Scanning Electron Microscopy and Energy-Dispersive X-Ray Spectroscopy as a Valuable Tool to Investigate the Ultra-High-Molecular-Weight Polyethylene Wear Mechanisms and Debris in Hip Implants.

BACKGROUND: The use of scanning electron microscopy (SEM) and energy-dispersive spectrometry (EDS) was investigated to understand the wear mechanisms from a metal-on-polyethylene bearing couple. Morphological features of femoral head acetabular liner, and isolated particles resulting from hip wear testing were evaluated. EDS was proposed to investigate the polymeric nature of the particles isolated from the wear testing. METHODS: In this work, 28-mm conventional ultra-high-molecular-weight polyethylene acetabular liners paired with metallic heads were tested in a hip wear simulator over 2 million cycles. SEM-EDS was employed to investigate wear mechanisms on hip implant components and associated wear debris. RESULTS: SEM showed worn surfaces for both hip components, and a significant volume of ultra-high-molecular-weight polyethylene wear particles resulting from hip wear testing. Particles were classified into 3 groups, which were then correlated to wear mechanisms. Group I had particles with smooth surfaces, group II consisted of particles with rough surfaces, and group III comprised aggregate-like particles. Group I EDS revealed that particles from groups I and II had a high C/O ratio raising a concern about the particle source. On the other hand, particles from group III had a low C/O ratio, supporting the hypothesis that they resulted from the wear of acetabular liner. Most of particles identified in group III were in the biologically active size range (0.3 to 20 µm). CONCLUSION: The use of optical and electron microscopy enabled the morphological characterization of worn surfaces and wear debris, while EDS was essential to elucidate the chemical composition of isolated debris.

Effects of decontamination solutions on the surface of titanium: investigation of surface morphology, composition, and roughness.

AIM: To investigate the impact of treatments used to detoxify dental implants on the oxide layer morphology and to infer how changes in morphology created by these treatments may impact re-osseointegration of an implant. MATERIALS AND METHODS: Pure titanium (cpTi) and the alloy Ti6Al4V were subjected to a series of chemical treatments and mechanical abrasion simulating surface decontamination of dental implants. The morphology and roughness of the surface layer before and after treatment with these solutions were investigated with optical and atomic force microscopy (OM, AFM). The solutions employed are typically used for detoxification of dental implants. These included citric acid, 15% hydrogen peroxide, chlorhexidine gluconate, tetracycline, doxycycline, sodium fluoride, peroxyacetic acid, and treatment with carbon dioxide laser. The treatments consisted of both immersions of samples in solution and rubbing with cotton swabs soaked in solution for 1, 2, and 5 min. Cotton swabs used were analyzed with energy dispersive spectroscopy (EDS). RESULTS: The microscopy investigation showed that corrosion and pitting of the samples were present in both metal grades with immersion and rubbing methods when employing more acidic solutions, which had pH <3. Mildly acidic solutions caused surface discoloration when coupled with rubbing but did not cause corrosion with immersion. Neutral or basic treatments resulted in no signs of corrosion with both methods. EDS results revealed the presence of titanium particles on all rubbing samples. CONCLUSION: It was demonstrated in this study that acidic environments coupled with rubbing are able to introduce noticeable morphological changes and corrosion on the surface of both titanium grades.

Dicationic Imidazolium-Based Ionic Liquid Coatings on Zirconia Surfaces: Physico-Chemical and Biological Characterization.

In the present work, dicationic imidazolium-based ionic liquids (ILs) were investigated as multi-functional coatings on a zirconia (ZrO2) surface to prevent biofilm formation and enhance the wear performance of zirconia while maintaining the material's compatibility with host cells. ILs containing phenylalanine and methionine were synthesized and deposited on zirconia. Intermolecular interactions driving IL deposition on zirconia were studied using X-ray photoelectron spectroscopy (XPS). Anti-biofilm activity and cell compatibility were evaluated in vitro after one and seven days, and wear performance was tested using a pin-on-disk apparatus. ILs were observed to form strong hydrogen bonds with zirconia. IL containing phenylalanine formed a stable film on the surface after one and seven days in phosphate-buffered saline (PBS) and artificial saliva and showed excellent anti-biofilm properties against Streptococcussalivarius and Streptococcussanguinis. Compatibility with gingival fibroblasts and pre-osteoblasts was maintained, and conditions for growth and differentiation were preserved. A significantly lower coefficient of friction and wear volume loss were observed for IL-coated surfaces as compared to non-coated substrates. Overall, zirconia is an emerging alternative to titanium in dental implants systems, and this study provides additional evidence of the materials' behavior and IL coatings as a potential surface treatment technology for improvement of its properties.

