Effect of TiO2 morphology on in vitro bioactivity of polycaprolactone/TiO2 nanocomposites

TiO₂ nanostructures with different morphologies (spherical, tube, leaf-like and flower-like particles) were synthesized via a facile hydrothermal process. Polycaprolactone (PCL)/10 vol.% TiO₂ nanocomposites were prepared by solvent casting methods. In vitro bioactivity of the nanocomposite films was examined by immersion in the simulated body fluid (SBF) for up to 28 days. It was found that the morphology of titania nanostructures significantly influence the in vitro bioactivity of PCL/TiO₂ nanocomposites. This observation was attributed to the amount of anatase phase and the specific surface area of the TiO₂ nanostructures, which provide high surface exposure to SBF.     

Thermodynamic Properties of Matrine in Ethanol

In this paper, the enthalpies of dissolution of matrine in ethanol (EtOH) were measured using a RD496-2000 Calvet microcalorimeter at 309.65 K under atmospheric pressure. The differential enthalpy (Δ_dif H _m) and molar enthalpy (Δ_sol H _m) of dissolution of matrine in ethanol were determined. And the relationship between heat and the amount of solute was also established. Based on the thermodynamic and kinetic knowledge, the corresponding kinetic equation that described the dissolution process was determined to be \fracdadt=2.36×10^-4(1-a)^1.09{\frac{{\rm d}\alpha}{{\rm d}t}=2.36\times 10^{-4}(1-\alpha )^{1.09}} . Moreover, the half-life, t _1/2 = 48.89 min, Δ_sol H _m = −12.40 kJ · mol⁻¹, Δ_sol S _m = −354.7 J · mol⁻¹ · K⁻¹, and Δ _sol G _m =  97.43  kJ · mol⁻¹ of the dissolution process were also obtained. The results show that this work not only provides a simple method for the determination of the half-life for a drug but also offers a theoretical reference for the clinical application of matrine.     

Curing characteristics of an epoxy resin in the presence of ball-milled graphite particles

The effects of simply-made graphite particles (GPs, 1 wt%) on curing kinetics of an epoxy resin were investigated by means of differential scanning calorimetry (DSC). Two approaches based on constant and variable activation energy were applied to analyze the DSC curves. Results from the constant energy method showed that addition of the GPs increased the activation energy E _c and the overall order of reaction m + n. With the variable energy method, the activation energy varied with curing conversion substantially in the GP/epoxy system; in contrast, the variation in the pure epoxy was very limited. The GPs also decreased the heat of reaction (ΔH) and increased the glass transition temperature (T _g) for the epoxy. Comprehensive analyses indicated that the GPs did not significantly impede the curing reaction, which can enable improvement of the composite functionalities without creating processing penalties. The information obtained from this study provides an understanding of multiple factors involved in the complex relationship of structure and properties of the composites.     

Effect of particle size on the in vitro bioactivity,hydrophilicity and mechanical properties of bioactive glass-reinforced polycaprolactone composites

Polycaprolactone (PCL) composite films containing 5 wt.% bioactive glass (BG) particles of different sizes (6 μm, 250 nm, < 100 nm) were prepared by solvent casting methods. The ultra-fine BG particles were prepared by high-energy mechanical milling of commercial 45S5 Bioglass® particles. The characteristics of bioactive glass particles were studied by field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), dynamic light scattering (DLS), and X-ray diffraction (XRD) methods. In vitro bioactivity of the PCL/BG composite films was evaluated through immersion in the simulated body fluid (SBF). The films were analyzed by FE-SEM, energy dispersive spectrometry (EDS), XRD, and atomic force microscopy (AFM). The mechanical properties of highly-porous PCL/BG composites were examined on cylindrical specimens under quasi-static compression load. It was found that partial crystallization of amorphous BG particles during a prolonged mechanical milling occurred and calcium silicate (CaSiO₃) and sodium calcium silicate (Na₂CaSiO₄) phases were formed. The introduction of submicron BG particles (250 nm) was shown to improve the bioactivity of PCL films. In contrast to BG microparticles, the submicron BG particles were distributed on the film surfaces, providing a high surface exposure to SBF with an improved nanotopography. A notable increase in the stiffness and elastic modulus of the composite was also obtained. As compared to submicron BG particles, lower bioactivity and elastic modulus were acquired for PCL/BG nanoparticles. It was also shown that in spite of high specific surface area of the nanoparticles, partial crystallization during mechanical milling and agglomeration of the nanoparticles during processing decrease the bioactivity, hydrophilicity and mechanical response of the BG-reinforced PCL composites.     

