Fabrication and characterization of needle-like nano-HA and HA/MWNT composites

Hydroxyapatite (HA) ceramic has been used in tissue engineering and orthopedics for its good biocompatibility and osteoconductivity. However, its clinical applications are usually limited by the low strength and brittleness. The objective of this research was to develop a new kind of HA composites in which multi-wall carbon nanotubes (MWNTs) were introduced to the HA ceramic matrix to improve the mechanical properties of the resulting composites. A simple chemical wet method was applied to synthesize the HA ceramic particles with the aid of surfactant and ultrasonication technique at normal atmospheric pressure. The morphology and microstructure of the synthesized HA were characterized by XRD and TEM as a function of treatment time. The results showed that the synthesized HA particles are needle-like with a length of 80–160 nm along the (211) direction and an aspect ratio of 5–15. MWNTs were treated with a mixture of nitric acid and sulfuric acid. The HA/MWNT composites were prepared by solution blending. The composites were sintered using a hot-press method. The mechanical properties of the HA/MWNT composites with different volume percentages of MWNTs were examined. The fracture toughness and flexural strength were improved by 50% and 28% separately when the volume percentage of MWNTs reached 7%.     

多孔α-Al2O3基陶瓷片状载体的制备与性能

采用干压成型法制备了多孔α-Al₂O₃基陶瓷片, 研究了烧结温度和掺杂SiO₂对其结构、形貌和性能的影响. 提高烧结温度能增加α-Al₂O₃基陶瓷片的抗压强度, 但收缩率也会随之增大。最佳烧结温度为1180℃, 收缩率小于0.5%, 抗压强度大于80 MPa。当掺杂SiO₂粉体后, 陶瓷片中的无定形SiO₂在烧结过程中晶化形成方石英, 能够促进α-Al₂O₃陶瓷片的烧结。当SiO₂含量为12wt%, 并在1180℃下烧结时, 陶瓷片的收缩率仅为1.2%, 抗压强度大于110 MPa。与α-Al₂O₃陶瓷片相比, 其孔径更小但孔径分布更宽。研究表明, α-Al₂O₃和SiO₂/Al₂O₃陶瓷片均具有良好的分子筛膜生长活性。但由于载体具有不同的物化性质, 所制备的ZSM-5分子筛膜具有不同的形貌和尺寸。     

Effects of rheological properties on ice-templated porous hydroxyapatite ceramics

Freeze casting of aqueous suspension was investigated as a method for fabricating hydroxyapatite (HA) porous ceramics with lamellar structures. The rheological properties of HA suspensions employed in the ice-templated process were investigated systematically. Well aligned lamellar pores and dense ceramic walls were obtained successfully in HA porous ceramics with the porosity of 68–81% and compressive strength of 0.9–2.4 MPa. The results exhibited a strong correlation between the rheological properties of the employed suspensions and the morphology and mechanical properties of ice-templated porous HA ceramics, in terms of lamellar pore characteristics, porosities and compressive strengths. The ability to produce aligned pores and achieve the manipulation of porous HA microstructures by controlling the rheological parameters were demonstrated, revealing the potential of the ice-templated method for the fabrication of HA scaffolds in biomedical applications.     

溶胶–凝胶法制备不同形态的半透明羟基磷灰石陶瓷

为探索制备不同形态半透明羟基磷灰石(T-HA)陶瓷的方法, 采用微米级HA粉体为原料, 甲壳素为粘结剂, 用溶胶–凝胶法制备出球状和纤维状的陶瓷初坯, 然后进行常压烧结得到纯HA陶瓷, 最后经过热等静压烧结得到T-HA陶瓷。溶胶–凝胶法赋形简单, 制备出的球状T-HA陶瓷的球形度良好, 纤维状T-HA陶瓷的纵横比高, 其致密度为99.1%, 平均晶粒尺寸为2.2 μm。其中球状半透明HA陶瓷的抗压强度为10.2 MPa, 高于常规烧结得到的球状致密和多孔HA陶瓷(分别为8.9和4.7 MPa)。仿生矿化和细胞培养的结果显示半透明HA陶瓷具有良好的生物相容性。     

