In Vitro Studies Regarding the Effect of Cellulose Acetate-Based Composite Coatings on the Functional Properties of the Biodegradable Mg3Nd Alloys.

Magnesium (Mg) alloys are adequate materials for orthopedic and maxilo-facial implants due to their biocompatibility, good mechanical properties closely related to the hard tissues, and processability. Their main drawbacks are the high-speed corrosion process and hydrogen release. In order to improve corrosion and mechanical properties, the Mg matrix can be strengthened through alloying elements with high temperature-dependent solubility materials. Rare earth elements (RE) contribute to mechanical properties and degradation improvement. Another possibility to reduce the corrosion rate of Mg-based alloys was demonstrated to be the different types of coatings (bioceramics, polymers, and composites) applied on their surface. The present investigation is related to the coating of two Mg-based alloys from the system Mg3Nd (Mg-Nd-Y-Zr-Zn) with polymeric-based composite coatings made from cellulose acetate (CA) combined with two fillers, respectively hydroxyapatite (HAp) and Mg particles. The main functions of the coatings are to reduce the biodegradation rate and to modify the surface properties in order to increase osteointegration. Firstly, the microstructural features of the experimental Mg3Nd alloys were revealed by optical microscopy and scanning electron microscopy (SEM) coupled with energy-dispersive spectroscopy. Apart from the surface morphology revealed by SEM, the roughness and wettability of all experimental samples were evaluated. The corrosion behavior of the uncoated and coated samples of both Mg3Nd alloys was investigated by immersion testing and electrochemical testing using Simulated Body Fluid as the medium. The complex in vitro research performed highlights that the composite coating based on CA with HAp particles exhibited the best protective effect for both Mg3Nd alloys.

Comparative Study on Interface Fracture of 4th Generation 3-Steps Adhesive and 7th Generation Universal Adhesive.

The purpose of this paper is to compare the fracture behavior of interfaces obtained using fourth-generation and universal dental adhesives. The study relies on optic and SEM to evaluate the dentin-adhesive-restoration material interface of the samples and also on FEA simulation of fracture behavior. Specimen fabrication relied on 20 extracted teeth, in which class I cavities were created according to a protocol established based on the rules of minimally invasive therapy. For the direct adhesive technique, the adhesives used were: three-step All Bond, three-batch A and one-step Clearfil Universal Bond Quick-batch B. The restoration was performed with the same composite for both adhesives: Gradia direct posterior. The simulation used a 3D reconstructed molar on which geometric operations were performed to obtain an assembly that replicated a physical specimen. Material properties were applied to each component based on the information found in the literature. A simplified model for crack propagation was constructed, and using the fracture mechanics tool in Ansys 2019, the stress intensity factors that act at the crack tip of the adhesive interface were obtained. Mechanical simulation and microscopic investigation showed us how the interface of the dentine-adhesive-filling material performed in cases of both dental adhesives and for a certain loading condition. Important differences were identified among the adhesives, the fourth generation being superior to the fourth generation especially due to the separate steps in which the tooth surface was prepared for adhesion.

Metal-Ceramic Compatibility in Dental Restorations According to the Metallic Component Manufacturing Procedure.

In terms of production technology, metal-ceramic systems for dental restorations comply with a concrete algorithm, the efficiency of which is always dependent on the applications for which they are intended. The first stage involves obtaining metal support, followed by firing the ceramic on the surface of the metal to meet the list of functional and aesthetic requirements of a future restoration. The compatibility of the two materials-the metal component and the ceramic component-must be ensured in several respects: chemical compatibility, thermo-chemical compatibility, and mechanical compatibility. Thus, there is a need to simulate the thermal behavior of the metal-ceramic couple in its processing to achieve appropriate dental prostheses. In this study, three types of Co-Cr metal frames were manufactured using three different production technologies: conventional casting, milling (CAM), and selective laser melting (SLM). Composition analyses, scanning electron microscopy (SEM), and microstructural analyses of the metal-ceramic interface for each type of production technology, as well as the determination of the hardness and the thermal expansion coefficients of experimental materials and three-point bending tests, were carried out in this study. Considering all these aspects, we demonstrated the influence of the technology of producing the metallic part of the metal-ceramic bonding process in dental prostheses.

