Numerical design of open-porous titanium scaffolds for Powder Bed Fusion using Laser Beam (PBF-LB).

The paper concerns the numerical design of novel three-dimensional titanium scaffolds with complex open-porous structures and desired mechanical properties for the Powder Bed Fusion using Laser Beam (PBF-LB). The 60 structures with a broad range of porosity (38-78%), strut diameters (0.70-1.15 mm), and coefficients of pore volume variation, CV(Vp), 0.35-5.35, were designed using the Laguerre-Voronoi tessellations (LVT). Their Young's moduli and Poisson's ratios were calculated using Finite Element Model (FEM) simulations. The experimental verification was performed on the representative designs additively manufactured (AM) from commercially pure titanium (CP Ti) which, after chemical polishing, were subjected to uniaxial compression tests. Scanning Electron Microscopy (SEM) observations and microtomography (µ-CT) confirmed the removal of the support structures and unmelted powder particles. PBF-LB structures after chemical polishing were in close agreement with the CAD models' dimensions having 4-12% more volume. The computational and experimental results show that elastic properties were predicted in very close agreement for the low CV(Vp), and with even 30-40% discrepancies for CV(Vp) higher than 4.0, mainly due to PBF-LB scaffold architecture drawbacks rather than CAD inaccuracy. Our research demonstrates the possibility of designing the open-porous scaffolds with pore volume diversity and tuning their elastic properties for biomedical applications.

Nanofunctionalization of Additively Manufactured Titanium Substrates for Surface-Enhanced Raman Spectroscopy Measurements.

Powder bed fusion using a laser beam (PBF-LB) is a commonly used additive manufacturing (3D printing) process for the fabrication of various parts from pure metals and their alloys. This work shows for the first time the possibility of using PBF-LB technology for the production of 3D titanium substrates (Ti 3D) for surface-enhanced Raman scattering (SERS) measurements. Thanks to the specific development of the 3D titanium surface and its nanoscale modification by the formation of TiO2 nanotubes with a diameter of ~80 nm by the anodic oxidation process, very efficient SERS substrates were obtained after deposition of silver nanoparticles (0.02 mg/cm2, magnetron sputtering). The average SERS enhancement factor equal to 1.26 × 106 was determined for pyridine (0.05 M + 0.1 M KCl), as a model adsorbate. The estimated enhancement factor is comparable with the data in the literature, and the substrate produced in this way is characterized by the high stability and repeatability of SERS measurements. The combination of the use of a printed metal substrate with nanofunctionalization opens a new path in the design of SERS substrates for applications in analytical chemistry. Methods such as SEM scanning microscopy, photoelectron spectroscopy (XPS) and X-ray diffraction analysis (XRD) were used to determine the morphology, structure and chemical composition of the fabricated materials.

Heat Treatment of NiTi Alloys Fabricated Using Laser Powder Bed Fusion (LPBF) from Elementally Blended Powders.

The use of elemental metallic powders and in situ alloying in additive manufacturing (AM) is of industrial relevance as it offers the required flexibility to tailor the batch powder composition. This solution has been applied to the AM manufacturing of nickel-titanium (NiTi) shape memory alloy components. In this work, we show that laser powder bed fusion (LPBF) can be used to create a Ni55.7Ti44.3 alloyed component, but that the chemical composition of the build has a large heterogeneity. To solve this problem three different annealing heat treatments were designed, and the resulting porosity, microstructural homogeneity, and phase formation was investigated. The heat treatments were found to improve the alloy's chemical and phase homogeneity, but the brittle NiTi2 phase was found to be stabilized by the 0.54 wt.% of oxygen present in all fabricated samples. As a consequence, a Ni2Ti4O phase was formed and was confirmed by transmission electron microscopy (TEM) observation. This study showed that pore formation in in situ alloyed NiTi can be controlled via heat treatment. Moreover, we have shown that the two-step heat treatment is a promising method to homogenise the chemical and phase composition of in situ alloyed NiTi powder fabricated by LPBF.

Chemical Polishing of Additively Manufactured, Porous, Nickel-Titanium Skeletal Fixation Plates.