Influence of preparation method on hydroxyapatite porous scaffolds

Hydroxyapatite (HA) is extensively used in medical applications as an artificial bone because of its similarity to the natural components of human bones and for its excellent biocompatibility. The porous structure of HA ceramics is more generally used as a scaffold. Many techniques, which are performed under fluid system, have been applied to fabricate HA porous scaffolds. In this work, polymeric sponge technique was employed in the preparation of HA slurry appropriated for porous ceramic fabrication. Effort for strength improvement was made on porous HA ceramic in several aspects. The effect of HA/water, binder/plasticizer ratios and dispersant content on the rheological properties of HA suspension in combination with the addition of SiC and SiO₂ on the compressive strength of porous bodies were investigated and discussed.     

Processing and properties of nanoporous hydroxyapatite ceramics

Method for fabrication and properties of nanoporous hydroxyapatite (HA) ceramic were described in the present work. The nanoporous hydroxyapatite was derived from nano hydroxyapatite powder and polyvinyl alcohol (as a pore former). The HA nanopowder was obtained from vibro-milling for 4 h. The nanoporous ceramics were sintered at 1200 °C. Properties of the nanoporous ceramics were investigated using various methods. Average porosity of the final product was found to be 64.6 ± 1.4%. Open and interconnected pores were obtained with an average pore size less than 100 nm, confirming the nanoporous structure of this ceramic. A high bending strength of 14.7 ± 3.2 MPa for the nanoporous ceramic, shows significant promise as a potential bone repairing material.     

3D打印氧化铝陶瓷的气氛脱脂热处理工艺研究

脱脂热处理工艺对于3D打印陶瓷的成形质量具有重要的影响。目前光固化3D打印制备得到的氧化铝生坯经过在空气中的脱脂热处理工艺后烧结最终得到的氧化铝陶瓷存在的微观裂纹等缺陷, 将导致其力学性能较差。本工作研究了基于数字光处理(Digital light processing, DLP)技术的氧化铝陶瓷打印热处理工艺, 将3D打印制备得到的氧化铝陶瓷生坯分别在空气与氩气中脱脂后比较其宏观形貌, 发现在空气下脱脂的氧化铝生坯存在微观裂纹。再将脱脂后的生坯在空气下烧结得到氧化铝陶瓷, 并对其微观形貌和宏观性能进行表征, 发现在氩气下脱脂的氧化铝陶瓷平均晶粒尺寸要比直接在空气中脱脂得到的氧化铝陶瓷平均晶粒尺寸大, 而且晶粒结构致密, 无明显气孔和杂相, 而且具有更高的抗压强度。这说明在氩气中脱脂后烧结得到的氧化铝陶瓷性能更好。在氩气中脱脂的氧化铝致密度最高可达到96.72%, 抗压强度可达到761.7 MPa, 相比于只在空气中脱脂的氧化铝陶瓷性能得到显著提升。     

采用定向SiC纳米线烧结制备高强多孔 SiC陶瓷

利用直接墨水打印方法制备了由定向SiC纳米线交错叠层组成的具备网络状孔隙结构的高强SiC多孔陶瓷.制备的碳化硅多孔陶瓷具有高的通孔结构和完全由定向SiC纳米线组装而成的结构特征.研究了烧结温度对定向SiC纳米线多孔陶瓷的微观结构、相组成演变及力学性能的影响.研究结果表明:烧结温度低于1900℃时,SiC纳米线能保持高长...     

Effect of sintering atmosphere on the microstructure and dielectric properties of barium strontium titanate glass–ceramics

The sintering of barium strontium titanate glass–ceramics in nitrogen modified their dielectric properties significantly compared to the sintering in air. The experimental results demonstrate that the glass–ceramics sintered at low temperatures contain a major phase Ba₂TiSi₂O₈ (BTS), known as fresnoite. The fresnoite phase disappeared and the barium strontium titanate perovskite phase became the major phase when the sintering temperature was increased. In addition, the microstructure observation showed that both the proportion of crystal phase and the crystal size increase obviously with the increase of sintering temperature. Most importantly, impedance spectroscopy has been employed to study the electrical responses arising from the glass and the crystal phases in the glass–ceramics sintered at low temperatures and high temperatures. The magnitudes of impedance and modulus changed significantly for the glass–ceramics sintered at the two temperature ranges. The activation energy calculated from the complex impedance, complex modulus and dc conductivity suggests that the dielectric relaxation for the glass phase and the glass–crystal interface may be attributed to the motion of the dipole associated with oxygen vacancy. And for the barium strontium titanate perovskite glass–ceramics, the motion of the electrons from the second ionization of oxygen vacancies leads to dc electrical conduction. The mechanism for the giant dielectric properties of the glass–ceramics sintered at high temperatures in nitrogen is discussed.     

