Functionally graded PCL/β-TCP biocomposites in a multilayered structure for bone tissue regeneration

Functionally graded (FG) composites consisting of polycaprolactone (PCL) and beta-tricalcium phosphate (β-TCP) particles were fabricated with a multilayered structure using a melt plotter with a two-heating-barrel system. Using this process, the concentration of β-TCP particles varied in each layered strut. Scanning electron microscopy (SEM) and energy dispersive spectroscopy mapping of calcium on the fabricated scaffolds indicated that the β-TCP particles were well distributed in each PCL strut, according to conceptual design. By incorporating β-TCP, the FG-PCL/β-TCP scaffolds had meaningful increases in water absorption (30 % increase) and showed good mechanical properties, although the mechanical properties are slightly low compared to pure PCL/β-TCP composite. We performed biological assessments to evaluate the capability of these FG scaffolds to act as a biomaterial for bone tissue regeneration with osteoblast-like cells (MG63). SEM images of cell-seeded FG scaffolds showed that the concentrated β-TCP struts were affected as good cell attachment/proliferation sites. Additionally, calcium deposition on the FG scaffolds was higher than that of normal scaffolds after 14 days. In particular, we observed high levels of mineralization in the highly concentrated β-TCP struts in the FG scaffolds. Based on these results, we believe that the FG scaffolds having various spatially designed structures with graded properties will be widely applicable for hard tissue engineering applications.     

Sol–gel synthesis of pure nano sized β-tricalcium phosphate crystalline powders

β-Tricalcium phosphate (β-TCP) nano powders (80 nm) were synthesized using a simple sol–gel route with calcium nitrate and potassium dihydrogenphosphate as calcium and phosphorus precursors, respectively. Double distilled water was used as a diluting media for β-TCP sol preparation and ammonia was used to adjust the pH. After aging, the β-TCP gel was dried at 40 °C and calcined to different temperatures ranging from 200 to 800 °C. The dried and calcined powders were characterized for phase composition using X-ray diffractrometry (XRD) and Fourier transform-infrared spectroscopy (FT-IR). The particle size and morphology was studied using Transmission electron microscopy (TEM). Calcination revealed that with increase in temperature, both the crystallinity and crystallite size of β-TCP particles increased. Particle size distribution analysis of the calcined β-TCP at 800 °C showed a narrow skewed distribution plot centered between 70 and 80 nm. This value was in closed agreement with particle size values obtained from XRD analysis (83 ± 6 nm). The present study showed that narrowly distributed, high crystalline, pure β-TCP could be obtained using this simple technique for biomedical applications.     

In-Vitro Degradation Behaviors of Composite Scaffolds Based on 1,4-Butadnediamine Modified Poly(lactide-co-glycolide) and Nanobioceramics

In-vitro degradation behaviors of composite scaffold materials composed of 1,4-butanediamine modified poly(lactide-co-glycolide) (BMPLGA), nanobioactive glass (NBG) and β-tricalcium phosphate (β-TCP) were systematically investigated in phosphate-buffered solution (PBS) at 37?°C. The properties of the BMPLGA/NBG-β-TCP and BMPLGA scaffolds, including the changes of pH value, mass, water uptake, compressive strength and molecular mass, were investigated as a function of degradation time. The results showed that the introduction of the NBG and β-TCP particles played important roles in the degradation of BMPLGA matrix. The degradation rate of the BMPLGA/NBG-β-TCP scaffolds was slower than that of the BMPLGA scaffolds.     

Fabrication of Degradable Bone-Like Substitutes Based on Poly-L-lactide and β-tricalcium Phosphate

Composite bone-like substitutes composed of poly-L-lactide (PLLA) and β-tricalcium phosphate (β-TCP) (average particle size: 4.43 μm) were fabricated and the properties were investigated. β-TCP was prepared by wet chemical precipitation, followed by calcining at 800°C. Composite films were obtained by completely mixing dissolved PLLA with granules of β-TCP; the agglomerated β-TCP powder granules were distributed homogeneously in the PLLA matrix. PLLA/β-TCP composite materials were obtained by cold and hot pressing the composite film at a pressure of 130 MPa and temperature of 185°C–195°C. With increase of the amount of β-TCP powder, the bending strength of the composites decreased while the bending modulus increased. The fracture mechanism of the composites was significantly influenced by the content of β-TCP powder, from ductile fracture to brittle fracture as the β-TCP powder content increased.     

