Enhanced Tribological and Bacterial Resistance of Carbon Nanotube with Ceria- and Silver-Incorporated Hydroxyapatite Biocoating.

Pertaining to real-life applications (by scaling up) of hydroxyapatite (HA)-based materials, herein is a study illustrating the role of carbon nanotube (CNT) reinforcement with ceria (CeO2) and silver (Ag) in HA on titanium alloy (TiAl6V4) substrate, utilizing the plasma-spraying processing technique, is presented. When compared with pure HA coating enhanced hardness (from 2.5 to 5.8 GPa), elastic modulus (from 110 to 171 GPa), and fracture toughness (from 0.7 to 2.2 MPa·m1/2) elicited a reduced wear rate from 55.3 × 10-5 mm³·N-1·m-1 to 2.1 × 10-5 mm³·N-1·m-1 in HA-CNT-CeO2-Ag. Besides, an order of magnitude lower Archard's wear constant and a 41% decreased shear stress by for HA-CNT-CeO2-Ag coating depicted the effect of higher hardness and modulus of a material to control its wear phenomenon. Antibacterial property of 46% (bactericidal) is ascribed to Ag in addition to CNT-CeO2 in HA. Nonetheless, the composite coating also portrayed exaggerated L929 fibroblast cell growth (4.8 times more than HA), which was visualized as flat and elongated cells with multiple filopodial protrusions. Hence, synthesis of a material with enhanced mechanical integrity resulting in tribological resistance and cytocompatible efficacy was achieved, thereupon making HA-CNT-CeO2-Ag a scalable potent material for real-life load-bearing implantable bio-coating.

Carbon Nanotube Functionalization Decreases Osteogenic Differentiation in Aluminum Oxide Reinforced Ultrahigh Molecular Weight Polyethylene.

Ultrahigh molecular weight polyethylene (UHMWPE) is one of the most preferred materials as an acetabular cup-liner for bone implant applications. The current work develops a correlation between wettability, protein adsorption with osteogenic differentiation upon reinforcement of functionalized carbon nanotube (f-CNT) and 10 wt % aluminum oxide (Al2O3) in compression molded UHMWPE composites. Phase characterization has confirmed the retention of CNTs after compression molding. The loading of 2 wt % f-CNT in UHMWPE has shown to increase the contact angle (CA, from 88.9° to ∼97.3°), decrease the surface free energy (SFE, 23.20 to ∼20.85 mJ/m2) and elicit enhanced adsorbed protein density (PD, from ∼0.26 to ∼0.32 mg/cm2) in comparison to that of virgin polymer. Similar trend also has observed with 5 and 10 wt % f-CNT reinforcement. Initially, a high density of L929 mouse fibroblast cells is observed for 10 wt % unfunctionalized CNT (u-CNT) loading (48 h of incubation) with high values of dispersion fraction of surface free energy (σd), i.e., 0.967, whereas a decrease in cell density after 48 h is attributed to significant apatite mineralization and low dispersion fraction (σd) of CNT-Al2O3-UHMWPE biocomposites. Interestingly, gene expression studies have corroborated low osteogenic differentiation (i.e., weaker intensity osteopontin and ß-actin) in 2-10 wt % f-CNT reinforced Al2O3-UHMWPE biocomposites in comparison to that of similar wt % reinforcement of u-CNT. Thus, implant material can be engineered, (bulk or surface-modified), possessing osteoanalogous and cytocompatible properties based on f-CNT-Al2O3-reinforced UHMWPE nanocomposites.

Dispersion fraction enhances cellular growth of carbon nanotube and aluminum oxide reinforced ultrahigh molecular weight polyethylene biocomposites.

Ultrahigh molecular weight polyethylene (UHMWPE) is widely used as bone-replacement material for articulating surfaces due to its excellent wear resistance and low coefficient of friction. But, the wear debris, generated during abrasion between mating surfaces, leads to aseptic loosening of implants. Thus, various reinforcing agents are generally utilized, which may alter the surface and biological properties of UHMWPE. In the current work, the cellular response of compression molded UHMWPE upon reinforcement of bioactive multiwalled carbon nanotubes (MWCNTs) and bioinert aluminum oxide (Al2O3) is investigated. The phase retention and stability were observed using X-ray diffraction, Raman spectroscopy and Fourier transform infrared (FTIR) spectroscopy. The reinforcement of MWCNTs and Al2O3 has shown to alter the wettability (from contact angle of ~88°±2° to ~118°±4°) and surface energy (from ~23.20 to ~17.75 mN/m) of composites with respect to UHMWPE, without eliciting any adverse effect on cytocompatibility for the L929 mouse fibroblast cell line. Interestingly, the cellular growth of the L929 mouse fibroblast cell line is observed to be dominated by the dispersion fraction of surface free energy (SFE). After 48 h of incubation period, a decrease in metabolic activity of MWCNT-Al2O3 reinforced composites is attributed to apatite formation that reduces the dispersion fraction of surface energy. The mineralized apatite during incubation was confirmed and quantified by energy dispersive spectroscopy and X-ray diffraction respectively. Thus, the dispersion fraction of surface free energy can be engineered to play an important role in achieving enhanced metabolic activity of the MWCNT-Al2O3 reinforced UHMWPE biopolymer composites.

Domination of volumetric toughening by silver nanoparticles over interfacial strengthening of carbon nanotubes in bactericidal hydroxyapatite biocomposite.

In order to address the problem of bacterial infections in bone-substitution surgery, it is essential that bone replacement biomaterials are equipped with bactericidal components. This research aims to optimize the content of silver (Ag), a well-known antibacterial metal, in a multiwalled carbon nanotube (CNT) reinforced hydroxyapatite (HA) composite, to yield a bioceramic which can be used as an antibacterial and tough surface of bone replacement prosthesis. The bactericidal properties evaluated using Escherichia coli and Staphylococcus epidermidis indicate that CNT reinforcement supports growth of Gram negative E. coli bacteria (~8.5% more adhesion than pure HA); but showed a strong decrease of Gram positive S. epidermidis bacteria (~diminished to 66%) compared to that of pure HA. Small amounts of silver (2-5wt.%) already show a severe bactericidal effect when compared to that of HA-CNT (by 30% and ~60% respectively). MTT assay confirmed enhanced biocompatibility of L929 cells on HA-4wt.% CNT (~121%), HA-4wt.% CNT-1wt.% Ag (~124%) sample and HA-4wt.% CNT-2wt.% Ag (~100%) when compared to that of pure HA. The samples with higher silver content showed decreased biocompatibility (77% for HA-4wt.% CNT-5wt.% Ag sample and 73% for HA-4wt.% CNT-10wt.% Ag). Though reinforcement of 4wt.% CNT has shown an increase of fracture toughness by ~62%, silver reinforcement has shown enhancement of up to 244% (i.e. 3.43 times). Accordingly, isolation of toughening contribution indicates that volumetric toughening by silver dominates over interfacial strengthening contributed by CNTs towards enhanced fracture toughness of potential HA-Ag-CNT biocomposites.