表面多孔NiTi-羟基磷灰石/NiTi生物复合材料的制备与性能

利用放电等离子烧结技术制备了表面多孔NiTi-羟基磷灰石(HA)/NiTi生物复合材料,研究了烧结温度对复合材料宏观形貌、微观结构、表面孔隙特征、力学性能及体外生物活性的影响。结果表明:随着烧结温度从800℃提高到950℃,NiTi-HA/NiTi复合材料由复杂的Ti、Ni、Ti_2Ni、Ni_3Ti、HA混合相逐渐转变为单一的NiTi+HA相,内外层界面形成稳定的冶金结合且表面孔隙率与平均孔径呈缓慢减小趋势;同时抗压强度显著提高而弹性模量变化不明显。与传统NiTi、多孔NiTi及多孔NiTi-HA材料相比,950℃温度下制备的NiTi-HA/NiTi复合材料不仅具有良好的界面结合和表面孔隙特征(孔隙率45.6%、平均孔径393μm)、较高的抗压强度(1 301MPa)、较低的弹性模量(10.2GPa)以及优异的超弹性行为(超弹性恢复应变4%)的最佳匹配,而且还具有良好的体外生物活性。     

Fabrication,chemical composition change and phase evolution of biomorphic hydroxyapatite

Biomorphous, highly porous hydroxyapatite (HA) ceramics have been prepared by a combination of a novel biotemplating process and a sol-gel method, using natural plants like cane and pine as biotemplates. A HA sol was first synthesized from triethylphosphate and calcium nitrate used as the phosphorus and calcium precursors, respectively, and infiltrated into the biotemplates, and subsequently they were sintered at elevated temperatures to obtain porous HA ceramics. The microstructural changes, phase and chemical composition evolutions during the biotemplate-to-HA conversion were investigated by scanning electron microscopy (SEM), X-ray powder diffraction (XRD), and Fourier-transform infrared (FT-IR) spectroscopy. The XRD and FT-IR analysis revealed that the dominant phase of the product was HA, which contained a small amount of mixed A/B-type carbonated HA, closely resembling that of human bone apatite. Moreover, the appearance of a small amount of secondary phase CaCO(3) seemed unavoidable. The HA was not transformed to the other calcium phosphate phases up to 1400 degrees C, but it contained a trace amount of CaO when sintered at above 1100 degrees C. The possible transformation mechanism was proposed. The SEM observation and mechanical property test showed that as-produced HA ceramics retained the macro-/micro-porous structures of the biotemplates with high precision, and possessed acceptable mechanical strength, which is suggested to be potential scaffolds for bone tissue engineering.     

Mn、Sb掺杂NBT—KBT—BT无铅压电陶瓷的研究

采用传统陶瓷制备工艺,利用XRD、SEM等测试分析方法,研究了MnCO3、Sb2O3掺杂对压电陶瓷晶体结构、表面形貌以及性能的影响。研究结果表明：所有组成均呈单一钙钛矿型固溶体特征,无其它晶相生成。掺杂陶瓷在1160℃左右烧结比较合适。MnCO3表现为典型的“受主”添加物特征。Sb2O3的掺杂对陶瓷性能的影响受多种因素共同作用,当Sb2O3的掺杂量为0.1％（质量分数）时,d33=148pC／N、tanδ=4.2％、εr=1516。MnCO3的掺杂可以促进晶粒生长,Sb2O3的掺杂使晶粒尺寸的均匀性降低。     

