电解液组成对医用钛合金微弧氧化生物陶瓷层的影响

采用微弧氧化技术在钛合金表面制备了羟基磷灰石(HA)陶瓷膜。研究了电解液中乙酸钙、乙二胺四乙酸二钠(EDTA-2Na)质量浓度对膜层Ca、P含量和二者原子比的影响。随电解液中乙酸钙质量浓度增大,膜层表面孔隙率基本不变,膜层Ca含量增大,P含量减少,钙磷原子比增大。随电解液中EDTA-2Na质量浓度增大,膜层表面孔隙率先增后减,膜层中Ca含量明显增大,P含量略微增大,钙磷原子比明显增大。电解液的最佳组成为:K2HPO4·3H2O 6.8 g/L,Ca(CH3COO)2 26.5 g/L,EDTA-2Na 20 g/L。此时陶瓷膜层表面孔隙率高达11.10%,钙磷原子比为1.65,十分接近HA的钙磷原子比(1.67)。     

骨组织工程支架材料磷酸钙双相生物陶瓷的研究进展

双相磷酸钙(biphasic calcium phosphate,BCP)生物陶瓷材料在整型外科领域是一类重要的骨修复材料。该材料由稳定相羟基磷灰石(hydroxyapatite,HA)和可溶解相β-磷酸三钙(β-tricalcium phosphate,β-TCP)双相平衡优化得到,其生物活性及生物降解性可调。模拟人体自然骨结构的多孔型BCP适宜细胞及骨组织的长入,是一类优异的骨组织工程支架材料。概述了BCP生物陶瓷材料的研究历史、制备工艺及材料表征;评价了多孔型BCP陶瓷的孔隙结构、力学性能及生物学性能;综合了多孔型BCP陶瓷作为骨组织工程支架材料的研究方向;并展望了组织工程化的BCP支架材料的研究未来。     

钛合金微弧氧化钙磷生物膜层形成机制研究

为了利用微弧氧化工艺生成钛合金生物钙磷陶瓷涂层,使用微弧氧化电源,在恒电流条件下制备试样。通过电子扫描电镜和电子能谱仪观测不同氧化阶段涂层形貌和元素组成,膜层厚度变化特点,并分析各阶段微弧放电特性,研究了钛合金微弧氧化生成羟基磷灰石(钙磷)医用陶瓷涂层机制。结果表明,各阶段膜层放电特性不同,膜层先向外生长,后向内生长,且所生成膜层元素成分有区别,致使在微弧放电阶段才有钙磷生物成分生成。结论:若想获得高质量钙磷生物膜层,需使微弧氧化达到微弧放电阶段,但应避免进入弧光放电阶段,所得结论可对研究微弧氧化成膜过程起到一定的指导作用。     

溶液浓度对TC4钛合金微弧氧化膜的影响

为了实现在钛合金表面制备微弧氧化膜层含有特定钙、磷比例关系,指导合理配置化学试剂。研究了不同质量浓度且不同钙、磷摩尔比溶液对微弧氧化膜层中钙、磷的影响。实验结果表明,随氧化液质量浓度的升高,膜层中钙、磷含量都降低,而膜层中钙、磷比例升高。溶液中钙、磷摩尔比越高,膜层中钙、磷含量越低。若希望制备某一钙、磷摩尔比的生物膜层,可据此确定不同钙、磷摩尔比的溶液,进而确定钙、磷化合物配比关系。     

医用钛合金微弧氧化复合陶瓷膜层断裂力学研究

以Ti6Al4V钛合金为基体材料,通过微弧氧化方法在电解液中制备多孔氧化锆和羟基磷灰石复合医用钛合金陶瓷膜层.利用能谱分析仪、扫描电镜和X-射线衍射仪分析膜层结构及相组成特点.对试样断裂韧性进行测量试验,通过测试结果对膜层断裂韧性进行了分析研究.探究了氧化锆对于钛合金羟基磷灰石膜层的增韧机制,并建立了适于多孔微裂纹膜层材料断裂韧性数学模型.结果表明,ZrO2/羟基磷灰石医用钛合金复合陶瓷膜层比单一的羟基磷灰石陶瓷膜层具有更好的断裂韧性.     