Nickel-titanium (NiTi) alloys have shown promise for a variety of biomedical applications because of their unique properties of shape memory, superelasticity, and low modulus of elasticity (Young's modulus). Nevertheless, NiTi bulk components cannot be easily machined (e.g., CNC, rolling, grinding, casting, or press molding) due to their thermomechanical sensitivity as well as inherent superelasticity and shape memory. Thus, powder bed fusion (PBF) additive manufacturing has been used to successfully fabricate NiTi medical devices that match the geometric and mechanical needs of a particular patient's condition. However, NiTi PBF fabrication leaves unmelted particles from the source powder adhered to external surfaces, which cause minor dimensional inaccuracy, increase the risk of mechanical failure, and once loose, may irritate or inflame surrounding tissues. Therefore, there is a need to develop a chemical polishing (cleaning) technique to remove unmelted powder from the surfaces of PBF-fabricated implants, especially from inner surfaces that are difficult to access with mechanical polishing tools. This technique is especially useful for highly porous devices printed at high resolution. In this study, a chemical polishing method utilizing HF/HNO3 solution was used to remove loosely attached (i.e., unmelted) powder particles from surfaces of porous, skeletal fixation plates manufactured by PBF AM. It was observed that 7 min of polishing in an HF/HNO3 solution comprising 7.5 HF: 50 HNO3: 42.5 H2O enabled successful removal of all relatively loose and unmelted powder particles. A microcomputed tomography study examination found that the volumetric accuracy of the polished skeletal fixation plates was ±10% compared with the computer-aided design (CAD) model from which it was rendered. This postprocessing chemical polishing protocol is also likely to be useful for removing loose powder, while maintaining CAD model accuracy and mechanical stability for other complexly shaped, porous, three-dimensional (3D), printed NiTi devices.

Biological and Corrosion Evaluation of In Situ Alloyed NiTi Fabricated through Laser Powder Bed Fusion (LPBF).

In this work, NiTi alloy parts were fabricated using laser powder bed fusion (LBPF) from pre-alloyed NiTi powder and in situ alloyed pure Ni and Ti powders. Comparative research on the corrosive and biological properties of both studied materials was performed. Electrochemical corrosion tests were carried out in phosphate buffered saline at 37 °C, and the degradation rate of the materials was described based on Ni ion release measurements. Cytotoxicity, bacterial growth, and adhesion to the surface of the fabricated coupons were evaluated using L929 cells and spherical Escherichia coli (E. coli) bacteria, respectively. The in situ alloyed NiTi parts exhibit slightly lower corrosion resistance in phosphate buffered saline solution than pre-alloyed NiTi. Moreover, the passive layer formed on in situ alloyed NiTi is weaker than the one formed on the NiTi fabricated from pre-alloyed NiTi powder. Furthermore, in situ alloyed NiTi and NiTi made from pre-alloyed powders have comparable cytotoxicity and biological properties. Overall, the research has shown that nitinol sintered using in situ alloyed pure Ni and Ti is potentially useful for biomedical applications.

Methods of Topical Administration of Drugs and Biological Active Substances for Dental Implants-A Narrative Review.

Dental implants are, nowadays, established surgical devices for the restoration of lost teeth. Considered as an alternative for traditional prosthetic appliances, dental implants surpass them in reliability and patient feedback. Local drug delivery around the implants promotes osseointegration and reduces peri-implantitis. However, there are currently no methods of a multiple, precise topical administration of drugs to the implant area. Engineering coatings on the implants, drug application on carriers during implantation, or gingival pockets do not meet all requirements of dental surgeons. Therefore, there is a need to create porous implants and other medical devices that will allow a multiple drug delivery at a controlled dose and release profile without traumatic treatment. Due to the growing demand for the use of biologically active agents to support dental implant treatment at its various stages (implant placement, long-term use of dental superstructures, treatment of the peri-implant conditions) and due to the proven effectiveness of the topical application of pharmacological biologically active agents to the implant area, the authors would like to present a review and show the methods and devices that can be used by clinicians for local drug administration to facilitate dental implant treatment. Our review concludes that there is a need for research in the field of inventions such as new medical devices or implants with gradient solid-porous structures. These devices, in the future, will enable to perform repeatable, controllable, atraumatic, and repeatable injections of active factors that may affect the improvement of osteointegration and the longer survival of implants, as well as the treatment of peri-implantitis.

