Physico-chemical and biological properties of novel Eu-doped carbonization modified tricalcium silicate composite bone cement

This paper introduces a novel composite bone cement (Eu:HAp/V-C₃S), which is composed of carbonated tricalcium silicate (V-C₃S) and europium-doped hydroxyapatite (Eu:HAp), and Eu:HAp was generated by hydrothermal synthesis. The physical and chemical properties, mineralization in vitro, biocompatibility and bacteriostasis of the composite bone cement were evaluated. The results show that the Eu:HAp/V-C₃S composite bone cement has good setting properties and a relatively low pH value. The composite bone cement with 0.1 wt% Eu has a higher compressive strength than pure V-C₃S (141.06% higher than pure V-C₃S), which can greatly improve the mechanical properties of the materials. The in vitro immersion test shows that composite bone cement has good mineralization ability. The cell test proves that it has good cell proliferation ability and low cytotoxicity. In addition, the bacteriostatic experiment also verifies that composite bone cement has bacteriostatic effect to some degree. These results indicate that Eu:HAp/V-C₃S composite bone cement is a promising biomedical material.     

Studies on novel bioactive glasses and bioactive glass-nano-HAp composites suitable for coating on metallic implants

A series of novel zinc oxide (ZnO) containing bioactive glass compositions in SiO₂-Na₂O-CaO-P₂O₅ system and composite with hydroxyapatite (HAp) nano-particles were developed and applied as coating on Ti-6Al-4V substrates. The bioactive glasses and their composites were also processed to yield dense scaffolds, porous scaffolds and porous bone filler materials. The coating materials and the coatings were characterized and evaluated by different in vitro techniques to establish their superior mechanical properties. The cytotoxicity test of the coating material, porous and dense scaffolds and coated specimens showed non-cytotoxicity, biocompatibility and promising in vitro bioactivity for all tested samples. The dissolution behaviour studies of the bioactive glasses and the composites in simulated body fluid showed promising in vitro release pattern and bioactivity for all tested samples. Addition of nanosized HAp improves mechanical properties of the bioactive glass coating without affecting the in vitro bioactivity.     

Microstructural,dielectric, mechanical,and biological properties of hydroxyapatite (HAp)/BZT-BCT (0.5Ba(Zr0.2Ti0.8)O3-0.5(Ba0.7Ca0.3)TiO3) bio-composites with improved mechano-electrical properties for bone repair

Hydroxyapatite (HAp; Ca₁₀(PO₄)₆(OH)₂) is a commonly used biomaterial for bone tissue repair applications but it has poor electrical conductivity. Whereas, BZT-BCT (0.5Ba(Zr_0.2Ti_0.8)O₃-0.5(Ba_0.7Ca_0.3)TiO₃) is a lead-free piezoelectric material which can mimic the stress-generated electric potential of electrically-excitable tissues such as bone. This study investigated the mechanical, electrical and bio properties of xHAp/(1-x)BZT-BCT composites. xHAp/(1-x)BZT-BCT composites (with x = 5, 10, 15 and 20 wt%) were synthesized by high energy ball milling (HEBM) assisted solid-state reaction route. X-ray diffraction, scanning electron microscopy, density measurements and cell-material interaction studies of sintered HAp/BZT-BCT composites were carried out and discussed in detail. Dielectric properties of sintered composites were evaluated and compared with the existing theoretical models. Different mechanical properties like Vicker's hardness, fracture toughness, and diametral tensile strength were measured to assess the usability of synthesized composites for load-bearing orthopaedic applications. These various studies showed that incorporation of BZT-BCT in HAp improved its mechanical and electrical properties and thereby significantly increased the proliferation of human osteogenic MG-63 cells. Among all the composites, better mechanical, electrical and biological properties were obtained in 10HAp/90BZT-BCT composites.     

Corrosion behaviour and biocompatibility of nanoporous niobium incorporated titanium oxide coating for orthopaedic applications

This study investigates the surface characteristics, in vitro biocompatibility and electrochemical behaviour of nanoporous niobium incorporated titanium dioxide (Nb-incorporated TiO₂) coated 316L stainless steel (SS) for orthopaedic applications. The coating material was synthesized by sol-gel methodology and was deposited on 316L SS by using spin coating technique and heat treatment. The experimental conditions were optimized to obtain a coating with nanoporous morphology. The coating was characterized using attenuated total reflectance-Infrared spectroscopy (ATR-IR), X-ray diffraction analysis (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX), atomic force microscopy (AFM) and transmission electron microscopy (TEM). The analysis confirmed the formation of a crystalline nanoporous Nb-incorporated TiO₂ coating with hydrophilic nature. Mechanical studies validated that the coating has excellent adhesion to the specimen and appreciable hardness value. In vitro bioactivity test confirmed that the nanoporous morphology of the coating facilitated enhanced hydroxyapatite (HAp) growth. Electrochemical studies established that the insulative nature of the coating provides excellent corrosion resistance to 316L SS.     

