冰醋酸介质中电泳共沉积制备生物玻璃/羟基磷灰石涂层

通过研究生物玻璃(bioglass，BG)微粉和羟基磷灰石(hydroxyapatite，HA)微粉在水和非水介质中的分散及带电特性，选择冰醋酸为介质，使分散在其中的BG颗粒和HA颗粒表面均带上正电荷，为电泳共沉积提供了前提条件。通过对BG颗粒和HA颗粒在冰醋酸介质中电泳共沉积以及后续低温快速热处理，在钛合金基体上成功地制备出了底层致密而表层附近多孔的BG／HA涂层。并对所制备的BG／HA涂层的力学性能和微观结构及组成进行了测试分析。     

壳聚糖/羟基磷灰石的pH敏感性

壳聚糖(CS)是甲壳素的脱乙酰基产品,是自然界中大量存在,并且可以生物降解的高分子化合物,是优良的天然高分子生物材料。羟基磷灰石(HA)是人体自然骨的主要成分(含60%~70%),具有极好的生物相容性和骨诱导性。文章通过合适的工艺条件制备了三种不同比例的CS/HA复合材料,测定CS/HA在不同pH缓冲溶液中的溶胀动力学特点。实验结果表明:CS/HA的吸水率呈pH依赖性,说明了壳聚糖本身吸水性能良好。     

Halloysite nanotubes immobilized by chitosan/tannic acid complex as a green flame retardant for bamboo fiber/poly(lactic acid) composites

In order to develop an environmentally benign flame retardant for bamboo/PLA composites (BPC), chitosan (CS) and tannic acid (TA) were used as cationic and anionic polyelectrolyte respectively to stabilize halloysite nanotubes (HNT) on the surface of bamboo fiber (BF) and poly(lactic acid) (PLA). Mechanical performance tests showed that the flexural properties of BPC were moderately enhanced with the addition of HNT, while the incorporation of CS/TA complex (FR) exhibited a slight increase. The results of thermogravimetric analysis demonstrated that CS/TA complex and HNT improved the thermal stability of the BPC synergistically, which increased the char residue. Limiting oxygen index and cone calorimetry tests were used to study the flammability of BPC and the results showed that the addition of CS/TA complex and HNT had a synergistic effect on the flame retardant performance of BPC materials. The macroscopic and microscopic morphological studies confirmed the formation of HNT layer in the matrix of BPC/5FR@5HNT samples, which facilitated more stabile char residue with the best flame retardant performance.     

两步电化学法制备羟基磷灰石/氧化铝复合生物涂层的研究

研究旨在开发一种可应用于医用金属表面生物学改性的复合生物陶瓷涂层。通过先阳极氧化、再电沉积的两步电化学方法成功制备了羟基磷灰石(hydroxyapatite,HA)／Al2O3复合生物涂层。利用扫描电子显微镜(SEM)研究了阳极氧化Al2O3(anodic aluminum oxide,AAO)膜的表面形貌与HA／Al2O3复合涂层的表面及截面形貌结构;用X射线衍射仪(XRD)、Fourier变换红外光谱仪(FT-IR)与能谱仪(EDS)表征了复合涂层的物相组成;用等离子原子发射光谱仪(ICP-AES)和粘接拉伸试验分别测定涂层在模拟体液(SBF)中的体外行为和浸渍后涂层间的结合强度,结果表明：所制备的HA含有少量碳酸根,在SBF中呈现优良的稳定性并能诱导新的磷灰石层的形成;HA底部嵌入AAO膜的孔洞中形成互锁界面,经模拟体液处理后两者之间结合强度为3．2MPa。     

Effects of halloysite nanotubes and kaolin loading on the tensile,swelling, and oxidative degradation properties of poly(vinyl alcohol)/chitosan blends

