Titanium Scaffolds Research Articles

Deferoxamine functionalized alginate-based collagen composite material enhances the integration of metal implant and bone interface

Poor osseointegration markedly compromises the longevity of prostheses. To enhance the stability of titanium implants, surface functionalization is a proven strategy to promote prosthesis-bone integration. This study developed a hydrogel coating capable of simultaneous osteoangiogenesis and vascularization by incorporating deferoxamine (DFO) into a sodium alginate mineralized collagen composite hydrogel. The physicochemical properties of this hydrogel were thoroughly analyzed. In vivo and in vitro experiments confirmed the hydrogel scaffold's osteogenic and angiogenic capabilities. Results indicated that sodium alginate notably enhanced the mechanical characteristics of the mineralized collagen, allowing it to fully infiltrate the interstices of the 3D-printed titanium scaffold. Furthermore, as the hydrogel degraded, collagen, calcium ion, phosphate ion, and DFO were gradually released around the scaffolds, altering the local osteogenic microenvironment and strongly inducing new bone tissue growth. These findings offer novel perspectives for the creation and utilization of functionalized bone implant materials.

Modified multilayered porous titanium scaffolds with silicon-doped coating surface-loaded BMP-2 prepared by microarc oxidation for bone defect repair

Modified multilayered porous titanium scaffolds with silicon-doped coating surface-loaded BMP-2 prepared by microarc oxidation for bone defect repair

Enhanced osseointegration and antimicrobial properties of 3D-Printed porous titanium alloys with copper-strontium doped calcium silicate coatings.

The 3D printing of porous titanium scaffolds reduces the elastic modulus of titanium alloys and promotes osteogenic integration. However, due to the biological inertness of titanium alloy materials, the implant-bone tissue interface is weakly bonded. A calcium silicate (CS) coating doped with polymetallic ions can impart various biological properties to titanium alloy materials. In this study, CuO and SrO binary-doped CS coatings were prepared on the surface of 3D-printed porous titanium alloy scaffolds using atmospheric plasma spraying and characterized by SEM, EDS, and XRD. Both CuO and SrO were successfully incorporated into the CS coating. The in vivo osseointegration evaluation of the composite coating-modified 3D-printed porous titanium alloy scaffolds was conducted using a rabbit bone defect model, showing that the in vivo osseointegration of 2% CuO-10% SrO-CS-modified 3D-printed porous titanium alloy was improved. The in vitro antimicrobial properties of the 2% CuO-10% SrO-CS-modified 3D-printed porous titanium alloy were evaluated through bacterial platform coating, co-culture liquid absorbance detection, and crystal violet staining experiments, demonstrating that the composite coating exhibited good antimicrobial properties. In conclusion, the composite scaffold possesses both osteointegration-promoting and antimicrobial properties, indicating a broad potential for clinical applications.

3D-ink-extruded titanium scaffolds with porous struts and bioactive supramolecular polymers for orthopedic implants