Porous bioceramics reinforced by coating gelatin

Porous bioceramics with high porosity for bone tissue engineering were fabricated by the foam impregnation technique, but their mechanical strength was poor, only a mean compressive strength of 1.04 ± 0.15 MPa and an mean elastic modulus of 0.1 GPa. In order to reinforce porous ceramics, the ceramic samples were immerged in 5% gelatin solution and gelatin coatings were formed on the inter-surface of their pores. It was found that the mean compressive strength value and the mean elastic modulus value of porous samples coated with gelatin were improved to 5.17 ± 0.17 MPa and 0.3 GPa respectively without sacrificing their porosity greatly. Moreover composite samples were not as fragile as sintered ceramics. The results indicated that the gelatin coatings on the inter-surface of pores reinforced porous bioceramics effectively.     

New concept bioceramics composed of octacalcium phosphate (OCP) and dicarboxylic acid-intercalated OCP via hydrothermal hot-pressing

Octacalcium phosphate (OCP) and adipic acid-intercalated complexed OCP (Adi-OCP) were synthesized. Moreover, we made ceramic bodies out of them through a hydrothermal hot-pressing (HHP) method. Characteristic features of both the powder and ceramics were investigated by the X-ray diffraction method (XRD). Surface morphology of the ceramics was observed by scanning electron microscopy (SEM). Density, compressive strength and pore size distribution of the ceramics were measured. Crystalline structure of the newly developed OCP ceramics had no phase transformation from the starting materials. Moreover, the newly developed OCP ceramics had good mechanical properties only through the HHP treatment with a temperature as low as 110 °C. In order to evaluate bioactivity, the ceramics were immersed in simulating body fluid (SBF). It was predicted that OCP and Adi-OCP had better bioactivity than that of conventional HAp ceramics.     

Effect of MgO contents on the mechanical properties and biological performances of bioceramics in the MgO–CaO–SiO2 system

The aim of this research was to investigate the effect of the chemical composition on the mechanical properties, bioactivity, and cytocompatibility in vitro of bioceramics in the MgO–CaO–SiO₂ system. Three single-phase ceramics (merwinite, akermanite and monticellite ceramics) with different MgO contents were fabricated. The mechanical properties were tested by an electronic universal machine, while the bioactivity in vitro of the ceramics was detected by investigating the bone-like apatite-formation ability in simulated body fluid (SBF), and the cytocompatibility was evaluated through osteoblast proliferation and adhesion assay. The results showed that their mechanical properties were improved from merwinite to akermanite and monticellite ceramics with the increase of MgO contents, whereas the apatite-formation ability in SBF and cell proliferation decreased. Furthermore, osteoblasts could adhere, spread and proliferate on these ceramic wafers. Finally, the elongated appearance and minor filopodia of cells on merwinite ceramic were more obvious than the other two ceramics.     

碳化硅网眼多孔陶瓷的制备

本工作采用有机泡沫浸渍工艺制备了具有相互贯通气孔的碳化硅网眼多孔陶瓷．通过选择合适的流变剂获得了对海绵具有良好涂覆性能的浆料．探讨了粘结剂对网眼多孔陶瓷性能的影响,结果表明：硅溶胶是一种比较理想的粘结剂．ＸＲＤ、ＳＥＭ研究了烧结制品的晶相组成及显微结构,同时还对烧结制品的孔筋密度、气孔率、力学性能等进行了表征．本工作在１４５０℃下保温１ｈ获得了气孔率为７５％～８５％、抗弯强度达２．５ＭＰａ以上的碳化硅网眼多孔陶瓷,其主要晶相由α－ＳｉＣ、α－Ａｌ_２Ｏ_３、方石英和莫来石组成．     

3D printing of hydroxyapatite scaffolds with good mechanical and biocompatible properties by digital light processing