[Halloysite nanotubes (HNT)]‐filled and kaolin filled composite films based on poly(vinyl alcohol) (PVA)/chitosan (CS) blend were prepared via solution casting method. Tensile properties, fracture morphology, FTIR spectra, thermal stability, swelling properties, moisture absorption, and oxidative degradation of the composite films were investigated. Addition of 0.5 wt% of filler led to the optimum tensile properties of the films. Increased roughness and tearing in the fracture surface morphology supported the tensile results. The FTIR results indicated there were physical interactions present in the composite films. Thermal stability of the composite films differed slightly where PVA/CS/HNT composite films showed better thermal stability than PVA/CS/kaolin composite films. Moreover, the presence of HNT and kaolin fillers in the blend reduced the swelling and moisture absorption properties of the films. Finally, the composite films were degraded by using Fenton's reagent. Degradation percentage of the composite films decreased with increasing filler loading. J. VINYL ADDIT. TECHNOL., 19:55–64, 2013. © 2013 Society of Plastics Engineers     

Comparative analysis and antibacterial properties of thermally sintered apatites with varied processing conditions

Hydroxyapatite (HA) and biphasic hydroxyapatite/beta-tricalcium phosphate (biphasic HA/β-TCP) were synthesized using thermal sintering. The parameters- sintering temperature (600°C, 900°C, and 1200°C), biological source used (fish bone, egg shells, and fish scales), and soaking time (2, 6, and 10 hours) were permuted to study their effects on the properties of the resultant apatite. Morphological study revealed that the smallest (60 nm) spherical particle and the largest (470 nm) irregular shaped particle were obtained from the fish bone sample sintered at 600°C and at 1200°C respectively. FTIR and XRD results showed that as the sintering temperature is increased, the phase transformation from HA to β-TCP takes place. Only the final products from fishbone sample at 600°C are pure carbonated HA. The crystallinity of synthesized particles ranged from 79% to 98%. Soaking time has no effect on phase composition of the apatite but has significant effect on crystallite size; increase in soaking time increases crystallite size and particle shape becomes more spherical. Interestingly, the fish bone sample sintered at 900°C has higher crystallinity and crystallite size compared to the fish scale sample sintered at the same temperature. EDX confirmed that non-stoichiometric apatite with Ca/P ratio ranging from 1.47 to 1.91 can be obtained by varying the sintering conditions. The antibacterial test revealed that both calcium apatite obtained from fish bones and fish scales have inhibited bacterial growth; apatite from fish bone works faster than fish scales. The in vitro cytotoxicity test ensured that all the calcium apatite except for eggshell are non-cytotoxic. Thus, apatite with excellent microbial activity can be obtained by using fish wastes, and by tuning the sintering parameters, the apatite with desired types and properties can be synthesized for different biomedical applications.     

Production, mechanical properties and in vitro biocompatibility of highly aligned porous poly(ε-caprolactone) (PCL)/hydroxyapatite (HA) scaffolds

We produced highly aligned porous poly(ε-caprolactone) (PCL)/hydroxyapatite (HA) scaffolds by unidirectionally freezing PCL/HA solutions with various HA contents (0, 5, 10 and 20 wt% in relation to the PCL polymer) and evaluated their mechanical properties and in vitro biocompatibility to examine their potential applications in bone tissue engineering. All the prepared scaffolds had a highly aligned porous structure, in which the HA particles were uniformly dispersed in the PCL walls. The elastic modulus of the PCL/HA scaffolds significantly increased from 0.12 ± 0.02 to 2.65 ± 0.05 MPa with increasing initial HA content from 0 to 20 wt%, whereas the pore size decreased from 9.2 ± 0.7 to 4.2 ± 0.8 μm. In addition, the PCL/HA scaffolds showed considerably enhanced in vitro cellular responses that were assessed in terms of cell attachment, proliferation and osteoblastic differentiation.     