In situ synthesis of silicon-substituted biphasic calcium phosphate and their performance in vitro

In situ preparation of silicon (Si) substituted biphasic calcium phosphate (BCP) of hydroxyapatite (HAp)/ β-tricalcium phosphate (β-TCP) were carried out through aqueous co-precipitation method. The concentrations of added silicon were varied with the phosphor in order to obtain constant Ca/(P+Si) ratios of 1.602. X-ray diffraction (XRD) and Fourier transformed infrared (FTIR) spectroscopy were used to characterize the structure of synthesized silicon substituted BCP powders. The characterization revealed that the formation of biphasic mixtures of different HAp/ β-TCP ratios was dependent on the content of silicon. After immersing in Hanks' balanced salt solution (HBSS) for 1 week, 3 wt% silicon substituted BCP powders were degraded and precipitation started to be formed with small granules consisting of number of flake-like crystal onto the surface of synthesized powders. In the case of 1 wt% silicon substituted BCP powders, the degradation behavior was detected after immersion in HBSS for 3 weeks. On the other hand, silicon unsubtituted BCP powders were not degraded even after that duration. On the basis of these results, silicon substituted BCP is able to develop a new apatite phase on the surface in contact with physiological fluids faster than BCP does. This enhanced reactivity resulted in reduction for the stability of the β-TCP structure due to SiO₄ tetrahedral distortion and disorder at the hydroxyl site when silicon incorporates into BCP.     

Substitution mechanism of Zn ions in β-tricalcium phosphate

Zn-doped β-tricalcium phosphate (β-TCP) is synthesized by the solid-state reaction method. The substitution mechanism of Zn ions in β-TCP synthesized here is investigated by carrying out a combination of near-edge X-ray absorption fine structure (NEXAFS) measurements and first-principles calculations. From the results of the present study, the substitution site for Zn ions in β-TCP is successfully determined.     

The microstructure and specific properties of La/HAP composite powder and its coating

La/HAP composite powder, a novel bioactive material, was prepared using co-precipitation method. The La/HAP coating was obtained for the first time through the dip-coating method, starting from the sols of La/HAP and TiO₂ particles. The compositions and coating of as-produced La/HAP composite powder sintered at temperatures from 300 to 750 °C were analyzed by means of X-ray diffraction (XRD). The changes of the ion groups in as-prepared La/HAP composite powder were characterized by using Fourier transform infrared (FTIR) spectroscopy. Their surface morphologies were observed by means of scanning electron microscope (SEM). The results show that the La/HAP composite powder has higher thermostability than pure HAP powder and La can refine HAP particle and restrain the decomposition of HAP. Consequently, in coating process the heat-treatment temperature is lower (750 °C) using the synthesized La/HAP powder than that using pure HAP (900 °C). The La/HAP coating mainly contains HAP, TiP or Ti₃P₅ and TiO₂ phases as well as a little CaTiO₃ crystal, a very ideal composition to enhance bioactivity of biomaterials. These unique properties of the La/HAP composite powder are beneficial to enhance the strength and bioactivity of coating when it is used as a starting material in coating process.     

Biomorphous SiC ceramics prepared from cork oak as precursor

Porous ceramic materials of SiC were synthesized from carbon matrices obtained via pyrolysis of natural cork as precursor. We propose a method for the fabrication of complex-shaped porous ceramic hardware consisting of separate parts prepared from natural cork. It is demonstrated that the thickness of the carbon-matrix walls can be increased through their impregnation with Bakelite phenolic glue solution followed by pyrolysis. This decreases the material’s porosity and can be used as a way to modify its mechanical and thermal characteristics. Both the carbon matrices (resulted from the pyrolysis step) and the resultant SiC ceramics are shown to be pseudomorphous to the structure of initial cork. Depending on the synthesis temperature, 3C-SiC, 6H-SiC, or a mixture of these polytypes, could be obtained. By varying the mass ratio of initial carbon and silicon components, stoichiometric SiC or SiC:С:Si, SiC:С, and SiC:Si ceramics could be produced. The structure, as well as chemical and phase composition of the prepared materials were studied by means of Raman spectroscopy and scanning electron microscopy.     