In Vitro and In Vivo Characterization of Premixed PMMA-CaP Composite Bone Cements.

Acrylic bone cements, although successful in the field of orthopedics, suffer from a lack of bioactivity, not truly integrating with surrounding bone. Bioactive fixation is expected to enhance cement performance because of the natural interlocking and bonding with bone, which can improve the augmentative potential of the material in applications such as vertebroplasty (VP). In a recent study, two composite cements (PMMA-hydroxyapatite and PMMA-brushite) showed promising results demonstrating no deterioration in rheological and mechanical properties after CaP filler addition. In this study, the dynamic properties of the cements were investigated in vitro and in vivo. The hypothesis was that these composite cements will provide osseointegration around the implanted cement and increase new bone formation, thus decreasing the risk of bone structural failure. The effects of CaP elution were thus analyzed in vitro using these cements. Mass-loss, pore formation, and mechanical changes were tracked after cement immersion in Hank's salt solution. PMMA-brushite was the only cement with a significant mass loss; however it showed low bulk porosity. Surface porosity increases were observed in both composite cements. Mechanical properties were maintained after cement immersion. In vitro culture studies tested preosteoblast cell viability and differentiation on the cement surface. Cell viability was demonstrated with MTT assay and confirmed on the cement surface. ALP assays showed no inhibition of osteoblast differentiation on the cement surface. In vivo experiments were performed using a rat tibiae model to demonstrate bone ingrowth around the implanted cements. Critical size defects were created and then filled with the cements. The animal studies showed no loss in mechanical strength after implantation and increased bone ingrowth around the composite cements. In summary, the composite cements provided bioactivity without sacrificing mechanical strength.

Ionic Liquid Coatings for Titanium Surfaces: Effect of IL Structure on Coating Profile.

Dicationic imidazolium-based ionic liquids (ILs) having bis(trifluoromethylsulfonyl)imide (NTf2) and amino acid-based (methionine and phenylalanine) anionic moieties were synthesized and used to coat titanium surfaces using a dip-coating technique. Dicationic moieties with varying alkyl chains (8 and 10 carbons) and anions with distinct characteristics were selected to understand the influence of IL structural features on deposition profile. X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) were used in this study to help elucidate intermolecular interactions within ILs as well as between ILs and TiO2 surfaces and to investigate IL coating morphology. Charge concentration on IL moieties, as well as the presence of functional groups that can interact via hydrogen bond, such as carboxylate and amino groups, were observed to influence the deposition profile. ILs containing amino acids as the anionic moiety were observed to interact strongly with TiO2, which resulted in more pronounced changes in Ti 2p binding energy. The higher hydrophobicity of the IL having NTf2 as the anionic moiety resulted in higher adhesion strength between the IL coating and TiO2.

In Vitro Investigation of the Effect of Oral Bacteria in the Surface Oxidation of Dental Implants.