Degradability and biocompatibility of bioglass/poly(amino acid) composites with different surface bioactivity as bone repair materials

Bioglass (BG) possesses excellent bioactivity and has been widely used in the manufacture of biomaterials. In this study, a composite with different surface bioactivity was fabricated via in situ melting polymerization by incorporating BG and poly(amino acid) (PAA) at a suitable ratio. The structure of the composite was characterized by Fourier transform infrared spectroscopy and XRD. The compressive strength of the BG/PAA composites was 139 MPa (BG:PAA = 30:70). The BG/PAA composites were degradable, and higher BG in composite showed higher weight loss after 4 weeks of incubation in simulated body fluid. In addition, the BG/PAA composite maintained adequate residual compressive strength during the degradation period. The SEM results showed the differences in surface bioactivities of the composites directly, and 30BG/PAA composite showed thicker apatite layer and higher Ca/p than 15BG/PAA. in vitro MG-63 cell culture experiments showed that the composite was noncytotoxic and thus allows cells to adhere, proliferate, and differentiate. This indicates that the composite has good biocompatibility. The implantations in the bone defects of rabbits for 4 and 12 weeks were studied. The composites had good biocompatibility and were capable of guiding new bone formation without causing any inflammation. The composite may be successfully used in the development of bone implants.     

Fabrication of a zirconia/calcium silicate composite scaffold based on digital light processing

Zirconia (ZrO₂) and calcium silicate (CS) are widely used in bone repair. Zirconia has excellent mechanical properties, while calcium silicate has exceptional biological activity. A porous ZrO₂/CS composite ceramic scaffold was formed by digital light processing (DLP) technology in this study. The microstructure analysis demonstrated that CS was embedded between ZrO₂ particles. Mechanical tests showed that interconnected CS particles could improve mechanical properties, while discrete CS particles led to a decrease in that. Cell experiments showed that adding CS to ZrO₂ had a positive effect on cell proliferation and differentiation. In vitro degradation test showed that the weight loss of scaffolds in four weeks increased form ?0.63%–1.42% with the increase of CS content. Moreover, the degradation of scaffold promoted the deposition of apatite, which was beneficial to the integration of the scaffold with living bone. In conclusion, the ZrO₂/CS composite scaffold had better biocompatibility compared with the ZrO₂ scaffold, which showed a potential solution for 3D printing bone repair scaffolds.     

Production of Hydroxyapatite/Bioactive Glass Biomedical Composites by the Hot-Pressing Technique

Biomedical composites of hydroxyapatite (HA) and bioactive glass (BG) have been difficult to obtain as a dense body without the undesirable occurrence of thermal reactions and phase degradation. Herein, HA–BG dense composites were produced by the hot-pressing technique. A range of HA–BG powder mixtures (30–50 wt% BG) was fully densified by hot pressing at temperatures as low as ∼700°–800°C. On the other hand, the HA–BG composites could not be densified by pressureless sintering because their composition was degraded due to a severe thermal reaction. The hot-pressed composites had significantly improved flexural strengths (∼60 MPa) as compared with those subjected to pressureless sintering (∼30 MPa) or the pure HA control (∼40 MPa). The hot-pressed HA–BG composites showed significantly enhanced bioactivity in a simulated body fluid, as well as osteoblast cell activity with respect to the pure HA, confirming their excellent in vitro biocompatibility.     

Ethylene–propylene‐diene terpolymer/halloysite nanocomposites: Thermal,mechanical properties,and foam processing

Ethylene–propylene‐diene terpolymer (EPDM)/halloysite nanotube (HNT) nanocomposites were prepared by melt mixing in an internal mixer using a commercially available maleated semicrystalline EPDM and HNT. Transmission electron microscopy analysis of the EPDM/HNT composites revealed that the HNTs are uniformly dispersed at a nanometer scale in the matrix. Differential scanning calorimeter studies indicated that the HNT caused an increase in the nonisothermal crystallization temperature of the EPDM. Tensile and dynamic mechanical analysis exhibited that a small amount of the HNTs effectively enhanced the stiffness of the EPDM without adversely affecting its elongation‐at‐break. The EPDM/HNT nanocomposites were used to produce foams by using a batch process in an autoclave, with supercritical carbon dioxide as a foaming agent. The nanocomposite foams showed a smaller cell size and higher cell density as compared to the neat EPDM foam, and the nanocomposite with 10 phr HNT produced a microcellular foam with average cell size as small as 7.8 μm and cell density as high as 1.5 × 10¹⁰ cell/cm³. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40307.     

