Evaluation of in vitro bioactivity and biocompatibility of Bioglass®-reinforced polyethylene composite

The bioactivity and biocompatibility of Bioglass®-reinforced high-density polyethylene composite (Bioglass®/HDPE) have been evaluated in simulated body fluid (SBF) and by in vitro cell culture, respectively. The formation of a biologically active hydroxy-carbonate apatite (HCA) layer on the composite surface after immersion in SBF was demonstrated by thin-film X-ray diffraction, infrared spectroscopy and scanning electron microscopy, indicating the in vitro bioactivity of Bioglass®/HDPE composites. The HCA layer was formed on the 40 vol% composite surface within 3 days immersion in SBF at a formation rate comparable to those on bioactive glass-ceramics, showing that in vitro bioactivity could be obtained in a composite. Furthermore, the composite was biocompatible to primary human osteoblast-like cells. In comparison with unfilled HDPE and tissue culture plastic control, a significant increase in cellular metabolic activity was found on the composite. Therefore, Bioglass®/HDPE composites have a promising biological response as a potential implant material.     

Processing and bioactivity of 45S5 Bioglass®-graphene nanoplatelets composites

Well dispersed 45S5 Bioglass^® (BG)-graphene nanoplatelets (GNP) composites were prepared after optimising the processing conditions. Fully dense BG nanocomposites with GNP loading of 1, 3 and 5 vol% were consolidated using Spark plasma sintering (SPS). SPS avoided any structural damage of GNP as confirmed using Raman spectroscopy. GNP increased the viscosity of BG-GNP composites resulting in an increase in the sintering temperature by ~50 °C compared to pure BG. Electrical conductivity of BG-GNP composites increased with increasing concentration of GNP. The highest conductivity of 13 S/m was observed for BG-GNP (5 vol%) composite which is ~9 orders of magnitude higher compared to pure BG. For both BG and BG-GNP composites, in vitro bioactivity testing was done using simulated body fluid for 1 and 3 days. XRD confirmed the formation of hydroxyapatite for BG and BG-GNP composites with cauliflower structures forming on top of the nano-composites surface. GNP increased the electrical conductivity of BG-GNP composites without affecting the bioactivity thus opening the possibility to fabricate bioactive and electrically conductive scaffolds for bone tissue engineering.     

Novel starch thermoplastic/Bioglass® composites: Mechanical properties, degradation behavior and in-vitro bioactivity

The present research aims to evaluate the possibility of creating new degradable, stiff and highly bioactive composites based on a biodegradable thermoplastic starch-based polymeric blend and a Bioglass® filler. Such combination should allow for the development of bioactive and degradable composites with a great potential for a range of temporary applications. A blend of starch with ethylene–vinyl alcohol copolymer (SEVA-C) was reinforced with a 45S5 Bioglass® powder presenting a granulometric distribution between 38 and 53 m. Composites with 10 and 40 wt % of 45S5 Bioglass® were compounded by twin-screw extrusion (TSE) and subsequently injection molded under optimized conditions. The mechanical properties of the composites were evaluated by tensile testing, and their bioactivity assessed by immersion in a simulated body fluid (SBF) for different periods of time. The biodegradability of these composites was also monitored after several immersion periods in an isotonic saline solution. The tensile tests results obtained indicated that SEVA-C/Bioglass® composites present a slightly higher stiffness and strength (a modulus of 3.8 GPa and UTS of 38.6 MPa) than previously developed SEVA-C/Hydroxylapatite (HA) composites. The bioactivity of SEVA-C composites becomes relevant for 45S5 amounts of only 10 wt %. This was observed by scanning electron microscopy (SEM) and confirmed for immersion periods up to 30 days by both thin-film X-ray diffraction (TF-XRD) (where HA typical peaks are clearly observed) and induced coupled plasma emission (ICP) spectroscopy used to follow the elemental composition of the SBF as function of time. Additionally, it was observed that the composites are biodegradable being the results correlated with the correspondent materials composition.     

The story of Bioglass®

Historically the function of biomaterials has been to replace diseased or damaged tissues. First generation biomaterials were selected to be as bio-inert as possible and thereby minimize formation of scar tissue at the interface with host tissues. Bioactive glasses were discovered in 1969 and provided for the first time an alternative; second generation, interfacial bonding of an implant with host tissues. Tissue regeneration and repair using the gene activation properties of Bioglass provide a third generation of biomaterials. This article reviews the 40 year history of the development of bioactive glasses, with emphasis on the first composition, 45S5 Bioglass, that has been in clinical use since 1985. The steps of discovery, characterization, in vivo and in vitro evaluation, clinical studies and product development are summarized along with the technology transfer processes.     

