60 years of Charnley-Muller Alivium hip prosthesis: the revision percentage and tribo-corrosion sequelae after a mean of 27 years.

INTRODUCTION: The main aim was to analyse the series of 29 collected cemented Charnley-Muller Alivium retrievals with the meantime in situ of 27 years. In addition, the revision rate of 1425 Alivium prostheses implanted at our institution between 1977 and 1992 was calculated. MATERIALS AND METHODS: The revision percentage of the Alivium cohort was calculated up to 45 years of follow-up and compared to that of all total hip arthroplasties (THAs) implanted in the same period (No. 5535). Metal and polyethylene retrieved components were inspected in 29 cases for wear damage and roughness. Wear particles were retrieved from periprosthetic tissue using digestion protocols and their composition, morphology, and size distribution were investigated. Periprosthetic tissue was analysed histologically. RESULTS: The revision percentage of the Alivium cohort was 16% at 45 years of follow-up. It was comparable to all the THAs implanted at the same time (18%). The shape of polyethylene particles isolated from periprosthetic tissue corresponded to the wear pattern on polyethylene cups. Polyethylene particles were the main wear product, with the majority (68%) of particles smaller than 0.1 µm. Metal particles were rare with two types: CoCr and Cr based. Histological analysis showed that in 14 out of 18 specimens, the metal particles were graded + 1, reflecting that the metal loading in the periprosthetic tissue was low. CONCLUSIONS: Our study represents valuable data not reported previously on the survival rate of Charnley-Muller prostheses at 45 years of follow-up and a unique insight into the collected retrievals from the materials' point of view.

Superhydrophobic Aluminium Surface to Enhance Corrosion Resistance and Obtain Self-Cleaning and Anti-Icing Ability.

A facile environmentally acceptable surface roughening method using chemical etching in HCl/H2O2 followed by grafting with n-octyltrimethoxysilane (AS-8) and 1H,1H,2H,2H-perfluorooctyltrimethoxysilane (FAS-8) was studied to fabricate a (super)hydrophobic aluminium surface. The ground aluminium surface after selected etching times (before and after grafting), was characterised using a contact profilometer, optical tensiometer, scanning electron microscope coupled with an energy-dispersive spectroscope and X-ray photoelectron spectroscope to evaluate surface roughness, wettability, surface morphology and composition. The durability of the grafted surface was tested using thermal and UV resistance tests. The corrosion properties were evaluated using potentiodynamic measurements and standard salts spray testing, ASTM B117-19. Finally, the self-cleaning and anti-icing abilities were assessed. The grafted aluminium surface with octyl- or perfluorooctyl silane reflected the highly hydrophobic (AS-8) and superhydrophobic behaviour (FAS-8). Moreover, the different behaviour of the octyl- or perfluorooctyl chain in the silane molecule on modified surface properties was also noticed because durability tests confirmed greater thermal, UV stability and corrosion resistance of FAS-8 compared to AS-8. The aluminium etched for 2 min and grafted with FAS-8 also demonstrated an excellent self-cleaning and anti-icing performance.

Risk of cancer after primary total hip replacement: The influence of bearings, cementation and the material of the stem.

Background and purpose - Despite the increasing number of total hip replacements (THRs), their systemic influence is still not known. We have studied the influence of specific features of THRs-the bearing surface, the use of bone cement and the material of the stem-on the cancer incidence. Patients and methods - In a retrospective cohort study we identified 8,343 patients with THRs performed at Valdoltra Hospital from September 1, 1997 to December 31, 2009. Patient data were linked to national cancer and population registries. The standardized incidence ratios (SIR) and Poisson regression relative risks (RR) were calculated for all and specific cancers. Results - General cancer risk in our cohort was comparable to the population risk. Comparing with population, the risk of prostate cancer was statistically significantly higher in patients with metal-on-metal bearings (SIR =1.35); with metal-on-polyethylene bearings (SIR =1.30), with non-cemented THRs (SIR =1.40), and with titanium alloy THRs (SIR =1.41). In these last 3 groups there was a lower risk of hematopoietic tumors (SIR =0.69; 0.66 and 0.66 respectively). Risk of kidney cancer was significantly higher in the non-metal-on-metal, non-cemented, and titanium alloy groups (SIR =1.30; 1.46 and 1.41 respectively). Risk of colorectal and lung cancer was significantly lower in the investigated cohort (SIR =0.82 and 0.83, respectively). Risk for all cancers combined as well as for prostate and skin cancer, shown by Poisson analysis, was higher in the metal-on-metal group compared with non-metal-on-metal group (RR =1.56; 2.02 and 1.92, respectively). Interpretation - Some associations were found between the THRs' features, especially a positive association between metal-on-metal bearings, and specific cancers.