Biofunctionalization of commercially pure titanium with chitosan/hydroxyapatite biocomposite via silanization: evaluation of biological performances

Chitosan (CS) and hydroxyapatite (HA) bioactive molecules have been grafted onto commercially pure titanium surfaces (cpTi) to promote osteoblast adhesion and bone growth. The major challenge of this type of grafting is the attachment of the CS/HA biocomposite to the cpTi surface. In this study cpTi is biofunctionalized with CS/HA biocomposite material via silanization and the coated specimens were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), water contact angle measurement and attenuated total reflectance-Fourier transform infrared (ATR-FTIR). The cpTi specimens were further evaluated for their in vitro bioactivity, hemocompatibility, protein adsorption and cell viability. The SEM micrographs showed uniform coatings adhered on cpTi specimens. The XRD and ATR-FTIR confirmed the presence of CS and HA on the cpTi specimens. The coated specimens showed improved in vitro bioactivity and hemocompatibilty along with enhanced adsorption of specific proteins. The cell viability studies showed non-cytotoxic nature of all the specimens and exhibited greater cell viability in the titanium CS/HA specimens. Hence, the studies showed that functionalized cpTi with covalent coating of CS/HA has significant potential in biomedical device implantation with improved bioactive properties.     

Microarchitectural and mechanical characterization of chitosan/hydroxyapatite/demineralized bone matrix composite scaffold

Porous degradable scaffolds are used extensively in bone tissue engineering. As well as material type, the architectural and mechanical characterizations of scaffolds are important to facilitate cell and tissue growth. Matrices composed of hydroxyapatite (HA), chitosan (CS) and demineralized bone matrix (DBM) may create an appropriate environment for the regeneration of bones. In this study, CS/HA/DBM scaffolds with sufficient structural integrity and high interconnected porosity were produced using different combinations of CS, HA and DBM. Both mechanical and biological properties of porous scaffolds were determined by local microarchitecture whose parameters were quantified based on micro computed tomography (Micro-CT) analysis. Within porosity range of 48–65%, the ranges of average compressive modulus and ultimate strength of the scaffolds were 3 ± 1–6 ± 1 kPa and 11 ± 2–24 ± 2 kPa, respectively. With the increase of HA concentration at the equal weight of DBM, the average trabecular thickness and trabecular separation increased and bone surface/volume ratio decreased, resulting in higher volume fraction and lower total porosity. In vitro, MC3T3-E1 preosteoblast cells were used to investigate cell attachment, spreading and proliferation on the scaffolds via hematoxyline and eosin (HE), scanning electron microscopy (SEM) and MTS assay. The results showed that MC3T3-E1 cells adhered to the surface of composite scaffolds, cell number increased with culture time. Cell viability increased with the HA particles decreased, changed little with the DBM increased. Consideration of the microarchitectural and mechanical characterization and biocompatibility of the scaffolds, 3:3:1.5 and 3:5:1.5 groups were believed to be the best in our study.     