Synthesis of aligned porous poly(ε-caprolactone) (PCL)/hydroxyapatite (HA) composite microspheres

We synthesized poly(ε-caprolactone) (PCL)/hydroxyapatite (HA) composite microspheres with an aligned porous structure and evaluated their potential applications in bone tissue engineering. A range of HA particles (0, 5, 10 and 20 wt.% in relation to the PCL polymer) were added to a PCL solution in order to improve the biocompatibility of the porous PCL/HA composite microspheres. All the synthesized microspheres showed that the HA particles were distributed well in the PCL matrix, while preserving their aligned porous structure. The average size of the PCL/HA composite microspheres increased from 62 ± 7 to 179 ± 95 μm with increasing HA content from 0 to 20 wt.%. The incorporation of the HA particles to the PCL polymer led to a considerable improvement in in vitro bioactivity, which was assessed by immersing the PCL/HA composite microspheres in simulated body fluid (SBF). A number of apatite crystals could be precipitated on the surface of the aligned porous PCL/HA composite microspheres after soaking in the SBF for 7 days.     

Electrochemical behavior of biocompatible AZ31 magnesium alloy in simulated body fluid

Dense oxidation coatings have been successfully developed on biocompatible AZ31 magnesium alloy, using microarc oxidation technique, to improve the corrosion resistance. Three different deposition voltages of 250, 300, and 350 V have been employed. The effect of voltage on the coating corrosion resistance has been evaluated through electrochemical experiments in a simulated body fluid (SBF) up to 7 days. Potentiodynamic polarization and electrochemical impedance spectroscopy scans were performed in the SBF solution, followed by optical microscopy surface inspection. The results indicate that the corrosion rates of the coatings are in the order of 250 < 300 < 350 V after immersion for 7 days, and the charge transfer resistance (R _ct) of the three samples is in the order of 250 > 300 > 350 V. Both the electrochemical tests and the surface inspection suggest that the 250 V coating has the highest corrosion resistance, with lowest corrosion current density, highest R _ct, and the best surface quality.     

Synthesis of nanocrystalline hydroxyapatite using surfactant template systems: Role of templates in controlling morphology

Hydroxyapatite (HA) nanopowder was synthesized by reverse microemulsion technique using calcium nitrate and phosphoric acid as starting materials in aqueous phase. Cyclohexane, hexane, and isooctane were used as organic solvents, and Dioctyl sulfosuccinate sodium salt (AOT), dodecyl phosphate (DP), NP5 (poly(oxyethylene)₅ nonylphenol ether), and NP12 (poly(oxyethylene)₁₂ nonylphenol ether) as surfactants to make the emulsion. Effect of synthesis parameters, such as type of surfactant, aqueous to organic ratio (A/O), pH and temperature on powder characteristics were studied. It was found that the surfactant templates played a significant role in regulating the morphology of the nanoparticle. Hydroxyapatite nanoparticle of different morphologies such as spherical, needle shape or rod-like were obtained by adjusting the conditions of the emulsion system. Synthesized powder was characterized using X-ray diffraction (XRD), BET surface area and transmission electron microscopy (TEM). Phase pure HA nanopowder with highest surface area of 121 m²/g were prepared by this technique using NP5 as a surfactant. Densification studies showed that this nanoparticle can give about 98% of their theoretical density. In vitro bioactivity of the dense HA compacts was confirmed by excellent apatite layer formation after 21 days in SBF solution. Cell material interaction study showed good cell attachment and after 5 days cells were proliferated on HA compacts in OPC1 cell culture medium. The results imply this to be a versatile approach for making hydroxyapatite nanocrystals with controlled morphology and excellent biocompatibility.     