Effect of Fluoride Coatings on the Corrosion Behavior of Mg-Zn-Ca-Mn Alloys for Medical Application.

The most critical shortcoming of magnesium alloys from the point of view of medical devices is the high corrosion rate, which is not well-correlated with clinical needs. It is well- known that rapid degradation occurs when an implant made of Mg-based alloys is placed inside the human body. Consequently, the implant loses its mechanical properties and failure can occur even if it is not completely degraded. The corrosion products that appear after Mg-based alloy degradation, such as H2 and OH- can have an essential role in decreasing biocompatibility due to the H2 accumulation process in the tissues near the implant. In order to control the degradation process of the Mg-based alloys, different coatings could be applied. The aim of the current paper is to evaluate the effect of fluoride coatings on the corrosion behavior of magnesium alloys from the system Mg-Zn-Ca-Mn potentially used for orthopedic trauma implants. The main functional properties required for the magnesium alloys to be used as implant materials, such as surface properties and corrosion behavior, were studied before and after surface modifications by fluoride conversion, with and without preliminary sandblasting, of two magnesium alloys from the system Mg-Zn-Ca-Mn. The experimental results showed that chemical conversion treatment with hydrofluoric acid is useful as a method of increasing corrosion resistance for the experimental magnesium alloys from the Mg-Zn-Ca-Mn system. Also, high surface free energy values obtained for the alloys treated with hydrofluoric acid correlated with wettability lead to the conclusion that there is an increased chance for biological factor adsorption and cell proliferation. Chemical conversion treatment with hydrofluoric acid is useful as a method of increasing corrosion resistance for the experimental Mg-Zn-Ca-Mn alloys.

Selection Route of Precursor Materials in 3D Printing Composite Filament Development for Biomedical Applications.

Additive manufacturing or 3D printing technologies might advance the fabrication sector of personalised biomaterials with high-tech precision. The selection of optimal precursor materials is considered the first key-step for the development of new printable filaments destined for the fabrication of products with diverse orthopaedic/dental applications. The selection route of precursor materials proposed in this study targeted two categories of materials: prime materials, for the polymeric matrix (acrylonitrile butadiene styrene (ABS), polylactic acid (PLA)); and reinforcement materials (natural hydroxyapatite (HA) and graphene nanoplatelets (GNP) of different dimensions). HA was isolated from bovine bones (HA particles size < 40 µm, <100 µm, and >125 µm) through a reproducible synthesis technology. The structural (FTIR-ATR, Raman spectroscopy), morphological (SEM), and, most importantly, in vitro (indirect and direct contact studies) features of all precursor materials were comparatively evaluated. The polymeric materials were also prepared in the form of thin plates, for an advanced cell viability assessment (direct contact studies). The overall results confirmed once again the reproducibility of the HA synthesis method. Moreover, the biological cytotoxicity assays established the safe selection of PLA as a future polymeric matrix, with GNP of grade M as a reinforcement and HA as a bioceramic. Therefore, the obtained results pinpointed these materials as optimal for future composite filament synthesis and the 3D printing of implantable structures.

Failure Analysis of Ultra-High Molecular Weight Polyethylene Tibial Insert in Total Knee Arthroplasty.