Fast-setting and high fracture toughness Ce-TZP/tricalcium silicate composite dental cement

For dental materials, a certain defect tolerance would be beneficial. Some Ceria-stabilized zirconia (Ce-TZP) composites are promising dental repair materials, as they have been shown to exhibit an obvious amount of transformation-induced plasticity with almost no dispersion in strength data. The purpose of this study was to design a novel tricalcium silicate (C₃S)-based dental repair material by adding 10 mol.% Ce-TZP to improve fracture toughness and dipotassium hydrogen phosphate (K₂HPO₄) as the setting accelerator. The study evaluated the physicochemical properties, in vitro cell activity, and antibacterial activity of Ce-TZP/C₃S composite cement, and the results revealed that Ce-TZP/C₃S cement showed a fast-setting ability and good washout resistance when the setting time was controlled within 26–43 min. With increasing Ce-TZP content, the mechanical properties, especially the flexural strength and fracture toughness, were gradually enhanced. Additionally, the 30% Ce-TZP/C₃S composite showed good antibacterial activity and in vitro cytocompatibility. The study concluded that 30% Ce-TZP/C₃S composites could be regarded as ideal candidates in the field of dental materials due to their excellent physical and chemical properties, antimicrobial activity, in vitro cytocompatibility, outstanding fracture toughness and fast-setting ability.     

Carbon fiber‐reinforced gelatin composites. I. Preparation and mechanical properties

Composites were made from carbon fibers and gelatin using a solvent‐casting or solution‐impregnation technique. Relationships between the fiber volume fraction (Vf), glycerol (plasticizer) content, gelatin content, fiber form, and mechanical properties (tensile strength and modulus, elongation at break, and shear strength) of the composites were investigated. In long carbon fiber gelatin composite (C_L/Gel), tensile strength, modulus, and shear strength increased steadily with the Vf. In the case of a short carbon fiber gelatin composite (C_S/Gel), an initial improvement in tensile strength and modulus was followed by a reduction, whereas the shear strength improved with the Vf and then reached a constant value. The elongation decreased with the Vf for both composites. It is shown that C_L/Gel had higher values of strength, modulus, and elongation than did C_S/Gel at any Vf level. The effects of glycerol and gelatin contents on the mechanical properties of the composites were found to be much less significant as compared to the Vf. According to scanning electron microscopic observation of the fracture surfaces, the fibers were uniformly distributed in the gelatin matrix, but the interfacial adhesion between the gelatin matrix and the carbon fibers was not very good for both composites. Fiber surface modification would be necessary to further improve the mechanical properties of the two composites. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 987–993, 2000     

Physicochemical and biological properties of composite bone cement based on octacalcium phosphate and tricalcium silicate

Biocompatible tricalcium silicate (C₃S) bone cement is widely used as dental and bone repair material; however, its long setting time, poor injectability and low initial mechanical properties limit clinical applications. In order to improve C₃S silicate bone cement and its derivatives to play a more important role in tooth restoration, bone defect repair, implant coating and tissue engineering scaffolds, a novel C₃S and octacalcium phosphate (OCP) composite bone cement (OCP/C₃S) was prepared and evaluated for setting time, injectability, anti-flocculation, pH, microstructure, bioactivity and cytotoxicity. The setting time of the OCP/C₃S composite bone cement was controlled within the clinically operable time range (8.3–13.7 min); the cement exhibited good compressive strength, injectability (93.54%), and anti-collapse performance. The 20% OCP/C₃S composite bone cement had a compressive strength of 28.94 MPa, 93% stronger than pure C₃S (14.98 MPa). An in vitro immersion test showed that the composite bone cement had excellent hydroxyapatite forming ability, proper degradation rate, and a low pH value. Cellular experiments confirmed the low cytotoxicity of the composite bone cement and its great capacity for cell proliferation. These results indicate that 20% OCP/C₃S composite bone cement is a promising biomaterial.     