Novel Cold Crucible Ultrasonic Atomization Powder Production Method for 3D Printing.

A new powder production method has been developed to speed up the search for novel alloys for additive manufacturing. The technique involves an ultrasonically agitated cold crucible installed at the top of a 20 kHz ultrasonic sonotrode. The material is melted with an electric arc and undergoes pulverization with standing wave vibrations. Several different alloys in various forms, including noble and metallic glass alloys, were chosen to test the process. The atomized particles showed exceptional sphericity, while powder output suitable for additive manufacturing reached up to 60%. The AMZ4 metallic glass powder remained amorphous below the 50 µm fraction, while tungsten addition led to crystallization in each fraction. Minor contamination and high Mn and Zn evaporation, especially in the finest particles, was observed in atomized powders. The innovative ultrasonic atomization method appears as a promising tool for material scientists to develop powders with tailored chemical composition, size and structure.

Analysis of Microstructure and Properties of a Ti-AlN Composite Produced by Selective Laser Melting.

Selective Laser Melting (SLM) is a manufacturing technique that is currently used for the production of functional parts that are difficult to form by the traditional methods such as casting or CNC (Computer Numerical Control) cutting from a wide range of metallic materials. In our study, a mixture of commercially pure titanium (Ti) and 15% at. aluminum nitride (AlN) was Selective Laser Melted to form three-dimensional objects. The obtained 4 mm edge cubes with an energy density that varied from 70 to 140 J/mm3 were examined in terms of their microstructure, chemical and phase composition, porosity, and Vickers microhardness. Scanning Electron Microscopy (SEM) observations of the etched samples showed inhomogeneities in the form of pores and unmelted and partly melted AlN particles in the fine-grained dendritic matrix, which is typical for titanium nitrides and titanium aluminum nitrides. The AlN particles remained unmelted in samples, but no porosity was observed in the interface area between them and the dendritic matrix. Additionally, samples fabricated with the presintering step had zones with different sizes of dendrites, suggesting a differing chemical composition of the matrix and the possibility of the formation of the phases forming an Ti-Al-N ternary system. The chemical composition in the microareas of the samples was determined using Energy Dispersive X-Ray Spectroscopy (EDS) and revealed differences in the homogeneity of the samples depending on the SLM process parameters and the additional presintering step. The phase composition, examined using X-ray Diffraction analysis (XRD), showed that samples were formed from Ti, TiN, and AlN phases. Porosity tests carried out using a computer microtomography revealed porosities in a range from 7% to 17.5%. The formed material was characterized by a relatively high hardness exceeding 700 HV0.2 over the entire cross-section, which depended on the manufacturing conditions.

The influence of chemical polishing of titanium scaffolds on their mechanical strength and in-vitro cell response.

Selective Laser Melting (SLM) is a powder-bed-based additive manufacturing method, using a laser beam, which can be used to produce metallic scaffolds for bone regeneration. However, this process also has a few disadvantages. One of its drawbacks is the necessity of post-processing in order to improve the surface finish. Another drawback lies in the removal of unmelted powder particles from the build. In this study, the influence of chemical polishing of SLM fabricated titanium scaffolds on their mechanical strength and in vitro cellular response was investigated. Scaffolds with bimodal pore size (200 µm core and 500 µm shell) were fabricated by SLM from commercially pure titanium powder and then chemically treated in HF/HNO3 solutions to remove unmelted powder particles. The cell viability and mechanical strength were compared between as-made and chemically-treated scaffolds. The chemical treatment was successful in the removal of unmelted powder particles from the titanium scaffold. The Young's modulus of the fabricated cellular structures was of 42.7 and 13.3 GPa for as-made and chemically-treated scaffolds respectively. These values are very similar to the Young's modulus of living human bone. Chemical treatment did not affect negatively cell proliferation and differentiation. Additionally, the chemically-treated scaffolds had a twofold increase in colonization of osteoblast cells migrating out of multicellular spheroids. Furthermore, X-ray computed microtomography confirmed that chemically-treated scaffolds met the dimensions originally set in the CAD models. Therefore, chemical-treatment can be used as a tool to cancel the discrepancies between the designed and fabricated objects, thus enabling fabrication of finer structures with regular struts and high resolution.