Thermodynamic behaviour of undercooled melts

The Gibbs free energy difference (ΔG) between the undercooled liquid and the equilibrium solid phases has been studied for the various kinds of glass forming melts such as metallic, molecular and oxides melts using the hole theory of liquids and an excellent agreement is found between calculated and experimental values of ΔG. The study is made for non-glass forming melts also. The temperature dependence of enthalpy difference (ΔH) and entropy difference (ΔS) between the two phases, liquid and solid, has also been studied. The Kauzmann temperature (T ₀) has been estimated using the expression for ΔS and a linear relation is found between the reduced glass transition temperature (T _g/T _m) and (T ₀)/T _m). The residual entropy (ΔS _R) has been estimated for glass forming melts and an attempt is made to correlate ΔS _R,T _g,T ₀, andT _m which play a very important role in the study of glass forming melts.     

Synthesis and thermal behavior of poly(ε-caprolactone) grafted on multiwalled carbon nanotubes with high grafting degrees

Poly(ε-caprolactone) (PCL) was grafted onto multiwalled carbon nanotubes (MWNTs) with high grafting degrees. The surface of MWNTs was first modified by 2-hydroxyethyl benzocyclobutene (BCB-EO) via a [2 + 4] cyclo-addition reaction. Polymerization of ε-caprolactone was conducted in the presence of BCB-EO modified MWNTs and the catalyst stannous octoate. Alternatively, the grafted-BCB-EO first reacted with CpTiCl₃ and then the reactant was used to catalyze polymerization of ε-caprolactone. The grafting degrees of PCL prepared from BCB-EO modified MWNTs can reach at least 94%, much higher than those prepared by other two conventional methods. TEM result shows that the morphology and thickness of the grafted PCLs strongly depend on the grafting degree and grafting method. The crystallization and melting behaviors of the MWNTs-grafted PCL were investigated. MWNTs can exert both nucleation and confinement effects on crystallization of the grafted PCL, leading to lower crystallinity but higher crystallization temperature (T_c) and melting temperature (T_m) of the grafted PCLs. It is found that crystallinity of the grafted PCLs increases with the grafting degree, but T_c and T_m also depend on the molecular weight.     

Glass transition and fragility of telluro-vanadate glasses containing antimony oxide

The activation energy (ΔH ^*) of the glass transition and the heating-rate dependence of the glass transition temperature (T _g) of V₂O₅–Sb₂O₃–TeO₂ glasses were determined using differential scanning calorimetry technique. Non-isothermal measurements were performed at different heating rates φ (=3, 6, 9, 10, 13 K/min). The heating rate dependence of T _g was used to investigate the applicability of different theoretical models describing the glass transition. The application of Moynihan and Kissinger et al. models to the present data led to different values of (ΔH ^*) at each different heating-rate regions. This behavior was attributed to the strong heating rate dependence of the activation energy of the process. The fragility parameter (m = ΔH ^*/RT _g) were ≲90, suggesting that these glasses may be classified as strong glasses. The viscosity, η, calculated at a few selected temperatures near the glass transition region increased with increasing Sb₂O₃ content at any given temperature, which is also expected. Also the compositional dependence of T _g and ΔH ^* was investigated.     

The effects of temperature gradient and growth rate on the microstructure of directionally solidified Sn–3.5Ag eutectic solder