Porous titanium addresses the longstanding orthopedic challenges of aseptic loosening and stress shielding. This work expands on the evolution of porous Ti with the manufacturing of hierarchically porous, low stiffness, ductile Ti scaffolds via direct-ink write (DIW) extrusion and sintering of inks containing Ti and NaCl particles. Scaffold macrochannels were filled with a subtherapeutic dose of recombinant bone morphogenetic protein-2 (rhBMP-2) alone or co-delivered within a bioactive supramolecular polymer slurry (SPS) composed of peptide amphiphile nanofibrils and collagen, creating four treatment conditions (Ti struts: microporous vs. fully dense; BMP-2 alone or with SPS). The BMP-2-loaded scaffolds were implanted bilaterally across the L4 and L5 transverse processes in a rat posterolateral lumbar fusion model. In-vivo bone growth in these scaffolds is evaluated with synchrotron X-ray computed microtomography (µCT) to study the effects of strut microporosity and added biological signaling agents on the bone formation response. Optical and scanning electron microscopy confirms the ∼100 µm space-holder micropore size, high-curvature morphology, and pore fenestrations within the struts. Uniaxial compression testing shows that the microporous strut scaffolds have low stiffness and high ductility. A significant promotion in bone formation was observed for groups utilizing the SPS, while no significant differences were found for the scaffolds with the incorporation of micropores. Statement of significanceBy 2050, the anticipated number of people aged 60 years and older worldwide is anticipated to double to 2.1 billion. This rapid increase in the geriatric population will require a corresponding increase in orthopedic surgeries and more effective materials for longer indwelling times. Titanium alloys have been the gold standard of bone fusion and fixation, but their use has longstanding limitations in bone-implant stiffness mismatch and insufficient osseointegration. We utilize 3D-printing of titanium with NaCl space holders for large- and small-scale porosity and incorporate bioactive supramolecular polymers into the scaffolds to increase bone growth. This work finds no significant change in bone ingrowth via space-holder-induced microporosity but significant increases in bone ingrowth via the bioactive supramolecular polymers in a rat posterolateral fusion model.

Effect of viscosity of gelatin methacryloyl-based bioinks on bone cells

The viscosity of gelatin methacryloyl (GelMA)-based bioinks generates shear stresses throughout the printing process that can affect cell integrity, reduce cell viability, cause morphological changes, and alter cell functionality. This study systematically investigated the impact of the viscosity of GelMA-gelatin bioinks on osteoblast-like cells in 2D and 3D culture conditions. Three bioinks with low, medium, and high viscosity prepared by supplementing a 5% GelMA solution with different concentrations of gelatin were evaluated. Cell responses were studied in a 2D environment after printing and incubation in non-cross-linked bioinks that caused the gelatin and GelMA to dissolve and release cells for attachment to tissue culture plates. The increased viscosity of the bioinks significantly affected cell area and aspect ratio. Cells printed using the bioink with medium viscosity exhibited greater metabolic activity and proliferation rate than those printed using the high viscosity bioink and even the unprinted control cells. Additionally, cells printed using the bioink with high viscosity demonstrated notably elevated expression levels of alkaline phosphatase and bone morphogenetic protein-2 genes. In the 3D condition, the printed cell-laden hydrogels were photo-cross-linked prior to incubation. The medium viscosity bioink supported greater cell proliferation compared to the high viscosity bioink. However, there were no significant differences in the expression of osteogenic markers between the medium and high viscosity bioinks. Therefore, the choice between medium and high viscosity bioinks should be based on the desired outcomes and objectives of the bone tissue engineering application. Furthermore, the bioprinting procedure with the medium viscosity bioink was used as an automated technique for efficiently seeding cells onto 3D printed porous titanium scaffolds for bone tissue engineering purposes.

Novel Chemical Treatment of Porous Titanium Structures for Nanotextured Surface and Bioactive Behavior

Macroporous titanium structures are of interest in bone reconstruction because of their reduced modulus of elasticity (compared to bulk titanium), possibility of being colonized by cells, and biocompatibility. However, they are not bioactive and are not able to actively facilitate bone ingrowth or reduce bacterial adhesion. In the present research, work porous titanium scaffolds with different features (porosity 30–60 vol% and pore size 100–200 or 355–500 μm) are obtained by the space holder technique. Samples are characterized using optical microscopy, computed tomography, scanning electron microscopy (SEM), and X‐ray diffraction. Moreover, the theoretical elastic modulus and yield strength are calculated. A patented chemical treatment, able to produce a bioactive nanotextured oxide layer, has been optimized and successfully applied, for the first time, to structures with 50 vol% porosity and 100–200 μm pore size (as the most promising for bone substitution due to the biomechanical and biofunctional balance). Bare and modified samples are characterized using field emission SEM, zeta potential measurements, and in vitro bioactivity tests (soaking in simulated body solution) to evaluate the effectiveness of the surface chemical treatment.

