Biodegradable PMMA coated Zn-Mg alloy with bimodal grain structure for orthopedic applications - A promising alternative.

The study examines the impact of microstructure and polymethyl methacrylate (PMMA) grafting on the degradability of Zn-Mg alloys. The mechanical properties of a Zn alloy containing 0.68 wt% Mg and extruded at 200 °C are enhanced for degradable load-bearing applications, addressing a crucial need in the field. The material exhibits a bimodal grain size distribution that is random texture, consisting of secondary phases, grains, and sub-grains. With an elongation to failure of 16 %, the yield and ultimate tensile strengths are 325.9 and 414.5 MPa, respectively, and the compressive yield strength is 450.5 MPa. The "grafting-from" method was used to coat a few micrometers thick of PMMA on both bulk and scaffold Zn alloys to mitigate the corrosion rate. The last one is a porous structure, with a porosity of 65.8 %, considered as in the first approach of an orthopedic implant. After being immersed for 720 h, the PMMA-grafted bulk alloy's corrosion rate decreased from 0.43 to 0.25 mm/y. Similarly, the scaffold alloy's corrosion rate reduced from 1.24 to 0.49 mm/y. These results indicate that the method employed could be used for future orthopedic applications.

Enhancing Polymethyl Methacrylate Prostheses for Cranioplasty with Ti mesh Inlays.

Biocompatible polymers such as polymethyl methacrylate (PMMA), despite fulfilling biomedical aspects, lack the mechanical strength needed for hard-tissue implant applications. This gap can be closed by using composites with metallic reinforcements, as their adaptable mechanical properties can overcome this problem. Keeping this in mind, novel Ti-mesh-reinforced PMMA composites were developed. The influence of the orientation and volume fraction of the mesh on the mechanical properties of the composites was investigated. The composites were prepared by adding Ti meshes between PMMA layers, cured by hot-pressing above the glass transition temperature of PMMA, where the interdiffusion of PMMA through the spaces in the Ti mesh provided sufficient mechanical clamping and adhesion between the layers. The increase in the volume fraction of Ti led to a tremendous improvement in the mechanical properties of the composites. A significant anisotropic behaviour was analysed depending on the direction of the mesh. Furthermore, the shaping possibilities of these composites were investigated via four-point bending tests. High shaping possibility was found for these composites when they were shaped at elevated temperature. These promising results show the potential of these materials to be used for patient-specific implant applications.

Use of a Photocleavable Initiator to Characterize Polymer Chains Grafted onto a Metal Plate with the Grafting-from Method.

The thorough characterization of polymer chains grafted through a "grafting-from" process onto substrates based on the determination of number (Mn) and weight (Mw) average molar masses, as well as dispersity (Ɖ), is quite challenging. It requires the cleavage of grafted chains selectively at the polymer-substrate bond without polymer degradation to allow their analysis in solution with steric exclusion chromatography, in particular. The study herein describes a technique for the selective cleavage of PMMA grafted onto titanium substrate (Ti-PMMA) using an anchoring molecule that combines an atom transfer radical polymerization (ATRP) initiator and a UV-cleavable moiety. This technique allows the demonstration of the efficiency of the ATRP of PMMA on titanium substrates and verification that the chains were grown homogeneously.

Effect of Mg Addition and PMMA Coating on the Biodegradation Behaviour of Extruded Zn Material.

Although zinc (Zn) is one of the elements with the greatest potential for biodegradable uses, pure Zn does not have the ideal mechanical or degrading properties for orthopaedic applications. The current research aims at studying the microstructure and corrosion behaviour of pure Zn (used as a reference material) and Zn alloyed with 1.89 wt.% magnesium (Mg), both in their extruded states as well as after being coated with polymethyl methacrylate (PMMA). The grafting-from approach was used to create a PMMA covering. The "grafting-from" method entails three steps: the alkali activation of the alloys, their functionalization with an initiator of polymerization through a phosphonate-attaching group, and the surface-initiated atom transfer radical polymerisation (SI-ATRP) to grow PMMA chains. Electrochemical and immersion corrosion tests were carried out in a simulated body fluid (SBF), and both confirmed the enhanced corrosion behaviour obtained after coating. The electrochemical test revealed a decrease in the degradation rate of the alloy from 0.37 ± 0.14 mm/y to 0.22 ± 0.01 mm/y. The immersion test showed the ability of complete protection for 240 h. After 720 h of immersion, the coated alloy displays minute crevice corrosion with very trivial pitting compared to the severe localized (galvanic and pitting) corrosion type that was detected in the bare alloy.

Novel Alkali Activation of Titanium Substrates To Grow Thick and Covalently Bound PMMA Layers.