Preparation and Characterization of Poly(L-lactide-co-glycolide-co-ε-caprolactone)/Nano-biaoactive Glass-Nano-β-tricalcium Phosphate Composite Scaffolds

Abstract

Polymeric/ceramic composite scaffolds that are biocompatible and biodegradable are widely used for tissue engineering applications. In this work a series of poly(L-lactide-co-glycolide-co-ε-caprolactone)/nano-biaoactive glass-nano-β-tricalcium phosphate composite scaffolds were successfully fabricated and the influences of the inorganic content and freezing temperature on the physical properties were studied. The composite scaffolds with various inorganic contents showed an interconnected pore structure with irregular shapes. The composite scaffolds had a porosity that was reduced with increasing inorganic content and decreasing freezing temperature. The incorporation of inorganic fillers and decreasing freezing temperature improved the mechanical properties of the hybrid scaffolds. By appropriate control of these two factors (10.0?wt% content of NBAG and β-TCP with freezing at ?30?°C) a suitable composite scaffold was prepared as a potential bone tissue engineering implant.     

Influence of the calcium phosphate content of the target on the phase composition and deposition rate of sputtered films

Calcium phosphate was coated from tetracalcium phosphate (TTCP), hydroxyapatite (HA), β-tricalcium phosphate (TCP), β-calcium pyrophosphate (CPP), and β-calcium metaphosphate (CMP) powder targets using radio frequency magnetron sputtering. The composition of the crystal phase of the coated films was changed, depending on the target materials, and the Ca/P molar ratios of the films varied from 0.74 to 2.54, increasing with the Ca/P molar ratio of the target. The solubility of the target, determined using a microwave-induced plasma-mass spectrometer was: TTCP ≈ β-CMP > β-TCP > β-CPP > HA, and the deposition rate from each target showed a similar order to the solubility: TTCP ≈ β-CMP > β-TCP > β-CPP ≈ HA.     

Biocompatible and bioactive coatings of Mn-doped β-tricalcium phosphate synthesized by pulsed laser deposition

The extension of pulsed laser deposition to the synthesis on Ti substrates of β-tricalcium phosphate (β-TCP) coatings doped with manganese is reported. Targets sintered from two crystalline Mn-doped β-TCP powders (with the composition Ca_2.9Mn_0.1(PO₄)₂ and Ca_2.8Mn_0.2(PO₄)₂) were ablated with an UV KrF* (λ = 248 nm, τ ∼ 7 ns) laser source. X-ray diffraction and energy dispersive X-ray spectroscopy investigations showed that the films, while prevalently amorphous, had a Ca/P ratio of about 1.50-1.52. Scanning electron microscopy analyses revealed a rather homogeneous aspect of the coatings which were molded to the relief of the chemically etched Ti substrate. Fluorescence microscopy was applied to test the proliferation of mesenchymal stem cells grown on the obtained biostructures. Our investigations found that, even 14 days after cultivation, the synthesized films were not cytotoxic. On the contrary, they showed excellent bioactivity, as demonstrated by the neat spread of the cells over the entire surface of Mn-doped β-TCP. When tested in osteoprogenitor cell culture, the Ca_2.8Mn_0.2(PO₄)₂ samples revealed a higher potential for proliferation and better viability compared with Ca_2.9Mn_0.1(PO₄)₂.     

Effect of surface roughness of chitosan-based microspheres on cell adhesion

Microspheres are novel candidate materials for microcarriers and tissue-engineering scaffolds. Chitosan microspheres were selected as the base materials because of their excellent properties for biomedical applications. But their smooth surfaces were not adapted for cell attachment. Hence, in order to improve the roughness of chitosan microspheres, β-TCP/chitosan composite microspheres were developed. From SEM photographs, the coarse surfaces of composite microspheres were observed, there were some ceramic particles standing out of the chitosan matrix. And their roughness measured by profilometers was about 2.0 μm. Mouse MC3T3-E1 osteoblasts were seeded on the microspheres for evaluating the attachment interaction between cells and materials. According to the ESEM photographs and MTT assay, the adherence and proliferation of osteoblasts on the surfaces of modified microspheres were better than those on the chitosan microspheres, which were mainly attributed to the improved roughness of surface.     