Enhanced bioactivity and mechanical properties of silicon-infused titanium oxide coatings formed by micro-arc oxidation on selective laser melted Ti13Nb13Zr alloy

The titanium scaffolds and surface-porous implants are manufactured by fast and cheap additive methods such as selective laser melting (SLM). The obtained irregularity and relative biological inertness of the titanium need proper surface modification. This research is aimed at forming bioactive multicomponent oxide coatings by micro-arc oxidation (MAO) at different process parameters on the selective laser-melted Ti13Zr13Nb alloy. The MAO process was carried out in a base solution containing 0.15 mol/L Ca and 0.1 mol/L GP, with different amounts of metasilicate added under two different applied voltages. Scanning electron microscopy, atomic force microscopy, X-ray electron diffraction spectroscopy, nanomechanical and nano scratch tests, water contact angle measurements, phosphate deposition observed in long-term immersion tests, and biological LDH and MTT assays were performed. The results showed that the coating microstructure, morphology, and properties were significantly dependent on process parameters. In particular, the metasilicate addition and its rising content in the electrolyte resulted in the higher development of the surface followed by better viability of osteoblasts at no necrosis, with no negative change in the other parameters, usually close to those obtained on silicon-free coatings. The obtained results prove that the addition of silicon to the electrolyte at the partial expense of calcium can be favorable for long-term titanium implants made by selective laser melting.

3D-printed titanium scaffolds loaded with gelatin hydrogel containing strontium-doped silver nanoparticles promote osteoblast differentiation and antibacterial activity for bone tissue engineering.

Bone tissue engineering offers a promising alternative to stimulate the regeneration of damaged tissue, overcoming the limitations of conventional autografts and allografts. Recently, titanium alloy (Ti) implants have garnered significant attention for treating critical-sized bone defects, especially with the advancement of 3D printing technology. Although Ti alloys have impressive versatility, their lack of cellular adhesion, osteogenic and antibacterial properties are significant factors that contribute to their failure. Hence, to overcome these obstacles, this study aimed to incorporate osteoinductive and antibacterial cue-loaded hydrogels into 3D-printed Ti (3D-Ti) scaffolds. 3D-Ti scaffolds were synthesized using the direct metal laser sintering method and loaded with a gelatin (Gel) hydrogel containing strontium-doped silver nanoparticles (Sr-Ag NPs). Compared with Ag NPs, Sr-doped Ag NPs increased the expression of Runx2 mRNA, which is a key bone transcription factor. We subjected the bioactive 3D-hybrid scaffolds (3D-Ti/Gel/Sr-Ag NPs) to physicochemical and material characterization, followed by cytocompatibility and osteogenic evaluation. The microporous and macroporous topographies of the scaffolds with Sr-Ag NPs showed increased Runx2 expression and matrix mineralization, with potent antibacterial properties. Therefore, the 3D-Ti scaffolds incorporated with Sr-Ag NP-loaded Gel hydrogels favored osteoblast differentiation and antibacterial activity, indicating their potential for orthopedic applications.

Modeling Mechanical Properties of Titanium Scaffolds with Variable Microporosity

The article introduces a two‐level finite element model for metallic scaffolds with porosity at both design and material levels. Despite several additive manufacturing methods producing structures with controlled hierarchical porosity, their functional properties remain largely unknown, hindering industrial utilization. This article examines how material microporosity affects the mechanical properties of a scaffold prepared by direct ink writing from pure titanium with dimensions typical for orthopedic implants. The study focuses on the compressive response of scaffolds with microporosity ranging from 0.05 to 0.65. The article demonstrates the practical application of the model by estimating the effective Young's modulus and the relative length of the fatigue crack initiation stage. Tensile plastic strains at critical sites exhibit a delocalization from around micropores followed by relocalization into thinning interpore walls with increasing microporosity, resulting in the highest fracture strain predicted for microporosities between 0.2 and 0.3. These strains enable the estimation of the length of the fatigue crack initiation stage, which proves to be very short for all microporosities. This emphasizes the crucial role of the crack growth stage in scaffold fatigue life and confirms the potential for additional experiments on scaffolds with microporosities exceeding 0.15 to enhance their fatigue resistance.

