Preparation of novel bioactive nano-calcium phosphate–hydrogel composites

Nano-sized hydroxyapatite (nHA) and carbonate-substituted hydroxyapatite (nCHA) particles were incorporated into a poly-2-hydroxyethylmethacrylate/polycaprolactone (PHEMA/PCL) hydrogel at a filler content of 10 wt%. Fourier transform infrared absorption, transmission electron microscopy, x-ray diffraction and scanning electron microscopy were used to analyse the physical and chemical characteristics of the calcium phosphate fillers and resultant composites. Nano-sized calcium phosphate particles were produced with a needle-like morphology, average length of 50 nm and an aspect ratio of 3. The nanoparticles were uniformly distributed in the polymer matrix. The addition of both HA and CHA in nano-form enhanced the bioactivity and biocompatibility of the PHEMA/PCL matrix. The carbonate-substitution has allowed for improved bioactivity and biocompatibility of the resultant composite, indicating the potential of this material for use in bone tissue engineering.     

Preparation of hydroxyapatite/α-tricalcium phosphate composites by colloidal process

Synthesised hydroxyapatite (HAp)/α-tricalcium phosphate (α-TCP) composites were prepared by colloidal process. Mixed slurries composed of 30 vol% HAp/α-TCP powder and 70 vol% aqueous solution containing a small amount of polymer dispersant were produced. HAp/α-TCP powder was blended with 0, 0.2, 0.4 or 1.0 mass fraction of α-TCP. Rheological behaviour of the HAp/α-TCP mixed slurries depended on the quantity of polymer dispersant and pH. Addition of suitable quantity of polymer dispersant at higher pH resulted in an increase in the stability of colloidal state due to electrostatic stabilisation. The optimum quantity of dispersant for the colloidal process was found to be proportional to the mass fraction of α-TCP. In the dehydration process of the slurries, pressure filtration technique was effective in preventing the gravity segregation of α-TCP. Thus, HAp/α-TCP composites with homogeneous microstructure and high relative density could be prepared by optimising the colloidal process.     

Characterisation of the bioactive behaviour of sol–gel hydroxyapatite–CaO and hydroxyapatite–CaO–bioactive glass composites

The fabrication and characterization of sol–gel derived hydroxyapatite–calcium oxide (HAp–CaO) material is investigated focusing on the effect of the addition of a bioactive glass on the material bioactive behaviour through the fabrication of a novel HAp–CaO (70 wt.%)–bioactive glass (30 wt.%) composite material. The bioactive behaviour of the materials was assessed by immersion studies in Simulated Body Fluid (SBF) and the alterations of the materials surfaces after soaking periods in SBF were characterized by Scanning Electron Microscopy (SEM) and Fourier Transform Infrared Spectroscopy (FTIR). A brittle and weakly crystalline carbonate hydroxyapatite (HCAp) layer was found to develop on the surface of all samples, few hours after immersion in SBF, confirming the high bioactivity of the material. Alterations of the morphology of the developed HCAp layer, which led to a more compact structure, were observed on the surface of composite samples after 7 days of immersion in SBF. The presence of the CaO phase seems to accelerate the formation of HCAp, while the bioactive glass affects both the morphology and cohesion of the developed layer.     

Preparation and characterization of polypropylene–wheat straw–clay composites

Preparation of polypropylene hybrid composite consisting of wheat straw and clay as reinforcement materials was investigated. The composite samples were prepared through melt blending method using a co-rotating twin-screw extruder. The composition of constituents of hybrid composite such as percentages of wheat straw, clay and maleic anhydride grafted polypropylene as a coupling agent was varied in order to investigate their influence on water absorption and flexural properties. The XRD analysis of composite samples containing clay showed shift in d₀₀₁ peak to lower 2θ indicating slight intercalation of polymer in clay sheets. The results of the study indicate that the increase in wheat straw and clay content in a composite increases the flexural modulus and reduces the resistance for water absorption. The increase in PP-MA coupling agent also increases the flexural modulus and resistance for water absorption. The morphological study by scanning electron microscope reveals that the addition of coupling agent increases the interfacial adhesion between the fibers and polymer matrix which is evidenced further from increased flexural modulus. Further, the particle size of wheat straw was analyzed before and after extrusion in order to investigate the effect of extrusion on wheat straw dimensions. The addition of clay as additional filler had no significant role on water absorption and flexural properties of the composite.     