Effect of Mercapto and Methyl Groups on the Efficiency of Imidazole and Benzimidazole-based Inhibitors of Iron Corrosion.

We report on the combined experimental and computational study of imidazole- and benzimidazole-based corrosion inhibitors containing methyl and/or mercapto groups. Electrochemical measurements and long-term immersion tests were performed on iron in NaCl solution, whilst computational study explicitly addresses the molecular level details of the bonding on iron surface by means of density functional theory calculations (DFT). Experimental data were the basis for the determination of inhibition efficiency and mechanism. Methyl group combined with mercapto group has a beneficial effect on corrosion inhibition at all inhibitor concentrations. The beneficial effect of mercapto group combined with benzene group is not so pronounced as when combined with methyl group. The latter is in stark contrast with the behaviour found previously on copper, where the effect of methyl group was detrimental and that of mercapto and benzene beneficial. Explicit DFT calculations reveal that methyl-group has a small effect on the inhibitor-surface interaction. In contrast, the presence of mercapto group involves the strong S-surface bonding and consequently the adsorption of inhibitors with mercapto group is found to be more exothermic.

Quaternary Ti-20Nb-10Zr-5Ta alloy during immersion in simulated physiological solutions: formation of layers, dissolution and biocompatibility.

Samples of the quaternary Ti-20Nb-10Zr-5Ta alloy were immersed in Hanks' simulated physiological solution and in minimum essential medium (MEM) for 25 days. Samples of Ti metal served as controls. During immersion, the concentration of ions dissolved in MEM was measured by inductively coupled plasma mass spectrometry, while at the end of the experiment the composition of the surface layers was analyzed by X-ray photoelectron spectroscopy, and their morphology by scanning electron microscopy equipped for chemical analysis. The surface layer formed during immersion was comprised primarily of TiO2 but contained oxides of alloying elements as well. The degree of oxidation differed for different metal cations; while titanium achieved the highest valency, tantalum remained as the metal or is oxidized to its sub-oxides. Calcium phosphate was formed in both solutions, while formation of organic-related species was observed only in MEM. Dissolution of titanium ions was similar for metal and alloy. Among alloying elements, zirconium dissolved in the largest quantity. The long-term effects of alloy implanted in the recipient's body were investigated in MEM, using two types of human cells-an osteoblast-like cell line and immortalized pulmonary fibroblasts. The in vitro biocompatibility of the quaternary alloy was similar to that of titanium, since no detrimental effects on cell survival, induction of apoptosis, delay of growth, or change in alkaline phosphatase activity were observed on incubation in MEM.

A comparative study of four bearing couples of the same acetabular and femoral component: a mean follow-up of 11.5 years.

We present a retrospective evaluation of 1369 hip arthroplasties performed using the Bicon-Plus cups and SL-Plus stems, differing only in the bearing combination. Four bearing combination groups were used: metal-on-polyethylene (MoP) group with 587 hips, ceramic-on-polyethylene (CoP) group with 161 hips, metal-on-metal (MoM) group with 322 hips and ceramic-on-ceramic (CoC) group with 299 hips. The mean follow-up was 11.5 years (4.1 to 15.0). Radiological evaluation was performed on implants failed due to aseptic loosening. The survival for prosthesis with revision for any reason at ten years was 96.1% (95% confidence interval (CI) 94.3 to 97.9) for MoP, 98.1% (CI 95.9 to 100) for CoP, 90.2% (CI 86.8 to 93.6) for MoM, and 95.6% (CI 93.0 to 98.2) for CoC. Survival for aseptic loosening was also determined.

Enhanced mechanical properties and environmental stability of polymer-bonded magnets using three-step surface wet chemical modifications of Nd-Fe-B magnetic powder.