Morphological and thermal characterization of zirconia/hydroxyapatite composites prepared via sol-gel for biomedical applications

The thermal behavior of pure ZrO₂ and hydroxyapatite (denoted as Z and HAp, respectively), as well as three composites with different content of Z and HAp (Z90HAp10, Z70HAp30 and Z50HAp50) prepared via sol-gel method has been studied by thermogravimetry (TG) and first-order derivative of TG up to 1200?°C under inert gas atmosphere. Dehydration, loss of alcohol and acetylacetone and a multi-step thermal decomposition processes has been identified by analyzing the gases evolved in each step by Fourier transform infrared spectroscopy (FTIR). Fresh samples of Z-rich composites undergo an abrupt ejection of material from the crucible around 200?°C with noticeable increase of the sample temperature. During the occurrence of this phenomenon FTIR spectra demonstrated the evolution of gases (CO, CO₂, acetone and ethylene) due to the simultaneous decomposition of acetylacetone and ethanol, not present in the samples calcined at 120?°C. As far as the structural study is concerned, pure Z crystallizes at 1000?°C in the monoclinic system, but the presence of HAp in the composite materials enables the crystallization of Z in the tetragonal phase. Finally, the amorphization degree increases with increasing the content of Z in all the composites treated at 600 and 1000?°C.     

Carbon fiber‐reinforced gelatin composites. II. Swelling behavior

Carbon fiber‐reinforced gelatin composites have been prepared in our laboratory to obtain a novel biomaterial of improved mechanical properties. The swelling behavior (swelling rate, swelling kinetics, maximum solvent uptake, etc.) for both continuous carbon fiber‐reinforced gelatin composite (C_L/Gel) and short carbon fiber‐reinforced gelatin composite (C_S/Gel) are investigated. Experimental data show that the swelling process of the original gelatin and gelatin matrixes in both composites follows a second‐order kinetics. The swelling of the gelatin matrixes in both composites proceeds slower than that of the pristine gelatin, and depends on fiber form and fiber volume fraction (Vf). Results indicate that the presence of carbon fibers suppresses the swelling of the gelatin matrixes in both composites. It is found that the gelatin matrix in C_S/Gel possesses a smaller swelling rate and maximum solvent uptake than that in C_L/Gel. A mechanism governing these phenomena is discussed in this article. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 994–998, 2000     

Titania/hydroxyapatite bi-layer coating on Ti metal by electrophoretic deposition: Characterization and corrosion studies

Titania–hydroxyapatite (HAp) bi-layer coating on Ti metal substrate with improved adhesion strength is fabricated by a simple two step processes: electrodeposition of Ti sol and electrophoretic deposition of HAp powder, followed by heat treatment at 800 °C. At optimized process parameters, the bi-layer developed consists of dense, thin and crystalline titania interlayer with porous, thick and crystalline HAp top layer. The heat treatment of bi-layer coating allows elemental intermixing at the interface of TiO₂ and HAp, as determined by energy dispersive X-ray spectroscopy (EDX) and Raman spectra analysis. Compared to monolithic HAp coating, the TiO₂/HAp bi-layer coating shows significant enhancement in the adhesion strength (48 MPa) as well as corrosion resistance without compromising its biocompatibility. The steep increase in adhesion strength is believed to be due to mechanical interlocking and diffusion bonding at the interface. Presence of dense titania interlayer in the bi-layer coating reduces the corrosion current in Ringer's solution to a negligible value (～100 nA).     

Piezoelectric and mechanical properties of hydroxyapatite/titanium oxide composites

Hydroxyapatite (HAp) is the most common bioactive ceramic used to replace hard tissue in the body. Because of its low resistance and fragile nature, more attention is being given to composites based on HAp such as HAp/TiO₂ composites. This study aims at reporting the synthesis of HAp/TiO₂ composites (hereafter named HT composite) by sol-gel and co-precipitation methods assisted by ultrasonic radiation. The structural characterization was carried out by X-ray Diffraction (XRD) and Scanning Transmission X-ray Microscopy (STXM) techniques using synchrotron radiation, which allowed a mixture of phases to be identified separately in the two materials once the composite was formed. A Rietveld refinement for XRD data determined the phase percentage and structural parameters obtained for each material. In addition, crystallite size using the modified Scherrer equation was determined. A piezoelectric character of the two materials was confirmed by Piezoresponse Force Microscopy (PFM) to determine the piezoelectric coefficient (d_eff). Finally, PinPoint-AFM force curves confirmed an increase in the Young's modulus value for the HT composite.     