Preparation of novel fibre–silica–Ag composites: the influence of fibre structure on sorption capacity and antimicrobial activity

Novel fibre–silica–Ag composites with biocidal activity were successfully produced by chemical modifying cotton (CO), wool (WO), silk (SE), polyamide (PA) and polyester (PES) fabrics and CO/PES and WO/PES fabric blends. A silica–Ag coating was prepared using a two-step procedure that included the creation of a silica matrix on the fibre surface via the application of an inorganic–organic hybrid sol–gel precursor [reactive binder (RB)] using a pad-dry-cure method, followed by the in situ synthesis of AgCl particles within the RB-treated fibres from solutions of 0.10 mM and 0.50 mM AgNO₃ and NaCl. The presence of the coating on the fibres was verified by scanning electron microscopy and energy-dispersive X-ray spectroscopy. The bulk concentration of Ag in the coated fibres was determined using inductively coupled plasma mass spectroscopy. The antimicrobial activity was determined for the bacteria Escherichia coli and Staphylococcus aureus and the fungus Aspergillus niger. The results show that the chemical and morphological structures of the fibres directly influenced their absorptivity and affinity for the Ag compound particles. As the amorphous molecular structure of the fibres and the amount of functional groups available as binding sites for Ag⁺ were increased, both the silver solution uptake and the concentration of the absorbed Ag compound particles increased. The chemical binding of Ag to the fibres significantly reduced the effectiveness of the antimicrobial activity of the Ag compound particles. Accordingly, an increase in the concentration of absorbed Ag was required to achieve a biocidal effect.     

Preparation of octacalcium phosphate by the hydrolysis of α-tricalcium phosphate

A new simple method of preparation for the thermodynamically unstable octacalcium phosphate [Ca₈H₂(PO₄)₆·5H₂O; OCP] has been developed using the hydrolysis of -Ca₃(PO₄)₂ instead of the conventional hydrolysis of CaHPO₄·2H₂O. The hydrolysis experiments were carried out by treating an -Ca₃(PO₄)₂(1 g)-H₂O(50 m) suspension for 3 h at temperatures in the range 40 to 80° C and at pHs in the range 3 to 7.5. The formation of OCR was limited to within a narrow region between formation regions of other phosphates. Favourable conditions for OCP preparation were, for example, 70° C, pH4.5 to 5.0 and 60° C, pH5.0. Particles of OCP were composed of tight aggregates of strip-like microcrystals growing probably along the [0 0 1] and (1 0 0) plane of the OCP structure. Nearly stoichiometric OCP was obtained under the most suitable conditions with good reproducibility. Pyrolytic processes of OCP were approximately consistent with the data published so far. However, the temperatures of the appearance and disappearance of pyrolytic crystalline phases and ionic species deviated slightly from the published data. Thermal dehydration up to 150° C without destruction of OCP and decomposition reactions above 300° C resulted in changes in surface area and average pore radius of OCP.     

Preparation and characterization of novel bioactive α-Tricalcium Phosphate doped with Dicalcium Silicate ceramics

This work describes the evaluation of pure α-Tricalcium Phosphate (TCP) and silica containing TCP ceramics in the system Dicalcium Silicate–Tricalcium Phosphate (C₂S–TCP) as a potential substrate for bone tissue engineering. The ceramics were soaked in dynamic simulated body fluid (SBF) for 2 weeks and characterized by SEM-WDS, XRD, and TEM analysis, and the results indicated that a carbonated hydroxyapatite (CHA) was formed on the surface of the ceramics. In addition, cell attachment assay showed that the ceramics supported the adult mesenchymal stem cells of human origin (hMSCs-A) adhesion and spreading, and the cells established close contacts with the ceramics after 24 h of culture. Also, cellular assays have shown a greater ability of hMSCs-A to express markers of the osteoblast phenotype (ALP, Col I, OC) in the C₂S doped α-TCP ceramics, indicating osteoblastic differentiation as a result of the increased concentration of silicon in solid solution in α-TCP. These findings indicate that the C₂S doped α-TCP ceramics possess good bioactivity, and biocompatibility, and might be promising for bone implant material.     

Preparation and characterization of BaTiO3–natural muscovite composites

Journal of Materials Science: Materials in Electronics - Natural muscovite (nM) exhibiting magnetic vortex states are ball milled into fine powder and mixed in different relative ratios (weight %)...     