BACKGROUND: Bacteria are major contributors to the rising number of dental implant failures. Inflammation secondary to bacterial colonization and bacterial biofilm is a major etiological factor associated with early and late implant failure (peri-implantitis). Even though there is a strong association between bacteria and bacterial biofilm and failure of dental implants, their effect on the surface of implants is yet not clear. PURPOSE: To develop and establish an in vitro testing methodology to investigate the effect of early planktonic bacterial colonization on the surface of dental implants for a period of 60 days. MATERIALS AND METHODS: Commercial dental implants were immersed in bacterial (Streptococcus mutans in brain-heart infusion broth) and control (broth only) media. Immersion testing was performed for a period of 60 days. During testing, optical density and pH of immersion media were monitored. The implant surface was surveyed with different microscopy techniques post-immersion. Metal ion release in solution was detected with an electrochemical impedance spectroscopy sensor platform called metal ion electrochemical biosensor (MIEB). RESULTS: Bacteria grew in the implant-containing medium and provided a sustained acidic environment. Implants immersed in bacterial culture displayed various corrosion features, including surface discoloration, deformation of rough and smooth interfaces, pitting attack, and severe surface rusting. The surface features were confirmed by microscopic techniques, and metal particle generation was detected by the MIEB. CONCLUSION: Implant surface oxidation occurred in bacteria-containing medium even at early stages of immersion (2 days). The incremental corrosion resulted in dissolution of metal ions and debris into the testing solution. Dissolution of metal ions and particles in the oral environment can trigger or contribute to the development of peri-implantitis at later stages.

Preparation and Characterization of Injectable Brushite Filled-Poly (Methyl Methacrylate) Bone Cement.

Powder-liquid poly (methyl methacrylate) (PMMA) bone cements are widely utilized for augmentation of bone fractures and fixation of orthopedic implants. These cements typically have an abundance of beneficial qualities, however their lack of bioactivity allows for continued development. To enhance osseointegration and bioactivity, calcium phosphate cements prepared with hydroxyapatite, brushite or tricalcium phosphates have been introduced with rather unsuccessful results due to increased cement viscosity, poor handling and reduced mechanical performance. This has limited the use of such cements in applications requiring delivery through small cannulas and in load bearing. The goal of this study is to design an alternative cement system that can better accommodate calcium-phosphate additives while preserving cement rheological properties and performance. In the present work, a number of brushite-filled two-solution bone cements were prepared and characterized by studying their complex viscosity-versus-test frequency, extrusion stress, clumping tendency during injection through a syringe, extent of fill of a machined void in cortical bone analog specimens, and compressive strength. The addition of brushite into the two-solution cement formulations investigated did not affect the pseudoplastic behavior and handling properties of the materials as demonstrated by rheological experiments. Extrusion stress was observed to vary with brushite concentration with values lower or in the range of control PMMA-based cements. The materials were observed to completely fill pre-formed voids in bone analog specimens. Cement compressive strength was observed to decrease with increasing concentration of fillers; however, the materials exhibited high enough strength for consideration in load bearing applications. The results indicated that partially substituting the PMMA phase of the two-solution cement with brushite at a 40% by mass concentration provided the best combination of the properties investigated. This alternative material may find applications in systems requiring highly injectable and viscous cements such as in the treatment of spinal fractures and bone defects.

Preparation of TiO2 nanoparticles coated with ionic liquids: a supramolecular approach.

Coated TiO2 nanoparticles by dicationic imidazolium-based ionic liquids (ILs) were prepared and studied by differential scanning calorimetry (DSC), dynamic light scattering (DLS), transmission electron microscopy (TEM), powder X-ray diffraction (XRD), and scanning electron microscopy (SEM). Three ILs with different hydrophobicity degrees and structural characteristics were used (IL-1, IL-2, and IL-3). The interaction between IL molecules and the TiO2 surface was analyzed in both solid state and in solution. The physical and chemical properties of coated nanoparticles (TiO2 + IL-1, TiO2 + IL-2, and TiO2 + IL-3) were compared to pure materials (TiO2, IL-1, IL-2, and IL-3) in order to evaluate the interaction between both components. Thermal behavior, diffraction pattern, and morphologic characteristics were evaluated in the solid state. It was observed that all mixtures (TiO2 + IL) showed different behavior from that detected for pure substances, which is an evidence of film formation. DLS experiments were conducted to determine film thickness on the TiO2 surface comparing the size (hydrodynamic radius, Rh) of pure TiO2 with coated nanoparticles (TiO2 + IL). Results showed the thickness of the film increased with hydrophobicity of the IL compound. TEM images support this observation. Finally, X-ray diffraction patterns showed that, in coated samples, no structural changes in TiO2 diffraction peaks were observed, which is related to the maintenance of the crystalline structure. On the contrary, ILs showed different diffraction patterns, which confirms the hypothesis of interactions happening between IL and the TiO2 nanoparticles surface.