The Influence of Selective Laser Melting (SLM) Process Parameters on In-Vitro Cell Response.

The use of laser 3D printers is very perspective in the fabrication of solid and porous implants made of various polymers, metals, and its alloys. The Selective Laser Melting (SLM) process, in which consolidated powders are fully melted on each layer, gives the possibility of fabrication personalized implants based on the Computer Aid Design (CAD) model. During SLM fabrication on a 3D printer, depending on the system applied, there is a possibility for setting the amount of energy density (J/mm³) transferred to the consolidated powders, thus controlling its porosity, contact angle and roughness. In this study, we have controlled energy density in a range 8⁻45 J/mm³ delivered to titanium powder by setting various levels of laser power (25⁻45 W), exposure time (20⁻80 µs) and distance between exposure points (20⁻60 µm). The growing energy density within studied range increased from 63 to 90% and decreased from 31 to 13 µm samples density and Ra parameter, respectively. The surface energy 55⁻466 mN/m was achieved with contact angles in range 72⁻128° and 53⁻105° for water and formamide, respectively. The human mesenchymal stem cells (hMSCs) adhesion after 4 h decreased with increasing energy density delivered during processing within each parameter group. The differences in cells proliferation were clearly seen after a 7-day incubation. We have observed that proliferation was decreasing with increasing density of energy delivered to the samples. This phenomenon was explained by chemical composition of oxide layers affecting surface energy and internal stresses. We have noticed that TiO2, which is the main oxide of raw titanium powder, disintegrated during selective laser melting process and oxygen was transferred into metallic titanium. The typical for 3D printed parts post-processing methods such as chemical polishing in hydrofluoric (HF) or hydrofluoric/nitric (HF/HNO3) acid solutions and thermal treatments were used to restore surface chemistry of raw powders and improve surface.

Post Processing and Biological Evaluation of the Titanium Scaffolds for Bone Tissue Engineering.

Nowadays, post-surgical or post-accidental bone loss can be substituted by custom-made scaffolds fabricated by additive manufacturing (AM) methods from metallic powders. However, the partially melted powder particles must be removed in a post-process chemical treatment. The aim of this study was to investigate the effect of the chemical polishing with various acid baths on novel scaffolds' morphology, porosity and mechanical properties. In the first stage, Magics software (Materialise NV, Leuven, Belgium) was used to design a porous scaffolds with pore size equal to (A) 200 µm, (B) 500 µm and (C) 200 + 500 µm, and diamond cell structure. The scaffolds were fabricated from commercially pure titanium powder (CP Ti) using a SLM50 3D printing machine (Realizer GmbH, Borchen, Germany). The selective laser melting (SLM) process was optimized and the laser beam energy density in range of 91-151 J/mm³ was applied to receive 3D structures with fully dense struts. To remove not fully melted titanium particles the scaffolds were chemically polished using various HF and HF-HNO3 acid solutions. Based on scaffolds mass loss and scanning electron (SEM) observations, baths which provided most uniform surface cleaning were proposed for each porosity. The pore and strut size after chemical treatments was calculated based on the micro-computed tomography (µ-CT) and SEM images. The mechanical tests showed that the treated scaffolds had Young's modulus close to that of compact bone. Additionally, the effect of pore size of chemically polished scaffolds on cell retention, proliferation and differentiation was studied using human mesenchymal stem cells. Small pores yielded higher cell retention within the scaffolds, which then affected their growth. This shows that in vitro cell performance can be controlled to certain extent by varying pore sizes.