Graded or random – Effect of pore distribution in 3D titanium scaffolds on corrosion performance and response of hMSCs

Researchers agree that the ideal scaffold for tissue engineering should possess a 3D and highly porous structure, biocompatibility to encourage cell/tissue growth, suitable surface chemistry for cell attachment and differentiation, and mechanical properties that match those of the surrounding tissues. However, there is no consensus on the optimal pore distribution. In this study, we investigated the effect of pore distribution on corrosion resistance and performance of human mesenchymal stem cells (hMSC) using titanium scaffolds fabricated by laser beam powder bed fusion (PBF-LB). We designed two scaffold architectures with the same porosities (i.e., 75 %) but different distribution of pores of three sizes (200, 500, and 700 μm). The pores were either grouped in three zones (graded, GRAD) or distributed randomly (random, RAND). Microfocus X-ray computed tomography revealed that the chemically polished scaffolds had the porosity of 69 ± 4 % (GRAD) and 71 ± 4 % (RAND), and that the GRAD architecture had the higher surface area (1580 ± 101 vs 991 ± 62 mm2) and the thinner struts (221 ± 37 vs 286 ± 14 μm). The electrochemical measurements demonstrated that the apparent corrosion rate of chemically polished GRAD scaffold decreased with the immersion time extension, while that for polished RAND was increased. The RAND architecture outperformed the GRAD one with respect to hMSC proliferation (over two times higher although the GRAD scaffolds had 85 % higher initial cell retention) and migration from a monolayer. Our findings demonstrate that the pore distribution affects the biological properties of the titanium scaffolds for bone tissue engineering.

Investigating mechanical properties of 3D printed porous titanium scaffolds for bone tissue engineering

Objective. Three-dimensional (3D) printed porous titanium scaffolds serve as a bone tissue engineering technology that offers a promising solution for addressing bone defects. The scaffold’s pore structure offers structural support and facilitates the proliferation of bone cells. Therefore, investigating the aperture and pore shape is of crucial for the development of 3D printed porous titanium scaffolds. Methods. Ti6Al4V scaffolds with the specified structure were fabricated using selective laser melting (SLM) technology. The scaffolds comprised fifteen cylindrical models measuring 20 mm in diameter and 20 mm in height. These models featured five scaffold shapes: imitation diamond-60°, imitation diamond-90°, imitation diamond-120°, regular tetrahedron and regular hexahedron. Each of these structural shapes was characterized by three different aperture sizes (400 μm, 600 μm and 800 μm). The porosity and mechanical properties of Ti6Al4V scaffolds were examined. Results. The measured porosity of Ti6Al4V scaffolds varied between 56.50% and 95.28%. The porosity increased with the size of the aperture. The mechanical properties tests revealed that, for identical apertures, the compressive strength and torsional strength were influenced by the configuration of the unit structure. Furthermore, the positive and lateral compressive strength as well as torsional strength of various unit structures exhibited distinct advantages and disadvantages. Within a uniform unit structure shape, the compressive strength and torsional strength were found to be correlated with the size of apertures, indicating that larger apertures result in decreased compressive and torsional strength. Conclusion. The configuration of the aperture and the shape of the pore were identified as significant factors that influenced the compressive strength. The compressive strength of Ti6Al4V scaffolds with various unit structure shapes exhibited both advantages and disadvantages when subjected to positive, lateral, and torsional forces. The enlarged aperture augmented the scaffold’s porosity while diminishing its compressive and torsional strength.