This research focuses on the surface modification of Nd-Fe-B magnetic powder to enhance its thermal and oxidation resistance without compromising magnetic properties and to improve adhesion to the polymer binder for enhanced mechanical properties. A three-step surface modification process involving phosphatization treatment, tetraethyl orthosilicate (TEOS) application, and 3-aminopropyltriethoxysilane (APTES) grafting, was applied to the powder, which was then compounded with polyamide 12 and injection-moulded into cylinders and dog-bone-shaped tubes. The resulting magnets exhibited remanence (Br) of 487.6 mT, coercivity (Hci) of 727.7 kA/m, and energy product (BHmax) of 39.3 kJ/m3. The modified magnets demonstrated exceptional corrosion resistance and thermal stability, with less than 5% irreversible flux loss after exposure to hot water, temperature shock, and pressurised steam. Furthermore, the modified magnets displayed significantly higher tensile strength, elongation at break, and elastic modulus with improvements of 62%, 16.7%, and 19.9%, respectively, compared to the non-modified batch. Additionally, the modified batch showed a notable 52% increase in flexural stress during flexural testing. These findings underscore the potential of silane surface modifications in producing injection-moulded permanent magnets based on Nd-Fe-B alloy, extending their shelf life and enhancing their overall performance.

Bilateral Acrylic Hip Mold Arthroplasty in a Child With a Revision 60 years After Implantation: Clinical Case and Chemical Analysis of Endoprosthetic Material.

A 68-year-old man was referred due to bilateral hip pain and gradual deterioration of walking. He had mold arthroplasties on both hips at the age of 7 years and has been functioning well for more than 5 decades. However, the original data on operative report and the prostheses were missing. The radiological examination revealed bilateral broken prosthetic material. Thus, stage bilateral revision total hip arthroplasty was performed. A detailed chemical analysis of retrieved mold arthroplasty implants proved that the acrylic material was noted to be the same composition with the difference in appearance likely being related to different thermal treatments originally applied to the implants. As presented in our clinical case, even obsolete implants may have good survivorship. According to the case presented, total hip arthroplasty could be considered an effective option with the desired functional outcome when conservative and joint-preserving measures are exhausted.

Development and Characterization of Gelatin-Based Hydrogels Containing Triblock Copolymer and Phytic Acid.

In recent research, significant interest has been directed towards gelatin-based hydrogels due to their affordable price, extensive availability, and biocompatibility, making them promising candidates for various biomedical applications. The development and characterization of novel hydrogels formed from varying ratios of gelatin, triblock copolymer Pluronic F-127, and phytic acid have been presented. Swelling properties were examined at different pH levels. The morphology of hydrogels and their thermal properties were analyzed using scanning electron microscopy (SEM), thermogravimetric analysis (TG), and differential scanning calorimetry (DSC). Fourier-transform infrared (FTIR) analysis of the hydrogels was also performed. The introduction of phytic acid in the hydrogel plays a crucial role in enhancing the intermolecular interactions within gelatin-based hydrogels, contributing to a more stable, elastic, and robust network structure.

Hyaluronic acid stimulates the formation of calcium phosphate on CoCrMo alloy in simulated physiological solution.

The behaviour of CoCrMo alloy has been studied in two simulated physiological solutions-NaCl and Hanks' solutions-each containing the sodium salt of hyaluronic acid. Hyaluronic acid is a component of synovial joint fluid, so the behaviour of orthopaedic alloys in its presence needs to be assessed. Electrochemical methods, X-ray photoelectron spectroscopy and scanning electron microscopy have been used to analyse the composition, thickness and morphology of any layers formed on the alloy. The addition of hyaluronic acid shifts the corrosion potential and increases the value of polarization resistance. The presence of hyaluronic acid in simulated Hanks' physiological solution stimulates the formation of a calcium phosphate layer, opening up the possibility for tailoring the surface properties of CoCrMo alloy. The viability of human osteoblast-like was determined using the Alamar(®) Blue Assay, while the osteogenic activity was evaluated by alkaline phosphatase activity. The presence of hyaluronic acid affects the alkaline phosphatase activity.

The effect of fluoride ions on the corrosion behaviour of Ti metal, and Ti6-Al-7Nb and Ti-6Al-4V alloys in artificial saliva.

Metallic materials used for manufacture of dental implants have to exhibit high corrosion resistance in order to prevent metal release from a dental implant. Oral cavity is aggressive towards metals as it represents a multivariate environment with wide range of conditions including broad range of temperatures, pH, presence of bacteria and effect of abrasion. An increasing use of various Ti-based materials for dental implants and orthodontic brackets poses the question of their corrosion resistance in the presence of fluoride ions which are present in toothpaste and mouth rinse. Corrosion behaviour of Ti metal, Ti-6Al-7Nb and Ti-6Al-4V alloys and constituent metals investigated in artificial saliva is significantly affected by the presence of fluoride ions (added as NaF), as proven by electrochemical methods. Immersion test was performed for 32 days. During that time the metal dissolution was measured by inductively coupled plasma mass spectrometry. At the end of the test the composition, thickness and morphology of the surface layers formed were investigated by X-ray photoelectron spectroscopy and scanning electron microscopy.