The surface functionalization of 45S5 Bioglass®-based glass-ceramic scaffolds and its impact on bioactivity

The first and foremost function of a tissue engineering scaffold is its role as a substrate for cell attachment, and their subsequent growth and proliferation. However, cells do not attach directly to the culture substrate; rather they bind to proteins that are adsorbed to the scaffold's surface. Like standard tissue culture plates, tissue engineering scaffolds can be chemically treated to couple proteins without losing the conformational functionality; a process called surface functionalization. In this work, novel highly porous 45S5 Bioglass-based scaffolds have been functionalized applying 3-AminoPropyl-TriethoxySilane (APTS) and glutaraldehyde (GA) without the use of organic solvents. The efficiency and stability of the surface modification was assessed by X-ray photoemission spectroscopy (XPS). The bioactivity of the functionalized scaffolds was investigated using simulated body fluid (SBF) and characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). It was found that the aqueous heat-treatment applied at 80 degrees C for 4 hrs during the surface functionalization procedure accelerated the structural transition of the crystalline Na2Ca2Si3O9 phase, present in the original scaffold structure as a result of the sintering process used for fabrication, to an amorphous phase during SBF immersion. The surface functionalized scaffolds exhibited an accelerated crystalline hydroxyapatite layer formation upon immersion in SBF caused by ion leaching and the increased surface roughness induced during the heat treatment step. The possible mechanisms behind this phenomenon are discussed.     

Photocatalytic decomposition of VOCs by AC–TiO2 and EG–TiO2 nanocomposites

Clean Technologies and Environmental Policy - In this study, TiO2 nanoparticles (NPs)-based catalysts were prepared for the photocatalytic removal of toluene as a model VOC from air under UV light....     

Preparation of TiO2, Ag-doped TiO2 nanoparticle and TiO2–SBA-15 nanocomposites using simple aqueous solution-based chemical method and study of their photocatalytical activity

Nanocrystalline TiO₂, Ag-doped TiO₂ and TiO₂–SBA-15 nanocomposites have been synthesised using a simple aqueous solution-based chemical method. Nanocrystalline TiO₂ was synthesised by calcining the precursor prepared by using ethylenediamine tetraacetic acid and TiCl₃ in aqueous medium. Formation of crystalline phase (anatase, rutile or mixed phase) and crystallite size were found to be dependent on calcination temperature. To enhance the photocatalytic activity, Ag-doped TiO₂ was synthesised by doping of Ag during the synthesis step of TiO₂. TiO₂–SBA-15 nanocomposites were synthesised by impregnation method. Pure anatase TiO₂ nanoparticle was formed in the amorphous matrix of the silicate SBA-15, even though the loading of the TiO₂ in the silicate matrix was as low as 5?wt%. The synthesised materials were characterised using thermal analysis, powder X-ray diffraction method, surface area and porosimetry analysis, diffuse reflectance analysis and transmission electron microscopy. The photocatalytic property of the synthesised materials was investigated towards the degradation of methyl orange under sunlight exposure and monitored by UV–visible spectrophotometer. Ag-doped TiO₂ exhibited enhanced photocatalytic activity than undoped TiO₂. TiO₂–SBA-15 nanocomposites showed impressive photocatalytic activity even with 10?wt% TiO₂ loading.     

Study on antibacterial effect of 45S5 Bioglass®

Previous studies have shown that bioactive glasses possessed antibacterial effect on common bacteria due to the high aqueous pH value caused by the bioactive glass dissolution. In the present study, the efficiency of the antibacterial effect of 45S5 Bioglass (45S5 BAG) against S. aureus, S. epidermidis and E. coli and its mechanism were investigated. The results showed that 45S5 BAG exhibited a strong antibacterial effect against the bacteria, and the sensitivity of gram-negative and gram-positive bacteria to Bioglass was different. Furthermore, a dose-dependent bacterial adhesion on 45S5 BAG particles and the formation of needle-like Bioglass debris were observed, which resulted in the damage of cell walls and inactivation of bacteria. The results suggested that both the high pH and bioglass debris on the surface of bacteria may be the possible mechanisms of the antibacterial effect of 45S5 BAG particulates.     