Preparation of chitosan bicomponent nanofibers filled with hydroxyapatite nanoparticles via electrospinning

Chitosan (CS) bicomponent nanofibers with an average diameter controlled from 100 to 50 nm were successfully prepared by electrospinning of CS and poly(vinyl alcohol) (PVA) blend solution. Finer fibers and more efficient fiber formations were observed with increased PVA contents. On this contribution, a uniform and ultrafine nanofibrous CS bicomponent mats filled with hydroxyapatite (HA) nanoparticles were successfully electrospun in a well devised condition. An increase in the contents of HA nanoparticles caused the conductivity of the blend solution to increase from 1.06 mS/cm (0 wt % HA) to 2.27 mS/cm (0.5 wt % HA), 2.35 mS/cm (1.0 wt % HA), respectively, and the average diameter of the composite fibers to decrease from 59 ± 10 nm(0 wt % HA) to 49 ± 10 nm (0.5 wt % HA), 46 ± 10 nm (1.0 wt % HA), respectively. SEM images showed that some particles had filled in the nanofibers whereas the others had dispersed on the surface of fibers, and EDXA results indicated that both the nanoparticles filled in the nanofibers and those adhered to the fibers were HA particles. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Glutaraldehyde‐crosslinked chitosan/hydroxyapatite bone repair scaffold and its application as drug carrier for icariin

Chitosan/hydroxyapatite (CS/HA) bone repair scaffolds crosslinked by glutaraldehyde (GA) were prepared. Characterization of morphology, structure, mechanical property, and porosity of scaffolds were evaluated. The influences of CS viscosity, HA content, and crosslinking degree on properties of scaffolds were discussed. SEM images showed that CS/HA scaffolds were porous with short rod‐like HA particles dispersing evenly in CS substrate. When [η]_CS = 5.75 × 10^?4, HA content = 65%, and crosslinking degree = 10%, the resulting CS/HA scaffolds had a flexural strength of 20 MPa and porosity of 60%, which could meet the requirements of bone repair materials. The scaffolds were used as drug carriers for icariin, and the impacts of loading time and crosslinking degree of scaffolds on drug‐loading dose were discussed. The suitable loading time was 24 h and it would be better to keep crosslinking degree no more than 10%. The drug release behavior demonstrated that the icariin‐loading CS/HA scaffolds could achieve basic drug sustained release effect. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1539–1547, 2013     

Tensile,Swelling, and Oxidative Degradation Properties of Crosslinked Polyvinyl Alcohol/Chitosan/Halloysite Nanotube Composites

Glutaraldehyde (GA) crosslinked polyvinyl alcohol (PVA)/chitosan (CS)/halloysite nanotube (HNT) composite films were prepared using a wet casting method. The tensile, morphology, thermal degradation, swelling, moisture, and oxidative degradation properties of crosslinked composite films were carried out. The presences of crosslinking in the composite films were confirmed by FTIR result. The tensile strength of the crosslinked composite films increased up to 0.5 wt% of HNTs loading. Increasing HNTs reduced the thermal degradation, swelling, and moisture properties of crosslinked composite films reduced with the increase of HNTs content. Results also indicated that the crosslinked composite films were degraded using Fenton reagent.     

Alternating Current Electrophoretic Deposition of Antibacterial Bioactive Glass-Chitosan Composite Coatings

Alternating current (AC) electrophoretic deposition (EPD) was used to produce multifunctional composite coatings combining bioactive glass (BG) particles and chitosan. BG particles of two different sizes were used, i.e., 2 μm and 20–80 nm in average diameter. The parameter optimization and characterization of the coatings was conducted by visual inspection and by adhesion strength tests. The optimized coatings were investigated in terms of their hydroxyapatite (HA) forming ability in simulated body fluid (SBF) for up to 21 days. Fourier transform infrared (FTIR) spectroscopy results showed the successful HA formation on the coatings after 21 days. The first investigations were conducted on planar stainless steel sheets. In addition, scaffolds made from a TiAl4V6 alloy were considered to show the feasibility of coating of three dimensional structures by EPD. Because both BG and chitosan are antibacterial materials, the antibacterial properties of the as-produced coatings were investigated using E. coli bacteria cells. It was shown that the BG particle size has a strong influence on the antibacterial properties of the coatings.     