Customized 3D printed porous titanium scaffolds with nanotubes loading antibacterial drugs for bone tissue engineering

Abstract Due to the uncertainty of trauma or infection, customized bone substitutes are often required in clinic. Meanwhile, excessive use of antibiotics may lead to drug resistance. Therefore, the design of anti-infection bone tissue engineering scaffold is of very important. In this study, porous titanium alloy bone tissue engineering scaffolds were designed and fabricated by 3D printing. TiO2 nanotubes were further constructed on the scaffolds through electrochemical anodic oxidation, achieving the drug loading and anti-infection functions. The micron-level bionic pores were fabricated by the 3D printing process, and the secondary nanoscale-level nanotubes were achieved through the anodic oxidation process. Thereafter, the micro–nano structured porous bone tissue engineering scaffolds are presented. This structure features that the drug release rate can be regulated by loading the anti-infection drug minocycline and coating them with poly(lactic-co-glycolic acid) (PLGA) in the nanotubes. According to the results, the micro–nano composite porous scaffold showed uniform and controllable micro–nano pores, it may load anti-infection drugs and shown anti-infection ability. In addition, the PLGA coating may delay the drug release and maintain a sustained anti-infection function for the scaffold in a week. This study provides new ideas for designing antibacterial bone tissue engineering scaffold.

Customized 3D‐printed heterogeneous porous titanium scaffolds for bone tissue engineering

AbstractBone defect is a common clinical disease. Due to the uncertainty of trauma or infection areas, customized size features are often required for bone substitutes. By inspiration of the natural bone structure, this study designs porous scaffolds with a biomimetic design perspective by using different inner and outer pore units. The outer pore units adopt body‐centered cubic (BCC) structure to simulate the weight‐bearing function of human cortical bone, while inner pore units using I‐Wrapped Package structure, a kind of three periods minimum surface, to obtain a good permeability and simulates the inner layer of cancellous bone. To further regulate the overall modulus of the scaffold within the range of natural bone modulus in the human body, the scaffold was designed to axial gradient structure. Compression experiments were conducted, and the results indicated that when the volume fraction linearly increased from 20% to 50%, the Young's modulus was close to the cortical bone modulus in the human body. In vitro cell experiments further proved that osteoblasts have good cellular activity and spreading morphology on the surface of this scaffold. The customized 3D‐printed heterogeneous porous titanium scaffold has great application potential in bone tissue engineering.

Highly biologically functional magnesium silicate-coated 3D printed round pore-shaped titanium scaffold alters exosomal miRNA expression to promote osteogenic differentiation for bone defect repair

Bone defects are a serious condition that has a significant impact on the function and quality of life of the patient. In severe bone defects, restoring the structure and function of bone tissue is a complex task, and titanium (Ti) implants designed with superior performance can be an alternative. In this study, in order to develop a Ti implant that effectively promotes osseointegration and new bone ingrowth, 3D printing-based magnesium silicate (MgSiO3)-coated round pore-shaped Ti scaffold (S-R/MgSi) was fabricated by standardizing pore size and porosity and designing different pore shapes and selecting the optimal pore shape (round) as well as subsequent hydrothermal synthesis to finally form MgSiO3 coating. The experimental results of Ti scaffolds with different pore shapes showed that S-R is optimal for promoting osteogenic differentiation. After S-R was coated with MgSiO3, S-R/MgSi enhanced the adhesion, proliferation, migration, and osteogenic differentiation of bone marrow mesenchymal stem cells (BMSCs), as well as regulated angiogenesis. In vivo studies, S-R/MgSi significantly promoted new bone ingrowth and was effective in repairing bone defects. Following the mechanism exploration, it was found that exosomes secreted by BMSCs co-cultured with S-R/MgSi (Exo_S-R/MgSi) were more able to promote the osteogenic differentiation of BMSCs. In conclusion, this study not only successfully prepared a new type of Ti implant with superior ability to promote new bone ingrowth, but also provided a new explanation for the mechanism of scaffold surface chemistry affecting osteogenesis from the viewpoint of scaffold surface coating affecting the amount and function of cellular exosome secretion.

Indications for Nonbiological Reconstruction of Posttraumatic Bone Defects About the Knee.

