the isothermal and dynamic oxidation behavior of the Ni50.4Ti29.6Hf20 at.% alloys for 75 h in dry air. After oxidation, X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy were used to analyze the oxide scale formed on the surface of the samples during the high-temperature oxidation. Two stages of oxidation were observed for the NiTiHf samples, an increasing oxidation rate during the early stage of oxidation followed by a lower oxidation rate after approximately 10 h. The isothermal oxidation curves were well matched with a logarithmic rate law in the initial stage and then by parabolic rate law for the next stage. The formation of multi-layered oxide was observed for NiTiHf, which consists of Ti oxide, Hf oxide, and NiTiO3. For the binary alloys, results show that by increasing the temperature, the oxidation rate increased significantly and fitted with parabolic rate law. Activation energy of 175.25 kJ/mol for additively manufactured (AM) NiTi and 60.634 kJ/mol for AM NiTiHf was obtained.
Laser powder bed fusion has been widely investigated for shape memory alloys, primarily NiTi alloys, with the goal of tailoring microstructures and producing complex geometries. However, processing high temperature shape memory alloys (HTSMAs) remains unknown. In our previous study, we showed that it is possible to manufacture NiTiHf HTSMA, as one of the most viable alloys in the aerospace industry, using SLM and investigated the effect of parameters on defect formation. The current study elucidates the effect of process parameters (PPs) on the functionality of this alloy. Shape memory properties and the microstructure of additively manufactured Ni-rich NiTiHf alloys were characterized across a wide range of PPs (laser power, scanning speed, and hatch spacing) and correlated with energy density. The optimum laser parameters for defect-free and functional samples were found to be in the range of approximately 60–100 J/mm3. Below an energy density of 60 J/mm3, porosity formation due to lack-of-fusion is the limiting factor. Samples fabricated with energy densities of 60–100 J/mm3 showed comparable thermomechanical behavior in comparison with the starting as-cast material, and samples fabricated with higher energy densities (>100 J/mm3) showed very high transformation temperatures but poor thermomechanical behavior. Poor properties for samples with higher energies were mainly attributed to the excessive Ni loss and resultant change in the chemical composition of the matrix, as well as the formation of cracks and porosities. Although energy density was found to be an important factor, the outcome of this study suggests that each of the PPs should be selected carefully. A maximum actuation strain of 1.67% at 400 MPa was obtained for the sample with power, scan speed, and hatch space of 100 W, 400 mm/s, and 140 µm, respectively, while 1.5% actuation strain was obtained for the starting as-cast ingot. These results can serve as a guideline for future studies on optimizing PPs for fabricating functional HTSMAs.