Silver-Doped Titanium Oxide Layers for Improved Photocatalytic Activity and Antibacterial Properties of Titanium Implants.

Titanium has a long history of clinical use, but the naturally forming oxide is not ideal for bacterial resistance. Anodization processes can modify the crystallinity, surface topography, and surface chemistry of titanium oxides. Anatase, rutile, and mixed phase oxides are known to exhibit photocatalytic activity (PCA)-driven bacterial resistance under UVA irradiation. Silver additions are reported to enhance PCA and reduce bacterial attachment. This study investigated the effects of silver-doping additions to three established anodization processes. Silver doping showed no significant influence on oxide crystallinity, surface topography, or surface wettability. Oxides from a sulfuric acid anodization process exhibited significantly enhanced PCA after silver doping, but silver-doped oxides produced from phosphoric-acid-containing electrolytes did not. Staphylococcus aureus attachment was also assessed under dark and UVA-irradiated conditions on each oxide. Each oxide exhibited a photocatalytic antimicrobial effect as indicated by significantly decreased bacterial attachment under UVA irradiation compared to dark conditions. However, only the phosphorus-doped mixed anatase and rutile phase oxide exhibited an additional significant reduction in bacteria attachment under UVA irradiation as a result of silver doping. The antimicrobial success of this oxide was attributed to the combination of the mixed phase oxide and higher silver-doping uptake levels.

Antibacterial and biocompatible polyaniline-doped titanium oxide layers.

Titanium anodization has been shown to produce crystalline oxides exhibiting photocatalytic reactions that form reactive oxygen species (ROS) when exposed to UV light. The ROS subsequently attack bacteria cells, and thus reduce bacteria attachment on titanium implant surfaces. Polyaniline (PANI) is a conductive polymer that has shown antibacterial properties when electropolymerized onto titanium. Our research group hypothesized the addition of PANI to crystalline titanium oxide surfaces would increase the available free electrons and thus increase photocatalytic activity (PCA). This research led to the development of a novel single-step anodization approach for PANI doping crystalline titanium oxide layers. The objective of the present study was to determine the proper aniline electrolyte concentration needed to maximize the PCA and reduce bacterial attachment on the formed oxides. Aniline concentrations up to 1 M were added into a 1 M sulfuric acid electrolyte. The formed oxides exhibited increased PANI surface coverage but decreased anatase and rutile crystalline titanium oxide phase formation with increasing aniline electrolyte concentrations. Despite exhibiting the lowest levels of anatase and rutile formation, the 0.75 M and 1 M aniline oxides with the greatest PANI surface coverage also exhibited the highest PCA levels. 1 M aniline oxides showed significantly higher PCA under UVA irradiation compared to oxides formed from aniline concentrations up to 0.5 M (p < 0.001). 0.75 M aniline oxides exhibited significant reductions in Staphylococcus aureus attachment with or without UVA irradiation compared to control oxides without PANI. MTT and live/dead assays confirmed cytocompatibility and nearly 100% cell viability for the PANI doped oxides.

A novel single-step anodization approach for PANI-doping oxide surfaces to improve the photocatalytic activity of titanium implants.

Crystalline titanium oxides have shown photocatalytic activity (PCA) and the formation of antibacterial reactive oxygen species (ROS) when stimulated with UV light. Polyaniline (PANI) is a conductive polymer that has shown antibacterial effects. Previously, titanium oxides have been PANI-doped using a multi-step approach. In the present study, we compared PANI-doped specimens produced with a two-step method (ACV), to PANI-doped specimens produced by a novel single-step direct anodization (AAn) method, and a control group of anodized un-doped specimens. The surface morphology, oxide crystallinity, surface elemental composition, surface roughness, surface wettability, oxide adhesion, corrosion resistance, PCA, and ROS generation of each oxide group were evaluated. All groups exhibited mixed anatase and rutile phase oxides. The AAn group revealed less anatase and rutile, but more PANI-surface coverage. The AAn group exhibited significantly increased PCA after 60 minutes of direct UVA illumination compared to the ACV group, despite containing lower amounts of anatase and rutile. The ACV and AAn groups showed significant increases in ROS production after 4 hours UVA illumination while the control group showed similar ROS production. These findings suggested that PANI doping using the novel direct anodization technique significantly improved PCA even for oxides containing less crystallinity. The S. aureus attachment response to each oxide group was also compared under UVA pre-illumination, UVA direct illumination, and no illumination (dark) lighting conditions. Although no significant differences were shown in the bacterial response, both PANI-doped groups exhibited less average bacterial attachment compared to the control group. The response of MC3T3-E1 pre-osteoblast cells to each oxide group was evaluated using MTT and live/dead assays, and no evidence of cytotoxicity was found. Since many, if not most, titanium implant devices are routinely anodized as a part of the manufacturing processes, these study findings are applicable to a wide variety of implant applications.