钛合金基材表面粗糙度对Ti/TiN/Zr/ZrN多层膜性能的影响

为提高钛合金的抗冲蚀性能,采用真空阴极电弧离子镀技术在不同表面粗糙度(Ra)的TC4钛合金表面制备了Ti/Ti N/Zr/Zr N多层膜。采用扫描电镜(SEM)、X射线衍射仪(XRD)、显微硬度计、划痕仪和砂粒冲刷试验仪分析了多层膜的截面形貌、微观结构、厚度、显微硬度、结合力和抗砂粒冲刷性能。重点研究了基体表面粗糙度对多层膜的结合力和抗砂粒冲刷性能的影响。结果表明,所得Ti/TiN/Zr/ZrN多层膜厚度约为12μm,显微硬度大于3 000 HV,能显著地提高TC4钛合金基材的抗砂粒冲刷性能。在相同工艺条件下,基体表面粗糙度越小,其表面膜层的结合力和抗砂粒冲刷性能越佳。为获得综合性能良好的Ti/TiN/Zr/ZrN多层膜,TC4钛合金基体的表面粗糙度必须控制在≤1.60μm。     

医用双相磷酸钙陶瓷的制备工艺研究

医用双相磷酸钙（BCP）陶瓷是β-磷酸三钙（β-TCP）和羟基磷灰石（HA）的复合体,其成分与骨矿物组成类似,在生理环境下能发生不同程度的降解,被组织吸收。通过化学沉淀法制备纳米羟基磷灰石,然后通过可溶性钙盐和磷酸盐反应工艺制得的β-磷酸三钙,最后将二者进行机械复合而制得双相磷酸钙,将所得样品用X射线衍射仪（XRD）对样品进行了表征。结果显示：所得的双相磷酸钙中掺杂有β-焦磷酸钙,但是它的结晶较好,并且可以改善双相磷酸钙陶瓷的力学性能。     

氧化时间对钛合金微弧氧化膜性能的影响

研究了在含钙、磷的电解液中氧化时间对Ti6Al4V钛合金微弧氧化生物活性膜的厚度、粗糙度、表面形貌、相成分及氧化膜与基体结合力的影响。结果表明,氧化t低于12min时,随着氧化时间增加,微弧氧化膜的厚度增加、表面粗糙度增大、微观孔洞变大、膜层中钙磷含量及钙磷比增大、氧化膜与基体的结合力增强。氧化t为12min时膜层与基体的结合力较好,约30N。氧化t超过12 min以后,膜层表面出现裂痕,与基体的结合力减小。     

手性选择性阳离子交换膜的制备及其评价

以聚乙烯醇(PVA)为基材,加入β环糊精(β-cyclodextrin,β-CD)作为手性选择剂,加入聚丙烯酸(PAA)促进离子传递,制得具有手性选择性的阳离子交换膜(chiral selective cation-exchange membrane, CSCM).通过电渗析过程拆分DL-对羟基苯甘氨酸(DL-4-hydroxyphenylglycine,DL-HPG)外消旋混合物以评价该膜的手性拆分效果.结果表明在酸性条件下D-对羟基苯甘氨酸优先通过手性阳离子交换膜,两种手性阳离子交换膜的选择性系数分别为1.21和1.34,验证了该膜的手性拆分效果.作为对比实验,还进行了料液中添加与不添加β环糊精,并以普通阳膜(cation-exchange membrane, CM)为分离介质时的电渗析实验,结果进一步验证了该膜的手性选择性来源于β环糊精.     