3D printing and modeling has continued to grow in popularity over the past decade because the technology has matured and become more affordable and widely available. The main indications for nonbiological reconstruction of large bone defects are principally those patients where the candidate is unlikely to be successful if reconstructed by other means. Bespoke, custom, patient-specific implants can be designed to very effectively address bone loss, incorporating design elements that are particular to the needs of any given unique clinical condition. These implants are generally designed as titanium scaffolds that encourage bony incorporation at the host implant junction both proximal and distal. These scaffolds are typically considered a cellular solid, with high porosity that also promotes bone ingrowth directly into the substance of the body of the implant. Titanium scaffolds of this type have become a useful treatment alternative for large segmental bone defects around the knee, especially distal femoral defects. These are often adult patients with local or systemic compromise, or instead they may be too young to be considered candidates for reconstruction using a megaprosthesis. The process requires careful evaluation of individual patients, then matching that patient with the best treatment option, while recognizing the expectations and demands specific to that particular patient. Several cases are presented here to illustrate the variety of indications that can be successfully addressed with this technology, highlighting the quality of the clinical outcome that can be achieved despite the complexity of the pathology encountered.

Chemical etching of Ti-6Al-4V biomaterials fabricated by selective laser melting enhances mesenchymal stromal cell mineralization.

Porous titanium scaffolds fabricated by powder bed fusion additive manufacturing techniques have been widely adopted for orthopedic and bone tissue engineering applications. Despite the many advantages of this approach, topological defects inherited from the fabrication process are well understood to negatively affect mechanical properties and pose a high risk if dislodged after implantation. Consequently, there is a need for further post-process surface cleaning. Traditional techniques such as grinding or polishing are not suited to lattice structures, due to lack of a line of sight to internal features. Chemical etching is a promising alternative; however, it remains unclear if changes to surface properties associated with such protocols will influence how cells respond to the material surface. In this study, we explored the response of bone marrow derived mesenchymal stem/stromal cells (MSCs) to Ti-6Al-4V whose surface was exposed to different durations of chemical etching. Cell morphology was influenced by local topological features inherited from the SLM fabrication process. On the as-built surface, topological nonhomogeneities such as partially adhered powder drove a stretched anisotropic cellular morphology, with large areas of the cell suspended across the nonhomogeneous powder interface. As the etching process was continued, surface defects were gradually removed, and cell morphology appeared more isotropic and was suggestive of MSC differentiation along an osteoblastic-lineage. This was accompanied by more extensive mineralization, indicative of progression along an osteogenic pathway. These findings point to the benefit of post-process chemical etching of additively manufactured Ti-6Al-4V biomaterials targeting orthopedic applications.

Anodic Oxidation of 3D Printed Ti6Al4V Scaffold Surfaces: In Vitro Studies

This study focuses on the surface modification of Ti6Al4V scaffolds produced through additive manufacturing using the Powder-Bed Fusion Electron-Beam Melting (PBF-EB) technique. From our perspective, this technique has the potential to enhance implant osseointegration, involving the growth of a layer of titanium dioxide nanotubes (TiO2) on surfaces through anodic oxidation. Scaffolds with anodized surfaces were characterized, and the formation of a nanoporous and crystalline TiO2 layer was confirmed. The analysis of cell morphology revealed that cells adhered to the anodized surfaces through their filopodia, which led to proliferation during the initial hours. However, it was observed that the adhesion of Saos-2 cells was lower on anodized scaffolds compared to both built and chemically polished scaffolds throughout the cell culture period. The results obtained here suggest that while anodic oxidation is effective in achieving a nanoporous surface, cell adhesion and interaction were affected by the weak adhesion of cell filopodia to the surface. Thus, combining surface treatment techniques to create micro- and nanopores may be an effective alternative for achieving a favorable cellular response when the objective is to enhance the performance of porous titanium scaffolds in the short term.