Knee osteoarthritis is treated based on total knee arthroplasty (TKA) interventions. The most frequent failure cause identified in surgical practice is due to wear and oxidation processes of the prothesis' tibial insert. This component is usually manufactured from ultra-high molecular weight polyethylene (UHMWPE). To estimate the clinical complications related to a specific prosthesis design, we investigated four UHMWPE tibial inserts retrieved from patients from Clinical Hospital Colentina, Bucharest, Romania. For the initial analysis of the polyethylene degradation modes, macrophotography was chosen. A light stereomicroscope was used to estimate the structural performance and the implant surface degradation. Scanning electron microscopy confirmed the optical results and fulfilled the computation of the Hood index. The oxidation process in UHMWPE was analyzed based on Fourier-transform infrared spectroscopy (FTIR). The crystallinity degree and the oxidation index were computed in good agreement with the existing standards. Mechanical characterization was conducted based on the small punch test. The elastic modulus, initial peak load, ultimate load, and ultimate displacement were estimated. Based on the aforementioned experimental tests, a variation between 9 and 32 was found in the case of the Hood score. The oxidation index has a value of 1.33 for the reference sample and a maximum of 9.78 for a retrieved sample.

Regulation and Certification of (Bio)Medical Engineers: A Case Study on Romania.

This paper analyzes the Romanian biomedical engineering educational path and certification process in European and international contexts and emphasizes the existence of a deficient operationalization of this qualification and profession, arguing that the domestic shortcomings are both a consequence of an unquestioned process of adopting European and even international classification schemes, and of insufficiently developed national administrative capabilities to properly implement the aforementioned classification frameworks. The core part of the article investigates the current academic track of the biomedical engineering specialization and scrutinizes the classification of occupations at different jurisdictional levels. The conclusions of the study indicate that one of the possible solutions for improving this unsatisfying status quo comes from a better communication between the national and European levels, and by their pro-active involvement in the international attempts of reviewing and refining the existing frameworks. The article ends with several recommendations and policy proposals meant to strengthen the role of various profession-certifying European documents, as well as to alleviate the regulatory deficiencies that this specialization has at Romanian level, in order to maximize its potential in the labor market.

Electrochemical and In Vitro Biological Evaluation of Bio-Active Coatings Deposited by Magnetron Sputtering onto Biocompatible Mg-0.8Ca Alloy.

The use of resorbable magnesium alloys in the design of implants represents a new direction in the healthcare domain. Two main research avenues are currently explored for developing or improving metallic biomaterials: (i) increase of their corrosion resistance by designed compositional and structural modifications, and (ii) functionalization of their surfaces by coating with ceramic or polymeric layers. The main objective of this work was to comparatively assess bio-functional coatings (i.e., highly-crystallized hydroxyapatite and silica-rich glass) deposited by radio-frequency magnetron sputtering (RF-MS) on a biodegradable Mg-0.8Ca alloy (0.8 wt.% of Ca). After probing their morphology (by scanning electron microscopy) and structure (by Fourier transform infrared spectroscopy and grazing incidence X-ray diffraction), the corrosion resistance of the RF-MS coated Mg-0.8Ca substrates was electrochemically tested (in synthetic biological media with different degrees of biomimicry), and their cytocompatibility was assessed in osteoblast and fibroblast cell cultures. By collective assessment, the most promising performances, in terms of mass loss (~7% after 12 days), hydrogen release rate (~6 mL/cm2 after 12 days), electrochemical corrosion parameters and cytocompatibility, were obtained for the crystalline HA coating.

Magnesium-Based Alloys Used in Orthopedic Surgery.

Magnesium (Mg)-based alloys have become an important category of materials that is attracting more and more attention due to their high potential use as orthopedic temporary implants. These alloys are a viable alternative to nondegradable metals implants in orthopedics. In this paper, a detailed overview covering alloy development and manufacturing techniques is described. Further, important attributes for Mg-based alloys involved in orthopedic implants fabrication, physiological and toxicological effects of each alloying element, mechanical properties, osteogenesis, and angiogenesis of Mg are presented. A section detailing the main biocompatible Mg-based alloys, with examples of mechanical properties, degradation behavior, and cytotoxicity tests related to in vitro experiments, is also provided. Special attention is given to animal testing, and the clinical translation is also reviewed, focusing on the main clinical cases that were conducted under human use approval.