电极电压对纯钛表面微弧氧化陶瓷膜结构及特性的影响

采用微弧氧化处理技术,在纯钛表面制备了含钙磷的多孔复合陶瓷膜,考察了微弧氧化时的电极电压对复合陶瓷膜的形貌、结构、成分和性能的影响.结果表明:在400～500 V的电压范围内,样品表面均形成了含有钙磷的多孔陶瓷膜,随着电极电压的升高,膜层表面微孔数日减少.孔径增大,膜层厚度增加.在400 V时,膜层的相构成为Ti 锐钛矿相TiO2 Ca3(PO4)2;在450 V和500 V时,膜层的相构成均为Ti 锐钛矿相TiO2 金红石相TiO2,Ca3(PO4)2消失,且随着电压的升高,锐钛矿相TiO2减少,金红石相TiO2增多.膜层中的钙磷摩尔比均随电压的升高而增大.在450V和500V时,膜层的临界载荷值分别为29.5N和14.8N.     

医用双相磷酸钙陶瓷的制备工艺研究

医用双相磷酸钙（BCP）陶瓷是β-磷酸三钙（β-TCP）和羟基磷灰石（HA）的复合体,其成分与骨矿物组成类似。它具有良好的生物相容性,在生物医学领域具有非常广阔的应用前景。且在生理环境下能发生不同程度的降解,被组织吸收。通过化学沉淀法制备纳米羟基磷灰石,然后通过可溶性钙盐和磷酸盐反应工艺制得β-磷酸三钙,最后将二者进行机械复合而制得双相磷酸钙,将所得样品用X射线衍射仪（XRD）进行了表征。结果显示：所得的双相磷酸钙中掺杂有β-焦磷酸钙,但是它的结晶较好,并且可以改善双相磷酸钙陶瓷的力学性能。     

The preparation and characterization of HA/β-TCP biphasic ceramics from fish bones

The aim of this research is to observe the physicochemical characterization and evaluate the biocompatibility of the HA/β-TCP biphasic calcium phosphate ceramics (BCP) produced from fish bones. In addition, the mechanism of the formation of BCP after calcination of fish bones was discussed. Three kinds of fish bones (Salmo salar, Anoplopoma fimbria and Sardine) were prepared and calcined for one hour at different temperatures ranging from 600 °C to 1100 °C in a muffle furnace. The calcined bones were analyzed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (GTA), inductively coupled plasma optical atom emissions spectroscopy (ICP-OES), X-ray fluorescence (XRF) and scanning electron microscopy (SEM). The in vitro cytotoxicity assessment was used to evaluate the biocompatibility of the biphasic ceramics. BCP materials were produced from all kinds of fish bones by calcination above 700 °C, the carbonated hydroxyapatite and multiple trace element were also found in the calcined bones. With the increase of temperature, the ratio of HA/β-TCP varied and the major organic components were progressively removed. The carbonated hydroxyapatite disappeared when temperature rises above 900 °C. Rising temperature also caused crystal growth that eventually gave rise to the increase of the BCP grain size and influenced the mesoporous structure. The BCP materials were confirmed to have no obvious cytotoxicity to mesenchymal stem cells (MSC) in the in vitro cytotoxicity assessment. Calcium-deficient hydroxyapatite(CDHA) may make up the major inorganic constituent of fish bones that could decompose to HA and β-TCP when calcined above 700 °C. 800–900 °C is considered to be the optimal temperature to fabricate BCP materials which contain more β-TCP, carbonated hydroxyapatite and retain distinct mesoporous structure while has good biocompatibility. With the unique composition and structure, these three kinds of fish-bone-derived BCP materials can be further applied to fabricate bioceramic scaffolds for biomedical applications.     