Preparation and characterization of hydroxyapatite/polycaprolactone–chitosan composites

Hydroxyapatite (HA)/polycaprolactone (PCL)–chitosan (CS) composites were prepared by melt-blending. For the composites, the amount of HA was varied from 0% to 30% by weight. The morphology, structure and component of the composites were evaluated using environmental scanning electron microscope, X-ray diffraction and Fourier transform infrared spectroscope. The tensile properties were evaluated by tensile test. The bioactivity and degradation property were investigated after immersing in simulated body fluid (SBF) and physiological saline, respectively. The results show that the addition of HA to PCL–CS matrix tends to suppress the crystallization of PCL but improves the hydrophilicity. Adding HA to the composites decreases the tensile strength and elongation at break but increases the tensile modulus. After immersing in SBF for 14 days, the surface of HA/PCL–CS composites are covered by a coating of carbonated hydroxyapatite with low crystallinity, indicating the excellent bioactivity of the composites. Soaking in the physiological saline for 28 days, the molecular weight of PCL decreases while the mass loss of the composites and pH of physiological saline increase to 5.86% and 9.54, respectively, implying a good degradation property of the composites.     

Preparation and magnetic characteristics of mesoporous nickel oxide–silica composites

Mesoporous NiO–SiO₂ (MCM-41) silica-matrix composites with various nickel oxide concentrations (NiO : SiO₂ = 0.025 : 1 to 0.2 : 1) have been produced by oxide cocondensation under hydrothermal synthesis conditions in the presence of cetyltrimethylammonium bromide as a template and (2-cyanoethyl) triethoxysilane as an organosubstituted trialkoxysilane additive. X-ray diffraction data have been used to evaluate the maximum nickel(II) oxide concentration (NiO : SiO₂ = 0.1 : 1) that allows the ordered mesopore structure of MCM-41 to persist in the silica-matrix composites. We have studied the magnetic properties of this material as functions of temperature and magnetic field. The results demonstrate that the magnetic properties of the nanocomposite with NiO : SiO₂ = 0.1 : 1 at low temperatures (T < 20 K) are determined by incomplete spin compensation in the matrix and on the surface of the NiO nanoparticles.     

The influence of hybrid phosphate–alumina pigments on properties of Ethylene-propylene-diene rubber composites

In this work Ethylene-propylene-diene (EPDM) rubber vulcanizates were pigmented with a new hybrid pigment containing nano-phosphate layer deposited on surface of micronized alumina. This new pigment contains both single and double-ion phosphates. Different rheological, chemical and physical properties of the nano-pigmented EPDM vulcanizates were studied and compared to the non-pigmented EPDM composites. These pigmented composite properties were studied in the presence and absence of maleic anhydride (MAH) which was employed as a compatibilizer. The bound rubber and cross-linking density were calculated. The results revealed that composites pigmented with 3Zn·1Ca phosphate/alumina/EPDM and 1Zn·3Ca phosphate/alumina/EPDM exhibited the best properties compared to other pigmented composites.     

Rheological evaluations and in vitro studies of injectable bioactive glass–polycaprolactone–sodium alginate composites

Composite pastes composed of various amounts of melt-derived bioactive glass 52S4 (MG5) and polycaprolactone (PCL) microspheres in sodium alginate solution were prepared. Rheological properties in both rotatory and oscillatory modes were evaluated. Injectability was measured as injection force versus piston displacement. In vitro calcium phosphate precipitation was also studied in simulated body fluid (SBF) and tracked using scanning electron microscopy, X-ray diffraction and FTIR analyses. All composite pastes were thixotropic in nature and exhibited shear thinning behavior. The magnitude of thixotropy decreased by adding 10–30 wt% PCL, while further amounts of PCL increased it again. Moreover, the composites were viscoelastic materials in which the elastic modulus was higher than viscous term. The pastes which were just made of MG5 or PCL had poor injectability, whereas the composites containing both of these constituents exhibited reasonable injectability. All pastes revealed adequate structural stability in contact with SBF solution. In vitro calcium phosphate precipitation was well observed on the paste made of MG5 and somewhat on the pastes with 10–40 wt% PCL, however the precipitated layer was amorphous in nature. Overall, the produced composites may be appropriate as injectable biomaterials for non-invasive surgeries but more biological evaluations are essential.     

Development of strong and bioactive calcium phosphate cement as a light-cure organic–inorganic hybrid