The mechanical properties (microhardness, tensile strength) of alloys are controlled by their microstructure, which depends strongly on temperature gradient (G) and growth rate (V). Thus, it is important to understand the relationships among G, V and microstructure (rod eutectic) of Sn–Ag solders. The Sn–3.5 wt% Ag eutectic alloy was directionally solidified upward with a constant growth rate, V (16.5 μm/s) at different temperature gradients, G (1.43–4.28 K/mm) and with a constant temperature gradient, G (3.93 K/mm) at different growth rates, V (8.3–500 μm/s) in a Bridgman–type directional solidification furnace. The rod spacings (λ) have been measured from both longitudinal section (parallel to the growth direction, λ _L ) and transverse section (perpendicular to the growth direction, λ _T ) of the samples. The undercooling values (ΔT) were calculated by using V, λ and system parameters (K ₁ and K ₂). It was found that the values of λ (λ _T , λ _L ) decrease while V and G are increasing. The relationships between rod spacing and solidification parameters (G and V) were obtained by linear regression analysis. The dependences of eutectic spacings λ on undercooling (ΔT) are also analyzed. λ² V, λΔT, ΔTV ^−0.5 and ΔTG ^−0.5 values were determined by using λ, ΔT, V and G values. The results obtained in this work are compared with the Jackson–Hunt eutectic theory and the similar experimental works. The experimental l_\textT ² \textV \lambda_{\text{T}}^{ 2} {\text{V}} value (159.3 μm³/s) is slightly lower than the result 174.6 μm³/s calculated from Jackson–Hunt eutectic theory.     

Dependence of electrical and thermal conductivity on temperature in directionally solidified Sn–3.5 wt% Ag eutectic alloy

Sn–3.5 wt% Ag alloy was directionally solidified upward with a constant growth rate (V = 16.5 μm/s) and a temperature gradient (G = 3.3 K/mm) in a Bridgman-type growth apparatus. The variations of electrical resistivity (ρ) with temperature in the range of 293–476 K for the directionally solidified Sn–3.5 wt% Ag eutectic alloy was measured. The measurements indicate that the electrical resistivity of the directionally solidified Sn–Ag eutectic solder increases with increasing temperature. The variations of thermal conductivity of solid phases versus temperature for the same alloy was determined from the Wiedemann-Franz and Smith-Palmer equations by using the measured values of electrical conductivity. From the graphs of electrical resistivity and thermal conductivity versus temperature, the temperature coefficient of electrical resistivity (α _TCR ) and the temperature coefficient of thermal conductivity (α _TCT ) for the same alloy were obtained. According to experimental results, the electrical and thermal conductivity of Sn–Ag eutectic solder linearly decrease with increasing the temperature. The enthalpy of fusion (ΔH) and the change of specific heat (ΔC _P ) during the transformation at the studied alloy were determined from heating curve during the transformation from eutectic solid to eutectic liquid by means of differential scanning calorimeter (DSC).     

Fatigue properties of a modified 7075 aluminum alloy containing scandium

Fatigue properties such as the fatigue strength, fatigue notch sensitivity, and fatigue crack propagation rate, of a modified Al-7075 + Sc aluminum alloy were investigated in this study. The effects of solution treatment on the fatigue performance of this alloy were also investigated. The ultimate tensile strength of the as-extruded sample was 705.5 MPa. The ultimate tensile strength decreased by 12% after solution treatment. The fatigue limit σ_e of the as-extruded sample decreased from 201.2 to 154.4 MPa after solution treatment. The fatigue notch sensitivity for the as-extruded and solution-treated (ST) samples was 0.97 and 0.64, respectively. The crack growth rate in the as-extruded sample with fine precipitates was clearly lower than that of the ST sample that had coarse precipitates at R = 0.1 when ΔK < 15 MPa?m \sqrt m . However, the growth rates of both the samples were approximately the same when ΔK > 15 MPa?m \sqrt m . The higher yield strength of the as-extruded sample led to a lower crack growth rate when compared to the ST sample.     