Effect of the HA/β-TCP Ratio on the Biological Performance of Calcium Phosphate Ceramic Coatings Fabricated by a Room-Temperature Powder Spray in Vacuum

Four calcium phosphate ceramic coatings, the less soluble hydroxyapatite (HA) coating, the more soluble β-tricalcium phosphate (β-TCP) coating, and two biphasic calcium phosphate (BCP) coatings with HA/β-TCP ratios of 70/30 and 30/70 were fabricated by spraying each corresponding powder onto a titanium substrate at room temperature (RT) in a vacuum, in order to investigate the effect of the HA/β-TCP ratio on the dissolution behavior and the cellular responses of the coating. No secondary phases, except for HA and β-TCP, were observed for the coatings in the X-ray diffraction results. The coating compositions were almost the same as those of the starting powders because the coating was conducted at RT. Microscopic examination of the coatings revealed crack-free and dense microstructures. The BCP coatings exhibited dissolution rates intermediate between those of the pure HA and β-TCP coatings. The dissolution rate of the coatings was largely dependent on their HA/β-TCP ratio. The cell proliferation and differentiation results indicated that the cellular responses of the coatings were not proportional to their dissolution rates. The 3HA–7TCP (HA/β-TCP ratio of 30/70) coating exhibited an optimal dissolution rate for excellent biological performance.     

β-TCP scaffold coated with PCL as biodegradable materials for dental applications

Requirements for an ideal scaffold include biocompatibility, biodegradability, mechanical strength and sufficient porosity and pore dimensions. Beta tricalcium phosphate (β-TCP) has competent biocompatibility and biodegradability, but has low mechanical strength because of its porous structure. Polycaprolactone (PCL) is a biodegradable polymer with elastic characteristics and good biocompatibility. In this study, β-TCP/PCL composites were prepared in different ratio and their morphology, phase content, mechanical properties, biodegradation and biocompatibility were investigated. After coating, surfaces of β-TCP scaffolds were covered with the PCL while some of the pores were partially clogged. The compression and bending strength of β-TCP scaffolds were significantly enhanced by PCL coating. The degradation rate of the scaffold in Tris buffer was reduced with higher content of the PCL coating. MTT and ALP assays showed that the osteoblast cells could proliferate and differentiate on PCL coated scaffolds as well as on bare β-TCP scaffolds. Based on the comprehensive analysis achieved in this study, it is concluded that the β-TCP/PCL composite scaffold fabricated with 40% β-TCP and 5% PCL exhibits optimum properties suitable for dental applications.     

A Novel Biphasic Bone Scaffold: β-Calcium Phosphate and Amorphous Calcium Polyphosphate

Calcium polyphosphate (CPP) was added to hydroxyapatite (HA) to develop a novel biphasic calcium phosphate (BCP). The effects of varying CPP dosage on the sintering property, the mechanical strength, and the phase compositions of HA were investigated. Results showed that CPP reacted with HA and produced β-calcium phosphate (β-TCP) and H₂O and that an excessive dosage of CPP (>10 wt%) obtained a novel BCP of β-TCP/amorphous-CPP, while a lesser dosage of CPP (<10 wt%) obtained a traditional BCP (HA/β-TCP). The porous β-TCP/amorphous-CPP scaffolds (porosity of 66.7%, pore diameter of 150–450 μm, and compressive strength of 6.70±1.5 MPa) were fabricated and their in vitro degradation results showed a significant improvement of degradation with the addition of CPP.     

In situ formation of biphasic calcium phosphates and their biological performance in vivo

The co-precipitation technique has been applied to synthesize biphasic calcium phosphate (BCP). After annealing at 900 °C for 24 h, hydroxyapatite (HAp) and β-tricalcium phosphate (β-TCP) were obtained as a single phase at 1.67 and 1.5 Ca/P ratios, respectively. Between these two extremes, a whole range of BCP preparations could be synthesized by using this technique with an accurate control of starting reactants. The biological performance of BCP granulates with a specific content of 62% HAp and 38% β-TCP was investigated. After immersion in Hanks’ balanced salt solution (HBSS) for 1 week, a precipitation started to be formed with individual small granules on the specimen surface. An MTT assay indicated that BCP granulates have no cytotoxic effects on MG-63 cells, and that they have good biocompatibility. An implantation experiment in mouse skulls revealed that BCP granulate provides a strong positive effect on bone formation in vivo in mice.     