Interfacial microstructure and strengthening mechanisms of Cf/Mg composite with double-layer interface

In order to overcome the interfacial incompatibility of carbon fiber reinforced magnesium matrix (C_f/Mg) composites, a double-layer interface (ZrO₂–MgO) is designed in this work. Carbon fiber was modified with ZrO₂ coating by sol-gel process. Microstructural examination reveals that MgO layer forms on the surface of ZrO₂ coating by ZrO₂ reacting with Mg during the composite fabrication. Such double-layer interface could inhibit Al₄C₃ and hence prevent fiber damage. Meanwhile, the wettability was improved for the reaction between ZrO₂ and Mg. Thus the tensile strength of ZrO₂-C_f/AZ91D composite was 68.0% higher than that of the unmodified one. Due to the fiber bundle pull-out, debonding and crack deflection, the toughness of C_f/Mg composite with double-layer interface is increased simultaneously.     

Deposition of hydroxyapatite coatings by axial plasma spraying: Influence of feedstock characteristics on coating microstructure,phase content and mechanical properties

Axial plasma spray is one of the thermal spray techniques to deposit multifunctional advanced coatings. The present work explores the use of this process to deposit thin, continuous, and adherent Ca₅ (PO₄)₃OH (hydroxyapatite, HAp) coatings and characterize its microstructure, phases, hardness and adhesion strength. Three different suspension-deposited HAp coatings were investigated and compared with powder-deposited HAp coating on a Ti6Al4V substrate. The effect of mean solute particle size and solid-loading in the suspension has been explored on the evolution of microstructure, phase content and mechanical properties of axial suspension plasma sprayed (ASPS) coatings. Phase-characterization has shown retention of hydroxyapatite phase and coating crystallinity in the deposited coatings, whereas the adhesion strength of the HAp coating decreased from ～40 MPa to ～13 MPa when bioglass was added to the feedstock material. The lower solid load content and lower mean solute particle size in the suspension were found to be beneficial in achieving porous, rougher, and well-adhering coatings. This work concludes that ASPS can potentially deposit thin HAp coatings (< 50 μm) with high adhesion strength.     

Mechanical properties of HAp–ZrO2 composites

Hydroxyapatite is a well-known and valuable implant material with bioactive properties. Full utilisation of the unique properties of hydroxyapatite ceramics is, however, possible only after its proper reinforcement, i.e., by preparation of composites. In the present work zirconia reinforced hydroxyapatite composites were obtained by hot pressing method. The reinforcing phase in the form of ZrO₂ particles was selected due to the satisfactory biocompatibility of ZrO₂ and also because of its exceptional mechanical properties.Our investigations were aimed at assessing the influence of varying ZrO₂ on the phase composition and mechanical properties of HAp–ZrO₂ composites. In order to produce dense sinters, we used three types of initial zirconia powders which differed in morphology and contents of the tetragonal and monoclinic phases. We studied the influence of these oxides on thermal stability of hydroxyapatite matrix as well as on the phase composition and mechanical properties of the composite materials produced.     

Dense Nanostructured Hydroxyapatite Coating on Titanium by Aerosol Deposition

In order to improve biocompatibility of Ti metal substrates, 1-μm-thick nanostructured hydroxyapatite (HAp) coatings were deposited on the substrates through aerosol deposition, which sprays HAp powder with an average particle size of 3.2 μm at room temperature in vacuum. The original HAp particles were fractured into nanoscale fragments to form highly dense coating during the deposition process. Density of the HAp coating was 98.5% theoretical density (TD). Transmission electron microscopy observation revealed that the as-deposited coating consisted of HAp crystallites with average grain size of 16.2 nm and amorphous phase. Tensile adhesion strength between the coating and the substrate was 30.5±1.2 MPa. Annealing up to 500°C in air increased crystallinity and grain size in the coating without any delamination or crack according to X-ray diffraction analysis and electron microscopy. MTS assay and alkaline phosphatase activity measurements with MC3T3-E1 preosteoblast cell revealed that the biocompatibility was greatly improved by postdeposition heat treatment at 400°C in air due to well-crystallized HAp with average grain size of 29.3 nm. However, further heat treatment at 500°C deteriorated biocompatibility due to rapid growth of HAp grains to average size of 99 nm. Cross section of the coating on a commercially available Ti dental implant revealed full coverage of the surface with HAp.     