In this research, light cured calcium phosphate cements (LCCPCs) were developed by mixing a powder phase (P) consisting of tetracalcium phosphate and dicalcium phosphate and a photo-curable resin phase (L), mixture of hydroxyethylmethacrylate (HEMA)/poly acrylic-maleic acid at various P/L ratios of 2.0, 2.4 and 2.8?g/mL. Mechanical strength, phase composition, chemical groups and microstructure of the cured cements were evaluated at pre-set times, i.e. before and after soaking in simulated body fluid (SBF). The proliferation of Rat-derived osteoblastic cells onto the LCCPCs as well as cytotoxicity of cement extracts were determined by cell counting and 3-{4,5-dimethylthiazol-2yl}-2,5-diphenyl-2H-tetrazolium bromide assay after different culture times. It was estimated from Fourier transforming infrared spectra of cured cements that the setting process is ruled by polymerization of HEMA monomers as well as formation of calcium poly-carboxylate salts. Microstructure of the cured cements consisted of calcium phosphate particles surrounded by polymerized resin phase. Formation of nano-sized needlelike calcium phosphate phase on surfaces of cements with P/L ratios of 2.4 and 2.8?g/mL was confirmed by scanning electron microscope images and X-ray diffractometry (XRD) of the cured specimen soaked in SBF for 21?days. Also, XRD patterns revealed that the formed calcium phosphate layer was apatite phase in a poor crystalline form. Biodegradation of the cements was confirmed by weight loss, change in molecular weight of polymer and morphology of the samples after different soaking periods. The maximum compressive strength of LCCPCs governed by resin polymerization and calcium polycarboxylate salts formation was about 80?MPa for cement with P/L ratio of 2.8?g/mL, after incubation for 24?h. The strength of all cements decreased by decreasing P/L ratio as well as increasing soaking time. The preliminary cell studies revealed that LCCPCs could support proliferation of osteoblasts cultured on their surfaces and no cytotoxic effect was observed for the extracts of them.     

Long-term conversion of 45S5 bioactive glass–ceramic microspheres in aqueous phosphate solution

The conversion of 45S5 glass and glass–ceramics to a hydroxyapatite (HA)-like material in vitro has been studied extensively, but only for short reaction times (typically <3 months). In this paper, we report for the first time on the long-term conversion of 45S5 glass–ceramic microspheres (designated 45S5c) in an aqueous phosphate solution. Microspheres of 45S5c (75–150 μm) were immersed for 10 years at room temperature (~25 °C) in K₂HPO₄ solution with a concentration of 0.01 M or 1.0 M, and with a starting pH of 7.0 or 9.5. The reacted 45S5c microspheres and solutions were analyzed using structural and analytical techniques. Only 25–45 vol% of the 45S5c microspheres were converted to an HA-like material after the 10 year reaction. In solutions with a starting pH of 9.5, an increase in the K₂HPO₄ concentration from 0.01 to 1.0 M resulted in a doubling of the volume of the microspheres converted to an HA-like material but had little effect on the composition of the HA-like product. In comparison, reaction of the 45S5c microspheres in the solution with a starting pH of 7.0 resulted in an HA-like product in the 0.01 M K₂HPO₄ solution but a calcium pyrophosphate product, Ca₁₀K₄(P₂O₇)₆.9H₂O, in the 1.0 M solution. The consequences of these results for the long-term use of 45S5 glass–ceramics in biomedical applications are discussed.     

A novel bioactive three-dimensional β-tricalcium phosphate/chitosan scaffold for periodontal tissue engineering

The development of suitable bioactive three-dimensional scaffold for the promotion of cellular proliferation and differentiation is critical in periodontal tissue engineering. In this study,porous β-tricalcium phosphate/chitosan composite scaffolds were prepared through a freeze-drying method. These scaffolds were evaluated by analysis of microscopic structure, porosity, and cytocompatibility. The gene expression of bone sialoprotein (BSP) and cementum attachment protein (CAP) was detected with RT-PCR after human periodontal ligament cells (HPLCs) were seeded in these scaffolds. Then cell–scaffold complexes were implanted subcutaneously into athymic mice. The protein expression of alkaline phosphatase (ALP) and osteopontin (OPN) was detected in vivo. Results indicated that composite scaffolds displayed a homogeneous three-dimensional microstructure; suitable pore size (120 μm) and high porosity (91.07%). The composite scaffold showed higher proliferation rate than the pure chitosan scaffold, and up-regulated the gene expression of BSP and CAP. In vivo, HPLCs in the composite scaffold not only proliferated but also recruited vascular tissue ingrowth. The protein expression of ALP and OPN was up-regulated in the composite scaffold. Therefore, it was suggested that the composite scaffold could promote the differentiation of HPLCs towards osteoblast and cementoblast phenotypes.     