Regulating the multifactor during wet chemical synthesis to obtain calcium phosphate powders with controllable phase purity for bone repair

Calcium phosphate ceramics are widely used as bone repair materials owing to their excellent biocompatibility, bone conductivity, bone induction, and degradability. Although there are many methods for synthesizing calcium phosphate and controlling its phase composition, it is necessary to explore effective preparation methods by understanding the formation of calcium phosphate and its influencing factors. In this study, calcium phosphate powders with controllable phase compositions were synthesized using a wet chemical precipitation method by adjusting the process parameters (aging time, bipolar solution, initial Ca-P molar ratio, capping agent concentration, and system concentration). Subsequently, a certain biphasic proportion of (biphasic calcium phosphate, BCP) products was prepared, and pure (β-tricalcium phosphate, β-TCP) can be obtained according to the customer's requirements. BCP ceramics with desired phase compositions were obtained by pressing and sintering different calcium-deficient powders. Specifically, β-TCP powder with a purity of 99.83 wt% was obtained when the aging time, bipolar solution, initial Ca-P molar ratio, capping agent concentration, and system concentration were 0 h, 50% ethanol, 1, 0.27 M, and 0.0135 M, respectively. The BCP synthesized in this study shows great application potential in the field of bone tissue repair materials.     

Properties of calcium phosphates ceramic composites derived from natural materials

In this study, ceramics containing mixed phases of hydroxyapatite/beta-tricalcium phosphate (HA/β-TCP) were fabricated by a solid-state reaction technique. The HA powder was synthesized from cockle shells while the β-TCP powder was synthesized from egg shells. Pure HA and β-TCP fine powders were successfully obtained. The HA and β-TCP were mixed and subjected to a thermal treatment up to 1100 °C. To form the mixed phase ceramics, the resulting powders were sintered at 1350 °C. Effects of HA concentration on the properties of the studied ceramic were investigated. X-ray diffraction analysis revealed that all samples presented multiphase of calcium phosphate compounds. Average grain size of the ceramics decreased with the HA additive content. The 75 wt% HA ceramic showed the maximum hardness value (5.5 GPa) which is high when compared with many calcium phosphate ceramics. In vitro bioactivity test indicated that apatite forming increased with the HA additive content. To increase antibacterial activity, selected ceramics were coated with AgNO₃. Antibacterial test suggested that an Ag compound coating on the ceramics could improve the antibacterial ability of the studied ceramics. In addition, the antibacterial ability for the Ag coated ceramics depended on the porosity of the ceramics.     

Fabrication,characterization and cellular biocompatibility of porous biphasic calcium phosphate bioceramic scaffolds with different pore sizes

Facile wet-chemical methods are applied to synthesize hydroxyapatite and β-tricalcium phosphate nanoparticles, respectively. Porous biphasic calcium phosphate (BCP) bioceramic scaffolds are then fabricated using as-prepared HA and β-tricalcium phosphate nanoparticle powders. The macro pore diameter of BCP bioceramic scaffolds can be controlled by adjusting the amount of surfactants. The average diameter of the macro pores in BCP bioceramic scaffolds increases from 100 to 600 µm with the decrease amount of sodium dodecyl sulfate from 0.8 to 0.5 g, respectively. The BCP bioceramic scaffolds gradually degrade and the calcium-phosphate compounds fully deposit when soaking in simulated body fluid solution. Moreover, The BCP bioceramic scaffolds have outstanding biocompatibility to promote the cellular growth and proliferation of human dental pulp stem cells (hDPSCs). The hDPSCs also demonstrate favorable cellular adhering capacity on the pore surface of scaffolds, especially on the scaffolds with 100–200 µm pore diameter. The porous BCP bioceramic scaffold with inter-connected pore structure, outstanding in vitro cellular biocompatibility, favorable cell viability and adhesion ability will be a promising biomaterial for bone or dentin tissue regeneration.