Fluoride Treatment and In Vitro Corrosion Behavior of Mg-Nd-Y-Zn-Zr Alloys Type.

Fluoride conversion coatings on Mg present many advantages, among which one can find the reduction of the corrosion rate under "in vivo" or "in vitro" conditions and the promotion of the calcium phosphate deposition. Moreover, the fluoride ions released from MgF2 do not present cytotoxic effects and inhibit the biofilm formation, and thus these treated alloys are very suitable for cardiovascular stents and biodegradable orthopedic implants. In this paper, the biodegradation behavior of four new magnesium biodegradable alloys that have been developed in the laboratory conditions, before and after surface modifications by fluoride conversion (and sandblasting) coatings, are analyzed. We performed structural and surface analysis (XRD, SEM, contact angle) before and after applying different surface treatments. Furthermore, we studied the electrochemical behavior and biodegradation of all experimental samples after immersion test performed in NaCl solution. For a better evaluation, we also used LM and SEM for evaluation of the corroded samples after immersion test. The results showed an improved corrosion resistance for HF treated alloy in the NaCl solution. The chemical composition, uniformity, thickness and stability of the layers generated on the surface of the alloys significantly influence their corrosion behavior. Our study reveals that HF treatment is a beneficial way to improve the biofunctional properties required for the studied magnesium alloys to be used as biomaterials for manufacturing the orthopedic implants.

Preliminary Studies on Graphene-Reinforced 3D Products Obtained by the One-Stage Sacrificial Template Method for Bone Reconstruction Applications.

The bone remodeling field has shifted focus towards the delineation of products with two main critical attributes: internal architectures capable to promote fast cell colonization and good mechanical performance. In this paper, Luffa-fibers and graphene nanoplatelets were proposed as porogen template and mechanical reinforcing agent, respectively, in view of framing 3D products by a one-stage polymer-free process. The ceramic matrix was prepared through a reproducible technology, developed for the conversion of marble resources into calcium phosphates (CaP) powders. After the graphene incorporation (by mechanical and ultrasonication mixing) into the CaP matrix, and Luffa-fibers addition, the samples were evaluated in both as-admixed and thermally-treated form (compact/porous products) by complementary structural, morphological, and compositional techniques. The results confirmed the benefits of the two agents' addition upon the compact products' micro-porosity and the global mechanical features, inferred by compressive strength and elastic modulus determinations. For the porous products, overall optimal results were obtained at a graphene amount of <1 wt.%. Further, no influence of graphene on fibers' ability to generate at high temperatures internal interconnected-channels-arrays was depicted. Moreover, its incorporation led to a general preservation of structural composition and stability for both the as-admixed and thermally-treated products. The developed CaP-reinforced structures sustain the premises for prospective non- and load-bearing biomedical applications.

Advanced Composite Biomaterials.

"Biomaterials" is one of the most important fields of study in terms of its development in the 21st century [...].

Comparative Assessment of In Vitro and In Vivo Biodegradation of Mg-1Ca Magnesium Alloys for Orthopedic Applications.

Use of magnesium implants is a new trend in orthopedic research because it has several important properties that recommend it as an excellent resorbable biomaterial for implants. In this study, the corrosion rate and behavior of magnesium alloys during the biodegradation process were determined by in vitro assays, evolution of hydrogen release, and weight loss, and further by in vivo assays (implantation in rabbits' bone and muscle tissue). In these tests, we also used imaging assessments and histological examination of different tissue types near explants. In our study, we analyzed the Mg-1Ca alloy and all the hypotheses regarding the toxic effects found in in vitro studies from the literature and those from this in vitro study were rejected by the data obtained by the in vivo study. Thus, the Mg-1Ca alloy represents a promising solution for orthopedic surgery at the present time, being able to find applicability in the small bones: hand or foot.