Photofunctionalization of anodized titanium surfaces using UVA or UVC light and its effects against Streptococcus sanguinis.

UV light preirradiation of anodized titanium oxide layers has recently been shown to produce a photocatalytic effect that may reduce early bacterial attachment on titanium surfaces. Streptococcus species have been identified as primary early colonizers and contribute to early biofilm formation on dental implant surfaces. Anodized layers with primarily amorphous, primarily anatase, primarily rutile, and mixtures of anatase and rutile phase oxides were preirradiated with UVA or UVC light for 10 min. Nanoscale surface roughness and pre- and post-UV-irradiated wettability were measured for each anodization group. Sample groups were subjected to streptococcus sanguinis for a period of 24 h. Bacterial attachment and killing efficacy were measured and compared to the corresponding non-UV control groups. UVA treatments showed trends of at least a 20% reduction in bacterial attachment regardless of the crystallinity, or combination of oxide phases present. Anodized layers consisting of primarily anatase phase on the outermost surface were shown to have a killing efficacy of at least 50% after preirradiation with UVA light. Anodized layers containing disperse mixtures of anatase and rutile phases at the outermost surface showed at least a 50% killing efficacy after pre-irradiation with either UVA or UVC light. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 2284-2294, 2018.

Alpha plus beta annealed and aged Ti-15 Mo alloy for high strength implant applications.

Management of femur fractures requires titanium alloy implants that provide a good combination of static strength and ductility plus sufficient high cycle fatigue strength to resist repetitive loading. A research program was initiated to determine whether aging treatments could increase the strength of alpha + beta Ti-15Mo while maintaining acceptable tensile ductility. A pilot heat treating study indicated the best combination of strength and ductility was obtained using an α + ß annealing temperature of 705°C ± 10°C followed by an aging treatment of 482°C ± 10°C. EBSD data for four suppliers revealed that the alpha phase ratios ranged from 16.3% to 18.6% and the beta phase ratios ranged from 81.4% to 83.7%. Mean beta grain size diameters ranged between 1.42 and 1.78 µm. Tensile testing qualification data from four suppliers was statistically analyzed and reviewed. Minimum reproducible tensile values were established and incorporated into ASTM F2066-13 implant material standard. Cantilever fatigue testing was performed with proximal femoral nail implants that were fabricated into fully finished implant constructs. Fatigue results for 125°, 130°, and 135° implant constructs met the acceptance criteria regarding the fatigue runout load limits and failure modes that were identified. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 2010-2018, 2017.

Failure of Emperion modular femoral stem with implant analysis.

Modularity in total hip arthroplasty provides multiple benefits to the surgeon in restoring the appropriate alignment and position to a previously damaged hip joint. The vast majority of modern implants incorporate modularity into their design with some implants having multiple modular interfaces. There is the potential for failure at modular junctions because of fretting and crevice corrosion in combination with mechanical loading. This case report details the failure of an Emperion (Smith and Nephew, Memphis, TN) femoral stem in a 67-year-old male patient 6 years after total hip replacement. Analysis of the implant revealed mechanically assisted crevice corrosion that likely accelerated fatigue crack initiation in the hip stem. The benefits of modularity come with the potential drawback of a combination of fretting and crevice corrosion at the modular junction, which may accelerate fatigue, crack initiation and ultimately reduce the hip longevity.

A comparison of the stress corrosion cracking susceptibility of commercially pure titanium grade 4 in Ringer's solution and in distilled water: a fracture mechanics approach.

From the results of laboratory investigations reported in the literature, it has been suggested that stress corrosion cracking (SCC) mechanisms may contribute to early failures in titanium alloys that have elevated oxygen concentrations. However, the susceptibility of titanium alloys to SCC in physiological environments remains unclear. In this study, a fracture mechanics approach was used to examine the SCC susceptibility of CP titanium grade 4 in Ringer's solution and distilled de-ionized (DI) water, at 37°C. The study duration was 26 weeks, simulating the non-union declaration of a plated fracture. Four wedge loads were used corresponding to 86-95% of the alloy's ligament yield load. The longest cracks were measured to be 0.18 mm and 0.10 mm in Ringer's solution and DI water, respectively. SEM analysis revealed no evidence of extensive fluting and quasi-cleavage fracture features which, in literature reports, were attributed to SCC. We thus postulate that the Ringer's solution accelerated the wedge-loaded crack growth without producing the critical stresses needed to change the fracture mechanism. Regression analysis of the crack length results led to a significant best-fit relationship between crack growth velocity (independent variable) and test electrolyte, initial wedge load, and time of immersion of specimen in electrolyte (dependent variables).