Durable Polyacrylic/Siloxane-Silica Coating for the Protection of Cast AlSi7Mg0.3 Alloy against Corrosion in Chloride Solution.

This study presented a novel corrosion protective coating based on polyacrylic/siloxane-silica (PEHA-SS) deposited on lightweight cast aluminium alloy AlSi7Mg0.3. The synthesis of PEHA-SS comprises organic monomer 2-ethylhexyl acrylate and organically modified silane 3-(trimethoxysilyl)propyl methacrylate as well as an inorganic silane, tetraethyl orthosilicate. The steps during the synthesis process were monitored using real-time infrared spectroscopy. The coating deposited onto the AlSi7Mg0.3 surface was characterised using various techniques, including infrared spectroscopy, 3D contact profilometry, and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy. The corrosion resistance of the coated alloy in sodium chloride solutions was evaluated using electrochemical impedance spectroscopy. The accelerated testing of the uncoated and coated sample was performed using the Machu test. This novel, nine micrometres thick PEHA-SS coating achieved durable corrosion (barrier) protection for the AlSi7Mg0.3 alloy in 0.1 M NaCl during the first four months of immersion or under accelerated corrosion conditions in a Machu chamber containing NaCl, acetic acid, and hydrogen peroxide at 37 °C.

The Effect of pH Value of a Simulated Physiological Solution on the Corrosion Resistance of Orthopaedic Alloys.

Metals and alloys used in orthopaedics and dentistry are exposed in vivo to various agents and environmental conditions. One of the important factors that determine the corrosion behaviour of metallic biomaterials is the pH of the environment. The corrosion resistance of stainless steel 316L (Fe/Cr18/Ni10/Mo3), titanium and titanium alloy Ti-6Al-4V (Ti90/Al6/V4) was studied in terms of their electrochemical properties and biodegradation in simulated physiological solutions of different pH values (4.5, 6.5, 7.5 and 8). The electrochemical characteristics of individual metal components were also investigated using cyclic voltammetry, linear polarization and potentiodynamic polarization methods. The concentration of dissolved metal ions released during 32 days immersion under simulated physiological conditions was determined by inductively coupled plasma mass spectroscopy. The corrosion behaviour of stainless steel 316L is strongly affected by the pH of the physiological solution in the range from 4.5 to 8.0. The corrosion resistance was enhanced at higher pH and the concentrations of released metal ions lower. The behaviour of titanium and its alloy however is almost independent of the pH.

Survival rate of total hip replacements with matched and with mixed components with 10.7 years mean follow-up.

BACKGROUND: Mixing and matching components from different manufacturers in total hip arthroplasty is a frequently used off-label praxis. The clinical consequences of this procedure have not been studied in detail. METHODS: 860 patients with matched and 1067 patients with mixed primary total hip replacement (THR) components carried out between 1 January 2002 and 31 December 2004, were selected from our Institution registry. The analysis endpoint was set at 1 January 2016. THRs with poorly performing components were excluded from study groups. Kaplan-Meier survival curves for both groups were calculated and compared using the Log-Rank test and the demographic data using the chi-square test. Correlations between demographic data and revisions were calculated using bivariate correlation. RESULTS: 28 revisions were carried out in the matched group and 67 in the mixed group. The 14-year overall survival probability was significantly better in the former (96.0%) than in the mixed group (92.7%) (p = 0.002). Survival, free of aseptic and septic failures, was statistically, significantly higher in the matched group (p = 0.026 and p = 0.007, respectively).The survival of the mixed subgroup with heads and stems from the same manufacturer did not differ statistically from that of the matched group (p = 0.079). CONCLUSIONS: In contrast to the results listed in the National Joint Registry and the New Zealand Joint Registry, the survival probability in our study was, statistically, significantly higher in total hip replacements using components of the same manufacturer. Importantly, mixing and matching the components of different manufacturers led to similar survival providing the head and the stem were from the same manufacturer.

Triazole, benzotriazole, and naphthotriazole as copper corrosion inhibitors: I. Molecular electronic and adsorption properties.

The gas-phase adsorption of 1,2,3-triazole, benzotriazole, and naphthotriazole-considered as corrosion inhibitors-on copper surfaces was studied and characterized using density functional theory (DFT) calculations. We find that the molecule-surface bond strength increases with increasing molecular size, thus following the sequence: triazole

Outcome after Two Sequential Revision Hip Arthroplasties for CoC Bearing Fracture with 10 Years Follow-up: A Case Report.