Titanium (Ti) is the most widely used metal in biomedical applications because of its biocompatibility; however, the significant difference in the mechanical properties between Ti and the surrounding tissues results in stress shielding which is detrimental for load-bearing tissues. In the current study, to attenuate the stress shielding effect, a new processing route was developed. It aimed at growing thick poly(methyl methacrylate) (PMMA) layers grafted on Ti substrates to incorporate a polymer component on Ti implants. However, the currently available methods do not allow the development of thick polymeric layers, reducing significantly their potential uses. The proposed route consists of an alkali activation of Ti substrates followed by a surface-initiated atom transfer radical polymerization using a phosphonic acid derivative as a coupling agent and a polymerization initiator and malononitrile as a polymerization activator. The average thickness of the grown PMMA layers is approximately 1.9 µm. The Ti activation-performed in a NaOH solution-leads to a porous sodium titanate interlayer with a hierarchical structure and an open microporosity. It promotes the covalent grafting reaction because of high hydroxyl groups' content and enables establishing a further mechanical interlocking between the growing PMMA layer and the Ti substrate. As a result, the produced graduated structure possesses high Ti/PMMA adhesion strength (∼260 MPa). Moreover, the PMMA layer is (i) thicker compared to those obtained with the previously reported techniques (∼1.9 µm), (ii) stable in a simulated body fluid solution, and (iii) biocompatible. This strategy opens new opportunities toward hybrid prosthesis with adjustable mechanical properties with respect to host bone properties for personalized medicines.

Harnessing the multifunctionality in nature: a bioactive agent release system with self-antimicrobial and immunomodulatory properties.

Major problems with biomedical devices in particular implants located in nonsterile environments concern: (i) excessive immune response to the implant, (ii) development of bacterial biofilms, and (iii) yeast and fungi infections. An original multifunctional coating that addresses all these issues concomitantly is developed. A new exponentially growing polyelectrolyte multilayer film based on polyarginine (PAR) and hyaluronic acid (HA) is designed. The films have a strong inhibitory effect on the production of inflammatory cytokines released by human primary macrophage subpopulations. This could reduce potential chronic inflammatory reaction following implantation. Next, it is shown that PAR, due to its positive charges, has an antimicrobial activity in film format against Staphylococcus aureus for 24 h. In order to have a long-term antimicrobial activity, a precursor nanoscale silver coating is deposited on the surface before adding the PAR/HA films. Moreover, the PAR/HA films can be easily further functionalized by embedding antimicrobial peptides, like catestatin (CAT), a natural host defense peptide. This PAR/HA+CAT film proves to be effective as an antimicrobial coating against yeast and fungi and its cytocompatibility is also assessed. Finally, this all-in-one system constitutes an original strategy to limit inflammation and prevents bacteria, yeast, and fungi infections.

Alternative technique for calcium phosphate coating on titanium alloy implants.

As an alternative technique for calcium phosphate coating on titanium alloys, we propose to functionalize the metal surface with anionic bath containing chlorides of palladium or silver as activators. This new deposition route has several advantages such as controlled conditions, applicability to complex shapes, no adverse effect of heating, and cost effectiveness. A mixture of hydroxyapatite and calcium phosphate hydrate is deposited on the surface of Ti-6Al-4V. Calcium phosphate coating is built faster compared with the one by Simulated Body Fluid. Cell morphology and density are comparable to the control one; and the results prove no toxic compound is released into the medium during the previous seven days of immersion. Moreover, the cell viability is comparable with cells cultivated with the virgin medium. These experimental treatments allowed producing cytocompatible materials potentially applicable to manufacture implantable devices for orthopedic and oral surgeries.

Investigation on the Residual Stress State of Drawn Tubes by Numerical Simulation and Neutron Diffraction Analysis.

Cold drawing is widely applied in the industrial production of seamless tubes, employed for various mechanical applications. During pre-processing, deviations in tools and their adjustment lead to inhomogeneities in the geometry of the tubes and cause a gradient in residuals. In this paper a three dimensional finite element (3D-FE)-model is presented which was developed to calculate the change in wall thickness, eccentricity, ovality and residual macro-stress state of the tubes, produced by cold drawing. The model simulates the drawing process of tubes, drawn with and without a plug. For finite element modelling, the commercial software package Abaqus was used. To validate the model, neutron strain imaging measurements were performed on the strain imaging instrument SALSA at the Institute Laue Langevin (ILL, Grenoble, France) on a series of SF-copper tubes, drawn under controlled laboratory conditions, varying the drawing angle and the plug geometry. It can be stated that there is sufficient agreement between the finite element method (FEM)-calculation and the neutron stress determination.

Structural, microstructural, and residual stress investigations of plasma-sprayed hydroxyapatite on Ti-6Al-4 V.

Plasma-spray (PS) is a classical technique usually employed to cover orthopaedic titanium implant surfaces with hydroxyapatite (HA - Ca(10)(PO(4))(6)(OH)(2)). The objective of the current study is to investigate the structure and microstructure of HA plasma-spray 50 mum thick coating on titanium alloy (Ti-6Al-4 V) and residual stress due to processing in the substrate and in HA coating. The structure of the coatings was determined by high-energy synchrotron X-ray diffraction in energy dispersive (HESXRD), selected area electron diffraction (saed), Scanning Electron Microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR). No impurity phases in the HA were identified by HESXRD to keep away from the decomposition of HA at high temperature. hcp phase of HA substrate was detected with slight amorphous background. FTIR spectrum of a HA powder shows a typical spectrum for HA material with the characteristic phosphate peaks for HA at wavenumbers of 1090, 1052, 963, 602, and 573 cm(-1) are present. The morphology of HA powder observed by SEM exhibits grains of ca. 0.1 mum well-adapted for cell proliferation. HA/Ti-6Al-4 V interface observed by cross-section scanning and transmission electron microscopy (TEM) presents microcracks. Residual stresses were analyzed by sin(2) Psi X-ray diffraction method on titanium substrates and HA coating. Although the Ti substrates are in a slightly tensile residual state, the coated ones show a compressive state.