Synthesis,characterization and in vitro bioactivity of sol-gel-derived SiO2–CaO–P2O5–MgO bioglass

In this study, the synthesis of SiO₂–CaO–P₂O₅–MgO bioactive glass was performed by the sol-gel method. Sol-gel-derived bioglass material was produced both in powder and in discs form by uniaxial pressing, followed by sintering at 700 °C. The obtained material was evaluated by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), thermal gravimetric analysis (TGA) and differential scanning caloremetry (DSC) analyses. The biocompatibility evaluation of the formed glass was assessed through in vitro cell culture [alkaline phosphatase (AP) activity of osteoblasts] experiments and immersion studies in simulated body fluid (SBF) for different time intervals while monitoring the pH changes and the concentration of calcium, phosphorus and magnesium in the SBF medium. The SEM, XRD and FTIR studies were conducted before and after soaking of the material in SBF. At first, an amorphous calcium phosphate was formed; after 7 days this surface consisted of deposited crystalline apatite. The present investigation also revealed that the sol-gel derived quaternary bioglass system has the ability to support the growth of human fetal osteoblastic cells (hFOB 1.19). Finally, this material proved to be non-toxic and compatible for the proposed work in segmental defects in the goat model in vivo.     

Studies on polymer electrolyte poly(vinyl) pyrrolidone (PVP) complexed with ionic liquid: Effect of complexation on thermal stability,conductivity and relaxation behaviour

Polymer electrolyte films of PVP + x wt% ionic liquid (IL) (1-ethyl-3-methylimidazolium tetrafluoroborate [EMIM][BF₄]) for x = 0, 5, 10, 15, 20, 25 wt% have been prepared using solution cast technique. These films were characterized by TGA, DSC, FT-IR and ac impedance spectroscopy techniques. From XRD studies it is found that the inclusion of IL increases the amorphocity of polymeric membranes. DSC thermograms show that the glass transition (T_g) and melting temperatures (T_m) of PVP shift upon complexation with IL. FT-IR analysis shows the complexation of PVP with IL. Thermogravimetric studies show that PVP decomposes in a single step while PVP/IL membranes exhibit two step decomposition; lower value of decomposition temperature corresponds to the decomposition of PVP/IL complex while the higher decomposition temperature has been attributed to the decomposition of PVP. The decomposition temperature of PVP/IL complex decreases with the increasing amount of IL in the PVP membrane. Temperature dependence of conductivity and dielectric relaxation frequencies have also been studied for PVP and PVP/IL membranes. Both show thermally activated Arrhenius behaviour.     

In vitro degradation of novel bioactive polycaprolactone—20% tricalcium phosphate composite scaffolds for bone engineering

Our group recently fabricated novel 3D polycaprolactone—20% tricalcium phosphate (PCL-TCP) composite scaffolds for applications in bone engineering. The bioactivity of such synthetic biomaterials can be evaluated by examining its ability to initiate the formation of apatite on its surface when immersed in simulated body fluids (SBF). In this study, the in vitro degradation behaviors of these scaffolds were systematically monitored for varying time periods of 1, 7, 14, 21 and 28 days post-immersion in SBF at 37 °C. Weight loss and water absorption of the samples indicated that PCL-TCP scaffolds were only slowly degraded. Biochemical assays and pH measurements revealed that hydroxyapatite, the main inorganic constituent of bone, commenced to form on the surface of the scaffolds after 17 days of immersion in SBF. Von Kossa assays demonstrated that calcium deposits increased progressively on the surface of the scaffolds after soaking in SBF for 2 weeks. Scanning electron microscopy verified the surface crystallization of the apatite layer formed over the entire period of time. In conclusion, the synergy of PCL with TCP in a composite scaffold confers both bioresorbability as well as bioactivity that offer an exciting approach for bone regeneration purposes.     

In vitro behavior of fluoridated hydroxyapatite coatings in organic-containing simulated body fluid

A dense and pure hydroxyapatite [HA, Ca₁₀(PO₄)₆(OH)₂] coating and a fluoridated HA [Ca₁₀(PO₄)₆(OH)_0.67F_1.33] are deposited on Ti6Al4V substrates by sol-gel dip coating method. Glucose and bovine serum albumin have been added in standard simulated body fluid (SBF) to form organic-containing SBF in simulation of the physiological blood plasma. The HA and the fluoridated HA coatings are immersed in the standard and modified SBF for time periods of 2, 4, 7, 14 and 28 days at 37 ± 0.1°C. After soaking, the coating surface is examined for nucleation and growth of apatite using SEM morphological observation. The post-soaking SBF solutions are analyzed via Inductively Coupled Plasma spectroscopy for calcium ion concentration. The results show that at concentration of 40 g/L, bovine serum albumin has significant retardation effect on apatite precipitation from SBF onto pure or fluoridated HA coatings; Fluorine-incorporation in HA has positive bio-activation effect in both standard SBF and organic-containing SBF. However, glucose addition in SBF does not generate significant influence on the bioactivity of HA and fluoridated HA.     