Effects of dispersion and interfacial modification on the macroscale properties of TiO2 polymer–matrix nanocomposites

This paper quantifies how the quality of dispersion and the quality of the interfacial interaction between TiO₂ nanoparticles and host polymer independently affect benchmark properties such as glass transition temperature (T_g), elastic modulus and loss modulus. By examining these composites with differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and scanning electron microscopy (SEM), we demonstrate changes in properties depending on the adhesive/wetting or repulsive/dewetting interactions the nanoparticles have with the bulk polymer. We further quantify the dispersion of TiO₂ nanoparticles in polymethylmethacrylate (PMMA) matrices by a digital–optical method and correlate those values to the degree of T_g depression compared to neat PMMA. Samples with the same weight percent of nanoparticles but better dispersion show larger shifts in T_g.     

A microstructural examination of apatite induced by Bioglass® in vitro

Bioglass®, a clinically used bone graft material, has been tested in vitro in a simulated body fluid (SBF) up to four weeks. Apatite crystals were not only found to form on its surface but also in the reaction solutions. The apatite crystals have been examined by high-resolution transmission electron microscopy (TEM). The crystals formed in the solutions appear identical in morphology and structure with those formed on the Bioglass® surface. It may be that the soluble Si in the solution serves as the nucleating site for the apatite crystal or that apatite nuclei are released from the Bioglass® surface to the solution resulting in crystal growth.     

XANES analysis of calcium and sodium phosphates and silicates and hydroxyapatite–Bioglass®45S5 co-sintered bioceramics

Bioglass®45S5 was co-sintered with hydroxyapatite at 1200 °C. When small amounts (< 5 wt.%) of Bioglass®45S5 was added it behaved as a sintering aid and also enhanced the decomposition of hydroxyapatite to β-tricalcium phosphate. However when 10 wt.% and 25 wt.% Bioglass®45S5 was used it resulted in the formation of Ca₅(PO₄)₂SiO₄ and Na₃Ca₆(PO₄)₅ in an amorphous silicate matrix respectively. These chemistries show improved bioactivity compared to hydroxyapatite and are the subject of this study. The structure of several crystalline calcium and sodium phosphates and silicates as well as the co-sintered hydroxyapatite–Bioglass®45S5 bioceramics were examined using XANES spectroscopy. The nature of the crystalline and amorphous phases were studied using silicon (Si) and phosphorus (P) K- and L_2,3-edge and calcium (Ca) K-edge XANES.Si L_2,3-edge spectra of sintered bioceramic compositions indicates that the primary silicates present in these compositions are sodium silicates in the amorphous state. From Si K-edge spectra, it is shown that the silicates are in a similar structural environment in all the sintered bioceramic compositions with 4-fold coordination.Using P L_2,3-edge it is clearly shown that there is no evidence of sodium phosphate present in the sintered bioceramic compositions. In the P K-edge spectra, the post-edge shoulder peak at around 2155 eV indicates that this shoulder to be more defined for calcium phosphate compounds with decreasing solubility and increasing thermodynamic stability. This shoulder peak is more noticeable in hydroxyapatite and β-TCP indicating greater stability of the phosphate phase. The only spectra that does not show a noticeable peak is the composition with Na₃Ca₆(PO₄)₅ in a silicate matrix indicating that it is more soluble compared to the other compositions.     

Surface modification of a Ti–7.5Mo alloy using NaOH treatment and Bioglass® coating

The objective of this study was to propose a surface modification for a low-modulus Ti–7.5Mo alloy to initiate the formation of hydroxyapatite (HA) during in vitro bioactivity tests in simulated body fluid (SBF). Specimens of commercially pure titanium (c.p. Ti) and Ti–7.5Mo were initially immersed in a 15 M NaOH solution at 60°C for 24 h, resulting in the formation of a porous network structure composed of sodium titanate (Na₂Ti₅O₁₁). Afterwards, bioactive Bioglass^® particles were deposited on the surface of NaOH-treated c.p. Ti and Ti–7.5Mo. The specimens were then immersed in SBF at 37°C for 1, 7 and 28 days, respectively. The apatite-forming ability of the NaOH-treated and Bioglass^®-coated Ti–7.5Mo was higher than that of the c.p. Ti under the same condition. The X-ray diffraction (XRD) and energy-dispersive X-ray spectroscopy (EDS) results indicated that the deposited amounts of calcium phosphate were much greater for the surface-treated Ti–7.5Mo than for the c.p. Ti, a finding attributable to or correlated with the higher pH value of the SBF containing surface-treated Ti–7.5Mo. Moreover, in the surface-treated Ti–7.5Mo, the pH value of the SBF approached a peak of 7.66 on the first day. A combination of NaOH treatment and subsequent Bioglass^® coating was successfully used to initiate in vitro HA formation in the surface of the Ti–7.5Mo alloy.     