A sorption balance study of water vapour sorption on anhydrous cement minerals and cement constituents

The phenomenon of water vapour sorption by powdered cement constituents exposed to different relative humidities and temperatures was studied. The individual clinker phases C₃S, C₂S, C₃A, C₄AF, calcium sulfates and CaO were tested. Using a water sorption balance, the amount of chemically and physically sorbed water per unit of surface area of the powders and the relative humidity at which water sorption starts to occur on the phases were determined. Various cement clinker phases prehydrate very differently. CaO and C₃A were found to be most reactive towards water vapour whereas the silicates react less. CaO starts to sorb water at very low RHs and binds it chemically. Beginning at 55% RH, orthorhombic C₃A also sorbs significant amounts of water and binds it chemically and physically. Water sorption of C₃S and C₂S only begins at 74% RH, and the amount of water sorbed is minor. Calcium sulfates sorb water predominantly physically.     

Influence of carbon black distribution on performance of oxide cathodes for Li ion batteries

The influence of carbon black content and carbon black distribution on performance of oxide-based cathodes, such as LiCoO₂ and LiMn₂O₄, is investigated. The electronic conductivity of oxide material/carbon black composites is compared with electrochemical characteristics of the same composites. Uniformity of carbon black distribution in cathode composites is achieved using novel coating technology in cathode preparation. In this technology, the active particles are first pretreated in a gelatin solution. The adsorbed gelatin then controls the deposition of carbon black so that carbon black particles are uniformly distributed in the final composite. The influence of various parameters, such as pH of gelatin, amount of gelatin and concentration of carbon black on the uniformity of carbon black distribution is investigated. It is shown that the conventional technology of cathode preparation yields quite non-uniform distribution of carbon black in cathode material. At the end, we demonstrate that uniformity of carbon black distribution has a crucial impact on reversible capacity, especially at high current densities.     

High-entropy environmental barrier coating for the ceramic matrix composites

A novel high-entropy material, (Yb_0.2Y_0.2Lu_0.2Sc_0.2Gd_0.2)₂Si₂O₇ ((5RE_0.2)₂Si₂O₇) was prepared by the sol-gel method and investigated as a promising environmental barrier coating (EBC) for SiC-based composites. The results of X-ray diffraction and transmission electron microscopy indicated that rare-earth elements were distributed homogeneously in the single monoclinic phase. Moreover, it was found that the new material (5RE_0.2)₂Si₂O₇ had good phase stability, well-matched coefficient of thermal expansion with SiC-based composite, and excellent resistance to water-vapor corrosion. The water-vapor corrosion test of (5RE_0.2)₂Si₂O₇ coated C_f/SiC composites further confirmed that (5RE_0.2)₂Si₂O₇ was suitable for application as EBC material and could provide effective protection to C_f/SiC composites from water-vapor damage.     

Fabrication of structure-controlled hydroxyapatite/zirconia composite

The structure-controlled hydroxyapatite/zirconia (HAp/ZrO₂) composites were fabricated. At first, cylindrical hydroxyapatite (HAp) samples were prepared by the extrusion process, and then the extruded HAp cylindrical samples were coated with 3 mol% of Y₂O₃ partially stabilized ZrO₂ slurry, dried and aligned unidirectionally to form a composite bulk. The volume fraction of ZrO₂ in the HAp/ZrO₂ composite was estimated to be about 23 vol%. Bulk density and bending strength of the composites increased with sintering temperature. Fracture energy of HAp/ZrO₂ composite sintered at 1350 °C was approximately 1.6 times higher than that of monolithic HAp. Although the bending strength of HAp/ZrO₂ composite prepared in this study was relatively low, it exhibited high fracture energy than HAp monolithic and a non-brittle fracture behavior was obtained without using fiber as the reinforcement.     

Fullerene (C60)–transitional metal (Ti) composites: Structural and biological properties of the thin films

Thin films of the binary C₆₀/Ti composites (with various phase ratios) were deposited on the Si(001) wafers and microscopic glass coverslips in continuous and micropatterned forms. The composites acquired a nanogranular structure with granules of about 50 nm in size. The RBS inspection confirmed homogeneous distribution of the phases and also the presence of oxygen. The Raman study suggested polymerization of the C₆₀/Ti composites into polymeric structures. The hybrid substrates were tested on biocompatibility—the films were seeded with human osteoblast-like MG 63 cells, and their proliferation was analyzed for 7 days. It has been found that the C₆₀/Ti composites can be counted as good supports for the adhesion of the selected MG 63 cells. The composites exhibited similar biocompatibility as the mix of amorphous carbon and titanium, but different than fullerene (C₆₀) solids.