In Vitro versus In Vivo Phase Instability of Zirconia-Toughened Alumina Femoral Heads: A Critical Comparative Assessment

A clear discrepancy between predicted in vitro and actual in vivo surface phase stability of BIOLOX (R) delta zirconia-toughened alumina (ZTA) femoral heads has been demonstrated by several independent research groups. Data from retrievals challenge the validity of the standard method currently utilized in evaluating surface stability and raise a series of important questions: (1) Why do in vitro hydrothermal aging treatments conspicuously fail to model actual results from the in vivo environment? (2) What is the preponderant microscopic phenomenon triggering the accelerated transformation in vivo? (3) Ultimately, what revisions of the current in vitro standard are needed in order to obtain consistent predictions of ZTA transformation kinetics in vivo? Reported in this paper is a new in toto method for visualizing the surface stability of femoral heads. It is based on CAD-assisted Raman spectroscopy to quantitatively assess the phase transformation observed in ZTA retrievals. Using a series of independent analytical probes, an evaluation of the microscopic mechanisms responsible for the polymorphic transformation is also provided. An outline is given of the possible ways in which the current hydrothermal simulation standard for artificial joints can be improved in an attempt to reduce the gap between in vitro simulation and reality

Multi-spectroscopic analysis of high temperature oxides formed on cobalt-chrome-molybdenum alloys

Thanks to their thermal stability, resistance to oxidation and mechanical strength, cobalt -chrome molybdenum alloys are considered an ideal alloy for high temperature applications. The surface oxide layer evolves as a function of time and temperature, changing its chemical structure and increasing its thickness from a few nanometers to various microns. Making use of various diffractographic and spectroscopic techniques, namely X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy and glow-discharge optical emission spectroscopy, coupled with complementary analysis, this work gives new insights on the chemical bonding, crystallographic structure, thickness and elemental composition of the oxide layers as a function of both time and temperature of oxidation. Results show that the initial nanometric passive layer of Co3O4 evolves into a metastable, sub-micrometric CoCrO4 structure and finally stabilizes into a micrometric Cr2O3 at the highest temperatures. This paper fills a fundamental gap in the understanding of the chemistry and stability of Cobalt-based alloys used for high temperature applications, such as in poppet or exhaust valves, aerospace components or hot gas turbines. Once calibrated, this innovative, complete surface characterization approach can be ideally extended to other metallic alloys. (C) 2022 The Author(s). Published by Elsevier B.V

Bioactive silicon nitride: A new therapeutic material for osteoarthropathy

While the reciprocity between bioceramics and living cells is complex, it is principally governed by the implant's surface chemistry. Consequently, a deeper understanding of the chemical interactions of bioceramics with living tissue could ultimately lead to new therapeutic strategies. However, the physical and chemical principles that govern these interactions remain unclear. The intricacies of this biological synergy are explored within this paper by examining the peculiar surface chemistry of a relatively new bioceramic, silicon nitride (Si3N4). Building upon prior research, this paper aims at obtaining new insights into the biological interactions between Si3N4 and living cells, as a consequence of the off-stoichiometric chemical nature of its surface at the nanometer scale. We show here yet unveiled details of surface chemistry and, based on these new data, formulate a model on how, ultimately, Si3N4 influences cellular signal transduction functions and differentiation mechanisms. In other words, we interpret its reciprocity with living cells in chemical terms. These new findings suggest that Si3N4 might provide unique new medicinal therapies and effective remedies for various bone or joint maladies and diseases

Wear and surface degradation of commercial ZTA femoral heads under boundary lubrication conditions

The effect of frictional sliding on the surface degradation of commercially available zirconia-toughened alumina (ZTA) femoral heads was studied using a pin-on-ball wear tester under three different lubricating conditions: dry, water, and squalene. Water and squalene were employed under boundary lubrication regimes. Despite the unique (non-standard) character of this apparatus, standard loading conditions could be applied, which effectively determined dynamic friction coefficients as basic material properties. Two types of surface degradation were observed: (i) the polymorphic tetragonal-to-monoclinic (t -> m) transformation of the zirconia (ZrO2) dispersoids; and (ii) the off-stoichiometry drift caused by oxygen vacancy formation within the alumina matrix. Scanning laser microscopy (SLM), Raman spectroscopy (RS), scanning electron microscopy (SEM), cathodoluminescence (CL), and X-ray photoelectron spectroscopy (XPS) were utilized to evaluate the fractions of transformed zirconia phase and the stoichiometric evolution of the oxygen sub-lattice at the surface of wear tested ZTA components. Wear tracks on the surface of the femoral heads were only detected under dry conditions. Dry wear also showed the highest frictional forces and the most pronounced formation of oxygen vacancies among the tested conditions. Conversely, equivalent or greater amounts of the t -> m transformation were observed with water and squalene lubrication when compared to the dry wear condition