Transmission electron microscopy of Ca oxide nano- and microcrystals in α-tricalcium phosphate prepared by sintering of β-tricalcium phosphate

Transmission electron microscopy (TEM) and X-ray diffraction (XRD) were used to study the porous and non-porous α-tricalcium phosphate (α-Ca₃(PO₄)₂, α-TCP) prepared through a sintering procedure at 1200–1400 °C of β-tricalcium phosphate (β-Ca₃(PO₄)₂, β-TCP). The interpretation of experimental and calculated X-ray and electron diffraction patterns showed that the final product at 1400 °C was primarily α-TCP but roughly 3.0–8.0 wt.% of the starting β-TCP phase and up to 8.0 wt.% of CaO were in the final product. TEM images and electron diffraction patterns showed that the CaO phase – formed by decomposition of TCP – exists as micron-sized areas of various oriented nanocrystals embedded into the bulk α-TCP material and also as self-standing spherulite particles of a few microns in size. Surprisingly, formation of CaO from TCP decomposition occurred at temperatures below those predicted from the phase diagram of the CaO–P₂O₅ system.     

Characterization of ceramic oxide refractories by XRF and XRD

The present study was undertaken to establish a methodology for characterizing ceramic oxide refractory materials, as no detailed information could be found in the literature on this point. The following refractories were analysed: two silica, one alumina, one silica–alumina, two zirconium, three chrome and three magnesia refractories. X‐ray fluorescence (XRF) spectrometry was used for chemical characterization and x‐ray diffraction (XRD) for phase analysis. Phases were determined because of their influence on the end properties of refractory materials. Five analytical programmes for XRF analysis and an XRD analysis method were established. We optimized sample preparation in the form of beads for the XRF measurement by determining the most appropriate sample/flux ratio for each type of refractory. Calibration and validation standards were prepared from mixtures of reference materials, owing to the scarcity of refractory reference materials. The chemical and phase composition of different ceramic oxide refractory bricks was determined and related to the deterioration of these refractories in industrial service, because refractories with a similar chemical composition and different crystalline phases can exhibit different properties. Copyright © 2004 John Wiley & Sons, Ltd.     

Preparation of ceramic coating on Ti substrate by plasma electrolytic oxidation in different electrolytes and evaluation of its corrosion resistance: Part II

The aim of this work is to discuss the growth characteristics and corrosion behavior of the prepared ceramic coatings on titanium by plasma electrolytic oxidation (PEO) technique in different electrolytes. PEO process was carried out on titanium under constant voltage regime using a pulse power supply. Three kinds of electrolytes, phosphate, silicate and borate based solutions, were used to evaluate the influence of electrolyte composition on the structure, surface morphology, phase composition and corrosion behavior of prepared ceramic oxide films (titania). The phase composition of the coatings was investigated by X-ray diffraction. Scanning electron microscopy was employed to evaluate the growth and surface morphology of coatings. Elements of coatings were investigated with energy dispersive spectrometer. Corrosion behavior of the coatings was also examined by potentiodynamic polarization and electrochemical impedance spectroscopy. The spark voltage of oxide films had a significant effect on the surface morphology, size and homogeneity of micro-pores, thickness and corrosion properties of coatings.     

烧结温度对Eu3+在羟基磷灰石中发光性能的影响

采用化学沉淀法制备了一系列Eu³⁺掺杂的羟基磷灰石样品,并在不同温度下对样品进行了烧结.使用X射线衍射、红外光谱以及荧光光谱等对样品的结构及发光特性进行了研究.分析表明,烧结对Eu掺杂羟基磷灰石的结构及结晶度产生了影响.在394 nm激发下,样品出现Eu的特征发射,掺杂摩尔分数一定时,随烧结温度增加,样品的荧光发光强度先增大后减小,在500 ℃达到峰值.其荧光寿命随烧结温度的升高而延长.此外,样品中电偶极跃迁与磁偶极跃迁强度之比(I_R:I_O)也随烧结温度的增加先增大后减小.分析表明,烧结温度的改变通过晶体结构对样品的荧光特性以及掺杂取代位置产生了影响.     