Al2TiO5–Al2O3–TiO2 nanocomposite: Structure,mechanical property and bioactivity studies

Novel biomaterials are of prime importance in tissue engineering. Here, we developed novel nanostructured Al₂TiO₅–Al₂O₃–TiO₂ composite as a biomaterial for bone repair. Initially, nanocrystalline Al₂O₃–TiO₂ composite powder was synthesized by a sol–gel process. The powder was cold compacted and sintered at 1300–1500 °C to develop nanostructured Al₂TiO₅–Al₂O₃–TiO₂ composite. Nano features were retained in the sintered structures while the grains showed irregular morphology. The grain-growth and microcracking were prominent at higher sintering temperatures. X-ray diffraction peak intensity of β-Al₂TiO₅ increased with increasing temperature. β-Al₂TiO₅ content increased from 91.67% at 1300 °C to 98.83% at 1500 °C, according to Rietveld refinement. The density of β-Al₂TiO₅ sintered at 1300 °C, 1400 °C and 1500 °C were computed to be 3.668 g cm^?3, 3.685 g cm^?3 and 3.664 g cm^?3, respectively.Nanocrystalline grains enhanced the flexural strength. The highest flexural strength of 43.2 MPa was achieved. Bioactivity and biomechanical properties were assessed in simulated body fluid. Electron microscopy confirmed the formation of apatite crystals on the surface of the nanocomposite. Spectroscopic analysis established the presence of Ca and P ions in the crystals. Results throw light on biocompatibility and bioactivity of β-Al₂TiO₅ phase, which has not been reported previously.     

Quantitative rates of in vivo bone generation for Bioglass® and hydroxyapatite particles as bone graft substitute

Rates of in vivo bone generation were characterized by point-counting analysis of particulate Bioglass® and synthetic hydroxyapatite (HA) in rabbit femora. New bony tissue was observed in 20% of the image area around Bioglass® particles at 1 wk, and the degree of trabecular bone growth increased with time. The interparticle space of Bioglass® was filled by 80% bonding bone between 6 and 12 wk. The rate constants of trabecular bone growth in the presence of Bioglass® were 10.9×10-3 d-1 at the periphery of the implantation site. HA particles led to smaller rate constants of 4.6×10-3 d-1 at the periphery, and the HA particles developed very small amounts of bridging bone. The quantitative rate of bone growth matched well with previously measured bioactive indices of the materials.     

Preparation and characterization of epoxy/γ-aluminum oxide nanocomposites

Epoxy/γ-Al₂O₃ nanocomposites were prepared with a homogenizer and followed by a stepwise thermal curing process in this study. The dispersion of γ-Al₂O₃ nanoparticles was examined with a transmission electron microscopy (TEM). Meanwhile, the effects of γ-Al₂O₃ nanoparticles on thermal, dynamic mechanical and tensile properties of epoxy/γ-Al₂O₃ nanocomposites were also investigated and discussed. When the γ-Al₂O₃ content was increased from 1phr to 5phr, results revealed that γ-Al₂O₃ nanoparticles were effective to enhance both the stiffness and toughness of epoxy resin. Meanwhile, the maximum properties of glass transition temperature (T_g), T_d5%, storage modulus, tensile modulus, and elongation at break were observed in the epoxy/5phr γ-Al₂O₃ nanocomposite.     

Mechanical and stress relaxation behavior of Santoprene® thermoplastic elastomer/boehmite alumina nanocomposites produced by water-mediated and direct melt compounding

Thermoplastic dynamic vulcanizate (TPV) was filled with synthetic boehmite alumina (BA) via water-mediated (WM) and direct melt compounding (DM) techniques. According to the WM an aqueous BA dispersion was injected into the molten TPV in a twin-screw extruder to prepare the related nanocomposite with 5 wt.% BA content. In DM the BA powder was mixed to the TPV granules in the hopper of the extruder. The dispersion of the BA was studied by atomic force microscopy (AFM), and discussed. The mechanical and thermo-mechanical properties of the composites were determined in uniaxial static tensile, dynamic-mechanical thermal analysis (DMTA), and short-time stress relaxation tests (performed at various temperatures). It was found that the WM technique yielded a finer BA dispersion in TPV than the DM one. Incorporation of BA increased the stiffness, elongation at break and relaxation modulus compared to the neat TPV. Effect of the BA incorporation route was most pronounced for the stress relaxation results. Master curves, displaying the relaxation modulus vs. time, were constructed by applying the time–temperature-superposition principle. It was established that the Williams–Landel–Ferry equation (WLF), and the generalized Maxwell model are fairly applicable to the stress relaxation results.     