Considerations and Influencing Parameters in EDS Microanalysis of Biogenic Hydroxyapatite.

Calcium phosphates (CPs) used as biomaterials have been intensively studied in recent years. In most studies, the determination of the chemical composition is mandatory. Due to the versatility and possibilities of performing qualitative and quantitative compositional analyses, energy dispersive spectrometry (EDS) is a widely used technique in this regard. The range of calcium phosphates is very diverse, the first method of approximating the type of compound being EDS microanalysis, by assessing the atomic Ca/P ratio. The value of this ratio can be influenced by several factors correlated with instrumental parameters and analysed samples. This article highlights the influence of the electron beam acceleration voltage (1 kV-30 kV) and of the particle size of calcium phosphate powders on the EDS analysis results. The characterised powders were obtained from bovine bones heat-treated at 1200 °C for 2 h, which have been ground and granulometrically sorted by mechanical vibration. The granulometric sorting generated three types of samples, with particle sizes < 20 µm, < 40 µm and < 100 µm, respectively. These were morphologically and dimensionally analysed by scanning electron microscopy (SEM) and compositionally by EDS, after the spectrometer was calibrated with a standard reference material (SRM) from NIST (National Institute of Standards and Technology). The results showed that the adjusting of acceleration voltage and of the powder particle size significantly influences the spectrum profile and the results of EDS analyses, which can lead to an erroneous primary identification of the analysed calcium phosphate type.

Naturally-Derived Biphasic Calcium Phosphates through Increased Phosphorus-Based Reagent Amounts for Biomedical Applications.

Calcium carbonate from marble and seashells is an eco-friendly, sustainable, and largely available bioresource for producing natural bone-like calcium phosphates (CaPs). Based on three main objectives, this research targeted the: (i) adaptation of an indirect synthesis route by modulating the amount of phosphorus used in the chemical reaction, (ii) comprehensive structural, morphological, and surface characterization, and (iii) biocompatibility assessment of the synthesized powdered samples. The morphological characterization was performed on digitally processed scanning electron microscopy (SEM) images. The complementary 3D image augmentation of SEM results also allowed the quantification of roughness parameters. The results revealed that both morphology and roughness were modulated through the induced variation of the synthesis parameters. Structural investigation of the samples was performed by Fourier transform infrared spectroscopy and X-ray diffraction. Depending on the phosphorus amount from the chemical reaction, the structural studies revealed the formation of biphasic CaPs based on hydroxyapatite/brushite or brushite/monetite. The in vitro assessment of the powdered samples demonstrated their capacity to support MC3T3-E1 pre-osteoblast viability and proliferation at comparable levels to the negative cytotoxicity control and the reference material (commercial hydroxyapatite). Therefore, these samples hold great promise for biomedical applications.

Synthesis and Characterization of Jellified Composites from Bovine Bone-Derived Hydroxyapatite and Starch as Precursors for Robocasting.

Hydroxyapatite-starch composites solidify rapidly via jellification, making them suitable candidates for robocasting. However, many aspects related to hydroxyapatite powder characteristics, hydroxyapatite-starch interaction, and composites composition and properties need to be aligned with robocasting requirements to achieve a notable improvement in the functionality of printed scaffolds intended for bone regeneration. This article presents a preliminary evaluation of hydroxyapatite-starch microcomposites. Thermal analysis of the starting powders was performed for predicting composites' behavior during heat-induced densification. Also, morphology, mechanical properties, and hydroxyapatite-starch interaction were evaluated for the jellified composites and the porous bodies obtained after conventional sintering, for different starch additions, and for ceramic particle size distributions. The results indicate that starch could be used for hydroxyapatite consolidation in limited quantities, whereas the composites shall be processed under controlled temperature. Due to a different mechanical behavior induced by particle size and geometry, a wide particle size distribution of hydroxyapatite powder is recommended for further robocasting ink development.