Effect of filler type on the mechanical properties of self-reinforced polylactide–calcium phosphate composites

Bioabsorbable polymers are of interest as internal fracture fixation devices. Self-reinforcement has been developed to improve the mechanical properties of the material and the addition of calcium phosphate fillers improves the bioactivity. Composite plates, produced by compression molding preimpregnated sheets of polylactide fibers coated in a polylactide matrix have been degraded in simulated body fluid for up to 12 weeks. Some samples also contained hydroxyapatite or tricalcium phosphate filler particles. Degradation was measured by monitoring the water uptake and mass decrease of the samples, as well as carrying out four point bend tests to assess the mechanical properties of the material. By 12 weeks, it was found that the unfilled samples absorbed more water and showed greater mass loss than the samples containing calcium phosphate fillers. Also, the flexural modulus and yield stress decreased significantly at week 12 for the unfilled samples. Adding hydroxyapatite (HA) or tricalcium phosphate (TCP) to the composite increased the flexural modulus and yield strength to values within the range of those reported for cortical bone and these values were maintained over the 12-week period.     

The effect of zinc oxide–phosphate core–shell pigments on the properties of blend rubber composites

In this work the rheological, physico-mechanical, thermal and morphology studies were performed on a blend of EPDM/SBR (ethylene propylene diene monomer/styrene butadiene rubber) (50/50) loaded with a new prepared core–shell pigment based on a core of zinc oxide which presents the major component of the prepared pigment (≈90%) covered with a shell of phosphate, this shell comprises only about (≈10%). The new pigments were added in different concentration to the rubber blend and were compared to blends pigmented with commercial zinc oxide and zinc phosphate. The results showed that the new pigments exhibited better rheometric, and physico-mechanical properties. In addition, these prepared pigments showed decrease of equilibrium swelling in toluene solvent and increase in crosslink density for EPDM/SBR blend. The efficiency of prepared core–shell pigments were also evaluated by studying the surface morphology (SEM) and thermal properties TGA (thermal gravimetric analysis). The prepared pigments loading of 10 phr (parts per hundred parts of rubber) showed the optimum properties of EPDM/SBR blend than rubber loaded with higher concentration of the commercial pigments, which indicated that the new core–shell pigment is more economic with better performance than commercial zinc oxide and phosphates individually.     

Fabrication and properties of novel composites in the system Al–Zr–C

Composite bodies in the system Al–Zr–C, with about 95% relative density, were obtained by heating the compact body of powder mixture consisting of Al and ZrC (5 : 1 mol %) in Ar at 1100–1500°C for various lengths of time. Components of the material heated at more than 1200°C were Al, Al3Zr, ZrC and AlZrC2. The Al3Zr exhibited plate-like aggregation, and its size increased with increasing temperature. In the material heated at 1500°C for 1 h, the largest plate-like Al3Zr aggregation was 2000 m long and 133 m thick. Then the AlZrC2 was present as well-proportioned hexagonal platelet particles with a 8–9 m diameter and a 1–2 m thickness in the interior of the plate-like Al3Zr aggregation and Al matrix phase. The average three-point bending strength of the bodies was 140–190 MPa, and the maximum strength was 203 MPa in the body heated at 1300°C for 1 h. The body heated at 1500°C for 1 h showed high oxidation resistivity to air up to 1000°C.     

Synthesis and characterization of novel γ-induced porous PHEMA–IL composites

A novel porous polymer-ionic liquid composite with poly(2-hydroxyethyl methacrylate) (PHEMA) and 1-butyl-3-methylimidazolium hexafluorophosphate (BMIPF₆) has been synthesized by γ-irradiation without heat or chemical initiators. The products can be reversibly converted into organogels. The composites are potential candidates for electrochemical applications. The use of γ-radiation can be a simple and versatile alternative way to obtain these materials.     

Preparation and characterization of hybrid antimicrobial materials based on Zn–Lu composites

The development of advanced functional materials, capable of providing effective antimicrobial activity, has a big demand from the contemporary society. Advanced functional antimicrobial amorphous silica composites (ASC) are prepared by using sol–gel process and modified by Zn ions and rare-earth element Lu. The preparation conditions are optimized by single-factor analysis, and as-prepared functional hybrids are characterized by scanning electron microscopy (SEM), X-ray diffraction analysis, X-ray photoelectron spectroscopy (XPS), atomic adsorption spectrometry and inductively coupled plasma analyses. The presence of homogeneously mixed Zn and Lu, in the form of ZnO and Lu₂O₃, and dense micropores is confirmed by SEM and XPS. The amorphous structure and large surface area are beneficial for better antimicrobial performance. The as-prepared Zn–Lu ASC exhibited excellent antimicrobial properties against Escherichia coli and Staphylococcus aureus. We demonstrate that the addition of rare-earth element, Lu, has rendered synergistic effect on antimicrobial properties by increasing the release of Zn ions and generating excess reactive oxygen species. The present study provides a mechanistic insight and novel approach to fabricate functional antimicrobial materials for a wide range of applications.