Influence of surface modified TiO2 nanoparticles on dielectric properties of PVdF–HFP nanocomposites

Polyvinylidene fluoride-co-hexaflouropropylene (PVdF–HFP)/TiO₂ hybrid nanocomposites membranes for electrical applications have been prepared using a solvent casting technique. The interface between PVdF–HFP and TiO₂ was modified using aminopropyltrimethoxysilane (APS) coupling agent. The silane linkages on the TiO₂ surface have been confirmed using Fourier transform infra red spectroscopy. WAXD and DSC analysis has been employed to estimate the variation in crystallinity within the membrane as a function of the incorporation of both untreated and APS treated TiO₂. The dispersion of both nanoparticles in the PVdF–HFP matrix were characterized by atomic force microscopy and differences were observed in the images of APS treated and untreated. Variation in electrical properties such as conductivity, dielectric constant, dielectric loss and electric modulus of the hybrid composite films were studied employing AC impedance spectroscopy over a range of frequency from 1 kHz to 1 MHz at room temperature. Theoretical models like Maxwell, Faruka, Rayleigh and Lichtenecker were employed to calculate the effective dielectric constant of hybrid nanocomposite membranes and the estimated values were compared with the experimental data. Further, the variation in thermal stability of PVdF–HFP membrane as a function of untreated and silane treated TiO₂ reinforcement has been estimated using thermogravimetric analysis.     

Preparation and Characterization of Nucleus/Shell TiO2/HAP Complex Nanophotocatalyst

A rapid and more efficient method was developed to prepare nucleus/shell titania/hydroxyapatite （TiO2/HAP） complex nanophotocatalyst. Hydroxyapatite （5 μm） which had been dissolved with 0.1 mol/L HCI was formed on the surface of the nanosized anatase titania powders by increasing the pH value of the solution at 90℃ in the water bath for only several hours .The microstructure and morphology of the resulting sample were investigated by X-ray diffraction （XRD）, Fourier-transform infrared spectroscopy （FT-IR）, scanning electron microscopy （SEM）, energy dispersive spectrum （EDS） and atomic force microscope （AFM）. The results indicated that nucleus/shell structural TiO2/HAP was formed in our experiments, and the thickness of the coating layer was about 5 nm. Photocatalytic decomposition of methyl orange was utilized to test the photocatalysis of the resulting samples and the result was compared with that of pure anatase titania powders （about 20 nm）. It was shown that the photocatalytic activity of the sample was not decreased due to the coating of HAP.     

Influence of calcinated and non calcinated nanobioglass particles on hardness and bioactivity of sol�Cgel-derived TiO2�CSiO2 nano composite coatings on stainless steel substrates

Thick films of calcinated and non calcinated nanobioglass (NBG)-titania composite coatings were prepared on stainless steel substrates by alkoxide sol-gel process. Dip-coating method was used for the films preparation. The morphology, structure and composition of the nano composite films were evaluated using environmental scanning electron microscope, X-ray diffraction and Fourier transform infrared spectroscope. The SEM investigation results showed that prepared thick NBG-titania films are smooth and free of macrocracking, fracture or flaking. The grain size of these films was uniform and nano scale (50-60 nm) which confirmed with TEM. Also FTIR confirmed the presence of Si-O-Si bands on the calcinated NBG-titania films. The hardness of the prepared films (TiO(2)-calcinated NBG and TiO(2)-Non calcinated NBG) was compared by using micro hardness test method. The results verified that the presence of calcinated NBG particles in NBG-titania composite enhanced gradually the mechanical data of the prepared films. The in vitro bioactivity of these films was discussed based on the analysis of the variations of Ca and P concentrations in the simulated body fluid (SBF) and their surface morphologies against immersion time. Surface morphology and Si-O-Si bands were found to be of great importance with respect to the bioactivity of the studied films. The results showed that calcinated NBG-titania films have better bioactivity than non calcinated NBG-titania films.