Human dental pulp stem cell-derived exosomes decorated titanium scaffolds for promoting bone regeneration

Exosomes, nanoscale extracellular vesicles crucial for intercellular communication, hold great promise as a therapeutic avenue in cell-free tissue regeneration. In this study, we identified and utilized exosomes to adorn anodized titanium scaffolds, inducing osteogenic differentiation in human dental pulp stem cells (hDPSCs). The osteogenesis of hDPSCs was stimulated by exosomes derived from hDPSCs that underwent various periods of osteogenic differentiation. After purification, these exosomes were loaded onto anodized titanium scaffolds. Notably, the scaffolds loaded with exosomes deriving from osteogenic differentiated hDPSCs demonstrated superior bone tissue regeneration compared to those loaded with exosomes deriving from hDPSCs within 10-week. RNA-sequencing analysis shed light on the underlying mechanism, revealing that the osteogenic exosomes carried specific cargo, which is due to upregulated miRNAs (Hsa-miR-29c-5p, Hsa-miR-378a-5p, Hsa-miR-10b-5p and Hsa-miR-9–3p) associated with osteogenesis. And down-regulated anti-osteogenic miRNA (Hsa-miR-31–3p, Hsa-miR-221–3p, Hsa-miR-183–5p and Hsa-miR-503–5p). In conclusion, the identification and utilization of exosomes derived from osteogenic differentiated stem cells offer a novel and promising strategy for achieving cell-free bone regeneration.

Fatigue performance of hierarchically porous titanium scaffolds produced by additive manufacturing and its possible improvement by gas nitriding

This contribution focuses on the nitriding of hierarchically porous titanium scaffolds to enhance their fatigue behaviour. Firstly, recent experimental findings that demonstrate the benefits of intra-filament porosity in improving fatigue resistance are discussed, providing details on crack growth shielding micromechanisms. Subsequently, the study explores the application of titanium scaffolds nitriding as a promising technique to prolong fatigue crack initiation. The scaffolds, prepared using the direct ink writing method with intra-filament porosity of ~ 6% and inter-filament porosity of ~ 68%, underwent gas nitriding at 1100 °C for 2 h. This process resulted in the formation of a consistent 42 μm thick nitriding case across the entire structure. Preliminary experiments showed a minimal decrease in fatigue strength within the low cycle fatigue region, attributed to the fracturing of a thick brittle compound zone under high applied loading. These results suggest that nitriding has the potential to improve fatigue performance after process optimization.

Microporous Ag/AgCl on a Titanium Scaffold for Use in Capillary Reference Electrodes.

AgCl-coated silver fabricated with the thermal-electrolytic method can be used to prepare more reproducible reference electrodes than Ag/AgCl prepared with alternative methods such as electrolytic and chemical AgCl deposition or thermal fabrication. However, thermal-electrolytic fabrication requires a scaffold material upon which to build the layers upon. Platinum and rhodium have been used for this purpose as they are mechanically strong and chemically inert, but their cost is prohibitive for wider application. Herein, we report the stability of Ag/AgCl reference electrodes built atop a titanium scaffold using the thermal-electrolytic method and the use of these Ti/Ag/AgCl constructs in capillary-based reference electrodes. Electrochemical characterization shows that the probable presence of small amounts of oxygen at the Ti/Ag interface does not affect the reference electrode performance; in particular, over a wide pH range, the half-cell potential is pH independent. The electrical resistance of the Ti/Ag/AgCl/KCl system is dominated by the charge transfer resistance at the interface of the AgCl to KCl solution but is kept very small by the large AgCl surface area and a high solution concentration of chloride. The resulting high exchange current minimizes the effect of system impurities on the reference half-cell potential. Capillary-based reference electrodes comprising Ti/Ag/AgCl show exceptionally low potential drifts (as low as 0.03 ± 2.01 μV/h) and standard deviations of the potential at or below ±0.5 mV over a 60 h period. These capillary-based reference electrodes are suitable for very small sample volumes while still providing a free-flowing liquid junction that prevents reference electrode contamination.