Bio-inspired lamellar hydroxyapatite/magnesium composites prepared by directional freezing and pressureless infiltration

Hydroxyapatite (HA)/magnesium (Mg) composites are a promising alternative material for bone repair in load-bearing sites. However, the poor wettability between Mg and HA as well as the extreme sensitivity of Mg to oxidation and high vapor pressure at elevated temperatures makes the preparation of HA/Mg composites rather difficult. Herein, a facile strategy for improving the wettability of HA by Mg was proposed to enable the successful preparation of bio-inspired HA/Mg composites via directional freezing and pressureless infiltration. SiO₂ nanoparticles were introduced into the freeze-cast HA scaffold by doping or soaking to promote the spontaneous infiltration of the Mg melt. The resulting HA/Mg composites displayed a delicate biomimetic lamellar structure with alternating ceramic/metal arrangements and demonstrated higher compressive strength (increased by 140%) and wear resistance (increased by 1200%) than porcine bones. In addition, the composites exhibited progressive degradation and surface apatite mineralization in a simulated body fluid environment, making them potentially promising for biomedical applications. This study provides a facile and tailorable method for the design and preparation of novel Mg-matrix composites with bio-inspired structures and biomedical functions.     

Electrochemical synthesis of silica-doped high aspect-ratio titania nanotubes as nanobioceramics for implant applications

The preparation of silica-doped high aspect-ratio TiO₂ nanotubes and their apatite-forming ability were demonstrated in this study. The high aspect-ratio TiO₂ nanotube layers were produced by electrochemical anodic oxidation of Ti in chloride-containing electrolytes. Nanotubes were doped with different concentrations of silica particles through anodization in NaCl electrolyte containing different concentrations of water glass (24 g/L or 48 g/L Na₂SiO₃). The biomimetic apatite deposition behavior was evaluated under simulated body fluid (SBF) with an ion concentration nearly equal to human blood plasma. The experimental results collectively demonstrate the successful silica doping of the resultant nanotube layers with significant abundant OH groups on their surfaces. The results of hydroxyapatite (HA) growth on nanotubes clearly show that the silica doping greatly enhances the fast nucleation and growth of HA, especially for the tubes in their “as-formed” amorphous state, which usually require a long time for apatite induction. The nanotubes doped with high silica content combined with an anatase or a mixture of anatase and rutile led to the formation of very thick and continuous apatite layers with a thickness of ∼7 μm in 21 days. In contrast, to the tubes doped with a low concentration of silica (grown in an electrolyte containing 24 g/L Na₂SiO₃), the HA deposited in the form of closely packed spheroid particles and never developed into continuous films. This effect could be attributed to the critical active-site density (silanol groups, >Si-OH), which provides the sterochemical match for apatite growth. Finally, the results of this study provide, for the first time, evidence for the dependence of HA morphology/microstructure on the crystallographic structure and the density of active sites (>Si-OH groups).     

Nano-hydroxyapatite and nano-hydroxyapatite/zinc oxide scaffold for bone tissue engineering application

This research aims to evaluate the mechanical properties, biocompatibility, and degradation behavior of scaffolds made of pure hydroxyapatite (HA) and HA-modified by ZnO for bone tissue engineering applications. HA and ZnO were developed using sol-gel and precipitation methods respectively. The scaffolds properties were characterized using X-ray diffraction (XRD), Fourier transform spectroscopy (FTIR), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM), atomic absorption (AA), and atomic force microscopy (AFM). The interaction of scaffold with cells was assessed using in vitro cell proliferation and alkaline phosphatase (ALP) assays. The obtained results indicate that the HA/ZnO scaffolds possess higher compressive strength, fracture toughness, and density—but lower hardness—when compared to the pure HA scaffolds. After immersing the scaffold in the SBF solution, more deposited apatite appeared on the HA/ZnO, which results in the rougher surface on this scaffold compared to the pure HA scaffold. Finally, the in vitro biological analysis using human osteoblast cells reveals that scaffolds are biocompatible with adequate ALP activity.