Raman spectroscopic investigation on the molecular structure of apatite and collagen in osteoporotic cortical bone

This study employed highly spectrally resolved Raman spectroscopy to examine the molecular composition of cortical bone tissue obtained from murine females in their healthy and ovariectomy- (OVX-) induced osteoporotic states. The aim of the study was to identify structural differences at the molecular scale both in apatite mineral and collagen fibrils between the two groups of samples. Raman spectroscopy was used to determine the chemical composition of cortical bone in regions including characteristic bands of both bone mineral and bone matrix. The results demonstrated that the mineral apatite of bone did not undergo significant amorphization in its diseased state, with the Raman microprobe also failing in recognizing a direct role of carbonate content in the embrittlement of OVX-diseased bone. On the other hand, complex off-stoichiometry variations could be detected in the columnar Ca-structure of the bony hydroxyapatite according to morphological variations of the Raman band belonging to the symmetric phosphate stretching (A1) band at ~959  cmâ1. A fundamental role was also recognized for collagen quality on the process of bone embrittlement. The so-called matrix maturity ratio, as systematically measured on Raman spectra in the Amide I region, increased with statistical significance in OVX-treated samples as compared to control samples. An 8% increase could be associated to a 115% increase in elastic stress intensification in the mineral phase of OVX-diseased tissue as compared to the control one, thus proving a degradation in the (elastic) energy-dissipative capacity of a diseased bone matrix

Study of the Failure Mechanism of a High-Density Polyethylene Liner in a Type IV High-Pressure Storage Tank

The use of Type IV cylinders for gas storage is becoming more widespread in various sectors, especially in transportation, owing to the lightweight nature of this type of cylinder, which is composed of a polymeric liner that exerts a barrier effect and an outer composite material shell that primarily imparts mechanical strength. In this work, the failure analysis of an HDPE liner in a Type IV cylinder for high-pressure storage was carried out. The breakdown occurred during a cyclic pressure test at room temperature and manifested in the hemispherical head area, as cracks perpendicular to the liner pinch-off line. The failed sample was thoroughly investigated and its characteristics were compared with those of other liners at different stages of production of a Type IV cylinder (blow molding, curing of the composite material). An examination of the liner showed that no significant chemical and morphological changes occurred during the production cycle of a Type IV cylinder that could justify the liner rupture, and that the most likely cause of failure was a design-related fatigue phenomenon

Green Tea Polyphenols Coupled with a Bioactive Titanium Alloy Surface: In Vitro Characterization of Osteoinductive Behavior through a KUSA A1 Cell Study

A chemically-treated titanium alloy (Ti6Al4V) surface, able to induce hydroxyapatite precipitation from body fluids (inorganic mineralization activity), was functionalized with a polyphenolic extract from green tea (tea polyphenols, TPH). Considering that green tea polyphenols have stimulating effects on bone forming cells (biological mineralization), the aim was to test their osteoinductive behavior due to co-operation of inorganic and biological mineralization on mesenchymal stem cells KUSA A1. The functionalized surfaces were characterized by using the Folin–Ciocalteu method and X-ray photoelectron spectroscopy to confirm the successful outcome of the functionalization process. Two cell cultures of mesenchymal stem cells, KUSA A1 were performed, with or without osteoinductive factors. The cells and surfaces were characterized for monitoring cell viability and hydroxyapatite production: Fourier Transform Infrared Spectroscopy and Raman spectroscopy analyses showed deposition of hydroxyapatite and collagen due to the cell activity, highlighting differentiation of KUSA A1 into osteoblasts. A higher production of extracellular matrix was highlighted on the functionalized samples by laser microscope and the fluorescence images showed higher viability of cells and greater presence of osteocalcin in these samples. These results highlight the ability of polyphenols to improve cell differentiation and to stimulate biological mineralization, showing that surface functionalization of metal implants could be a promising way to improve osteointegrability