Growth of Bi-Sb alloy thin films and their characterization by TEM, PIXE and RBS

Polycrystalline bulk materials of Bi₉₃Sb₇ Bi₈₈Sb₁₂, Bi₈₅Sb₁₅ and Bi₈₀Sb₂₀ were synthesized by melt-quench technique starting from the stoichiometric mixture of constituent elements. The phase purity and compositional uniformity of bulk materials were investigated using powder X-ray diffraction (XRD) and proton induced X-ray emission (PIXE) experiments. The single phase formation and the compositional analysis of thin films were confirmed by transmission electron microscopy (TEM) and Rutherford backscattering spectroscopy (RBS). X-ray diffraction studies confirmed the phase homogeneity of the materials. Atomic concentration ratio of constituent elements (Bi and Sb) determined by PIXE and RBS revealed that near-stoichiometric composition is nearly the same in the bulk as well as in thin film forms.     

Effect of pulse frequency on the microstructure, phase composition and corrosion performance of a phosphate-based plasma electrolytic oxidation coated AM50 magnesium alloy

An AM50 magnesium alloy was plasma electrolytic oxidation treated using a pulsed DC power supply at three different pulse frequencies viz., 10 Hz, 100 Hz and 1000 Hz with a constant pulse ratio for 15 min in an alkaline phosphate electrolyte. The resultant coatings were characterized by X-ray diffraction, energy dispersive spectroscopy and scanning electron microscopy for their phase composition and microstructural features. The 10 Hz condition yielded relatively thick and rough coatings, which was attributed to the higher energy input per individual pulse during the PEO processing. The phase composition was also found to be influenced by the processing frequency. Electrochemical impedance spectroscopy studies performed in 0.1 M NaCl solutions revealed that the coatings produced at 10 Hz condition had a better corrosion resistance, which was attributed to the higher thickness, more compact microstructural features and a relatively stable phase composition.     

Crystal growth,structure and optical properties of Pr~(3+) -doped yttria-stabilized zirconia single crystals

The development of blue semiconductor light-emitting diodes(LEDs) has produced potential applications for Prdoped materials that can absorb blue light, especially crystals, and we now report structure and optical properties for high-quality Pr-doped single crystals of yttria-stabilized zirconia(YSZ) grown by the optical floating zone(FZ) method.X-ray diffraction(XRD) and Raman spectroscopy showed that all of the single crystal samples were in the cubic phase,whereas the corresponding ceramic samples contained a mixture of monoclinic and cubic phases. X-ray photoelectron spectroscopy(XPS) and electron paramagnetic resonance(EPR) spectroscopy showed that Pr was present as the Pr~(3+) ion in ceramic rods and single crystals after heating to high temperatures. The absorption and photoluminescence excitation(PLE) spectra of the Pr-doped YSZ crystals measured at room temperature showed strong absorption of blue light, while their photoluminescence(PL) spectra showed five emission peaks at 565 nm, 588 nm, 614 nm, 638 nm, and 716 nm under450 nm excitation. The optimum luminescence properties were obtained with the crystal prepared using 0.15 mol% Pr_6O_(11),and those with higher concentrations showed evidence of quenching of the luminescence properties. In addition, the color purity of Pr-doped YSZ single crystal reached 98.9% in the orange–red region.     

Influence of gelatin on the properties of hydroxyapatite–polyacrylamide nanocomposite as a potential bone substitute

The controlled integration of organic and inorganic components confers superior mechanical properties onto natural bone. The present work adds to the continuing efforts of designing a natural bone-like structure. In this study, the hydroxyapatite (HAP) impregnated polymeric composites of polyacrylamide (PAM) and the same with gelatin have been synthesized by a suspension polymerization method in order to study their blood compatibility, water sorption behavior, and mechanical properties; and network parameters, such as average molecular weight between crosslinks (M _c), crosslink density (q) have been calculated. Both, HAP–PAM and PAM–gelatin–HAP composites were characterized using techniques like Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) studies, thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The composites were also evaluated for their mechanical properties like compressive strength and modulus (E).