Highly adherent bioactive glass thin films synthetized by magnetron sputtering at low temperature

Thin (380–510 nm) films of a low silica content bioglass with MgO, B₂O₃, and CaF₂ as additives were deposited at low-temperature (150°C) by radio-frequency magnetron sputtering onto titanium substrates. The influence of sputtering conditions on morphology, structure, composition, bonding strength and in vitro bioactivity of sputtered bioglass films was investigated. Excellent pull-out adherence (~73 MPa) was obtained when using a 0.3 Pa argon sputtering pressure (BG-a). The adherence declined (~46 MPa) upon increasing the working pressure to 0.4 Pa (BG-b) or when using a reactive gas mixture (~50 MPa). The SBF tests clearly demonstrated strong biomineralization features for all bioglass sputtered films. The biomineralization rate increased from BG-a to BG-b, and yet more for BG-c. A well-crystallized calcium hydrogen phosphate-like phase was observed after 3 and 15 days of immersion in SBF in all bioglass layers, which transformed monotonously into hydroxyapatite under prolonged SBF immersion. Alkali and alkali-earth salts (NaCl, KCl and CaCO₃) were also found at the surface of samples soaked in SBF for 30 days. The study indicated that features such as composition, structure, adherence and bioactivity of bioglass films can be tailored simply by altering the magnetron sputtering working conditions, proving that this less explored technique is a promising alternative for preparing implant-type coatings.     

Corrosion behavior in SBF for titania coatings on Mg–Ca alloy

TiO₂ coating was obtained by sol–gel method to improve the corrosion resistance of Mg–Ca alloy in human body environment. The corrosion behavior of Mg–1.0 Ca alloy with TiO₂ coating was investigated by electrochemical tests and immersion tests in simulated body fluid (SBF). Bare Mg–1.0 Ca alloy suffered serious attack after immersed in simulated body fluid only for 48 h. While for the Mg–1.0 Ca alloy with TiO₂ coating, the surface almost maintained intact with only several collapses after immersed in SBF for 168 h. The electrochemical test results showed that the free corrosion current (i _corr) of Mg–1.0 Ca alloy substrate was 3.3275e−2A/cm², while the i _corr of TiO₂ coating was only 1.58549e−5A/cm². Therefore, TiO₂ coating significantly improved the corrosion resistance of Mg–1.0 Ca alloy in SBF. This enhances the potential of Mg–Ca alloy used as biodegradable orthopedic material.     

Prediction of osteoconductive activity of modified potassium fluorrichterite glass-ceramics by immersion in simulated body fluid

Potassium fluorrichterite (KNaCaMg₅Si₈O₂₂F₂) glass-ceramics were modified by either increasing the concentration of calcium (GC5) or by the addition of P₂O₅ (GP2). The stoichiometric composition (GST), GC5 and GP2 were soaked in simulated body fluid (SBF) along with 45S5-type bioglass as a control. After immersion, surface analyses were performed using thin-film X-ray diffraction (TF-XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and Fourier-transform infrared (reflection) spectroscopy (FT-IR). All compositions showed the formation of a calcium phosphate rich surface layer in SBF; GST, GP2 and the bioglass control within 7 days of immersion and GC5 after 14 days. It was concluded that all compositions were likely to be osteoconductive in vivo, with GP2 providing the best performance in terms of the combination of rapid formation of the surface layer and superior mechanical properties. This glass-ceramic system has potential as a load bearing bioceramic for fabrication of medical devices intended for skeletal tissue repair.