INTRODUCTION: Revisions due to the fracture of ceramic-on-ceramic (CoC) bearing are rare, however when they occur, they represent a major challenge to an orthopedic surgeon for ensuring safe and long-term survival of the replaced bearing. CASE REPORT: We present a case of fractured ceramic liner of total hip prosthesis that underwent revision to a metal-on-polyethylene (MoP) bearing couple, with consequent huge periprosthetic metallosis. Shortly after, the second revision operation followed using the third bearing couple of ceramic-on-polyethylene (CoP). At 10 years follow-up after the operation due to ceramic fracture, the patient is now pain free with full range of motion of the revised hip. CONCLUSION: Establishment of diagnostic routes and recommended protocols for CoC bearing fracture would allow easier recognition of potential fracture and diminish its consequences for the patients.

What determines the inhibition effectiveness of ATA, BTAH, and BTAOH corrosion inhibitors on copper?

Three corrosion inhibitors for copper-3-amino-1,2,4-triazole (ATA), benzotriazole (BTAH), and 1-hydroxybenzotriazole (BTAOH)-were investigated by corrosion experiments and atomistic computer simulations. The trend of corrosion inhibition effectiveness of the three inhibitors on copper in near-neutral chloride solution is determined experimentally as BTAH ≳ ATA ≫ BTAOH. A careful analysis of the results of computer simulations based on density functional theory allowed to pinpoint the superior inhibiting action of BTAH and ATA as a result of their ability to form strong N-Cu chemical bonds in deprotonated form. While these bonds are not as strong as the Cl-Cu bonds, the presence of solvent favors the adsorption of inhibitor molecules onto the surface due to stronger solvation of the Cl(-) anions. Moreover, benzotriazole displays the largest affinity among the three inhibitors to form intermolecular aggregates, such as [BTA-Cu](n) polymeric complex. This is another factor contributing to the stability of the protective inhibitor film on the surface, thus making benzotriazole an outstanding corrosion inhibitor for copper. These findings cannot be anticipated on the basis of inhibitors' molecular electronic properties alone, thus emphasizing the importance of a rigorous modeling of the interactions between the components of the corrosion system in corrosion inhibition studies.

Acrylate-Based Hybrid Sol-Gel Coating for Corrosion Protection of AA7075-T6 in Aircraft Applications: The Effect of Copolymerization Time.

Pre-hydrolysed/condensed tetraethyl orthosilicate (TEOS) was added to a solution of methyl methacrylate (MMA) and 3-methacryloxypropyltrimethoxysilane (MAPTMS), and then copolymerised for various times to study the influence of the latter on the structure of hybrid sol-gel coatings as corrosion protection of aluminium alloy 7075-T6. The reactions taking place during preparation were characterised using real-time Fourier transform infrared spectroscopy, dynamic light scattering and gel permeation chromatography. The solution characteristics were evaluated, using viscosimetry, followed by measurements of thermal stability determined by thermogravimetric analysis. The optimal temperature for the condensation reaction was determined with the help of high-pressure differential scanning calorimetry. Once deposited on 7075-T6 substrates, the coatings were evaluated using a field emission scanning electron microscope coupled to an energy dispersive spectrometer to determine surface morphology, topography, composition and coating thickness. Corrosion properties were tested in dilute Harrison's solution (3.5 g/L (NH4)2SO4 and 0.5 g/L NaCl) using electrochemical impedance spectroscopy. The copolymerization of MMA and MAPTMS over 4 h was optimal for obtaining 1.4 µm thick coating with superior barrier protection against corrosion attack (Z10 mHz 1 GΩ cm2) during three months of exposure to the corrosive medium.

Contemporary Modes of Corrosion Protection and Functionalization of Materials.

Corrosion protection is an important global issue. Corrosion affects all metal materials in industry, infrastructure, civil engineering, transport, biomedicine, etc. causing their deterioration and degradation. Corrosion protection is a necessity which enables the safe and well-functioning of metal structures and devices. In addition to long-term efficiency, corrosion protection should be environmentally and economically acceptable. Growing population with needs on modern and high-tech technologies is boosting consumption of base and rare earth metals. All these issues are putting high demands on area of corrosion protection with the main goal to prolong the life-time of metal materials, reduce the need for steeply increasing production and thus preserve resources. In this review contemporary modes of corrosion protection of metal materials with the emphasis on copper and aluminium base alloys as one of most important base metals are presented. These include corrosion inhibitors, conversion, sol-gel and hydrophobic coatings. Examples are our research studies over the last decade are presented.