Hydroxyapatite is a scaffold material widely used in clinical repair of bone defects, but it is difficult for traditional methods to make customized artificial bone implants with complicated shapes. 3D printing biomaterials used as personalized tissue substitutes have the ability to promote and enhance regeneration in areas of defected tissue. The present study aimed at demonstrating the capacity of one 3D printing technique, digital light processing (DLP), to produce HA scaffold. Using HA powder and photopolymer as raw materials, a mixture of HA mass ratio of 30 wt% was prepared by viscosity test. It was used for forming ceramic sample by DLP technology. According to differential scanning calorimetry and thermal gravity analysis, it was revealed that the main temperature range for the decomposition of photopolymer was from 300 to 500 °C. Thus, the two-step sintering process parameters were determined, including sintering temperature range and heating rate. XRD analysis showed that the phase of HA did not change after sintering. SEM results showed that the grain of the sintered ceramic was compact. The compression model was designed by finite element analysis. The mechanical test results showed that the sample had good compression performance. The biological properties of the scaffold were determined by cell culture in vitro. According to the proliferation of cells, it was concluded that the HA scaffold was biocompatible and suitable for cell growth and proliferation. The experimental results show that the DLP technology can be used to form the ceramic scaffold, and the photopolymer in the as-printed sample can be removed by proper high-temperature sintering. The ceramic parts with good compression performance and biocompatibility could be obtained.     

Preparation of novel ceramics with high CaO content from steel slag

Steel slag, an industrial waste discharged from steelmaking process, cannot be extensively used in traditional aluminosilicate based ceramics manufacturing for its high content of calcium oxide. In order to efficiently utilize such solid waste, a method of preparing ceramics with high CaO content was put forward. In this paper, steel slag in combination with quartz, talcum, clay and feldspar was converted to a novel ceramic by traditional ceramic process. The sintering mechanism, microstructure and performances were studied by scanning electron microscope (SEM), X-ray diffraction (XRD) techniques, combined experimenting of linear shrinkage, water absorption and flexural strength. The results revealed that all crystal phases in the novel ceramic were pyroxene group minerals, including diopsite ferrian, augite and diopsite. Almost all raw materials including quartz joined the reaction and transformed into pyroxene or glass phase in the sintering process, and different kinds of clays and feldspars had no impact on the final crystal phases. Flexural strength of the ceramic containing 40 wt.% steel slag in raw materials can reach 143 MPa at sintering temperature of 1210 °C and its corresponding water absorption, weight loss, linear shrinkage were 0.02%, 8.8%, 6.0% respectively. Pyroxene group minerals in ceramics would contribute to the excellent physical and mechanical properties.     

羟基磷灰石/Ti-13Nb-13Zr复合材料的组织性能与细胞相容性评价

为了改善Ti-13Nb-13Zr医用钛合金的生物活性与细胞相容性,利用放电等离子烧结(SPS)技术制备了Ti-13Nb-13Zr合金和羟基磷灰石(HA)含量5wt%的5HA/Ti-13Nb-13Zr复合材料并进行退火处理,研究了两种材料的显微组织、力学性能、表面润湿性、体外矿化行为及细胞增殖与凋亡等生物学性能。结果表明：合金主要由β-Ti和α-Ti相组成,复合材料由β-Ti、α-Ti、HA相及少量陶瓷反应相(Ca₃(PO₄)₂、CaZrO₃、CaO)组成,退火后部分初生α-Ti转变为β-Ti且组织更均匀,HA的加入会使得晶粒细化;退火后两种材料抗压强度、屈服强度、屈强比和弹性模量均略微下降;HA的加入提高了复合材料亲水性、类骨磷灰石形成能力、细胞增殖率并降低了细胞凋亡率;综合分析,退火后的5HA/Ti-13Nb-13Zr复合材料抗压强度、屈服强度和弹性模量分别为(1 744±9) MPa、(1 493±12) MPa和(43±1.6) GPa,具有优异的类骨磷灰石形成能力,同时细胞增殖率达到99.1...     

熔融沉积法3D打印制备氧化锆陶瓷及其力学性能研究

在传统熔融沉积方法的基础上,采用颗粒混合料和螺杆挤出机构3D打印制备了致密和多孔氧化锆陶瓷,系统研究了颗粒原料的打印性能、坯体显微结构特征和陶瓷材料的力学性能。研究结果表明,该方法可以实现倾角达165°和跨度为5.5mm的无支撑结构的打印成型。研究了两种打印路径对致密氧化锆陶瓷抗弯强度及抗弯强度Weibull模数的影响,结果表明与传统单线填充模式相比,"单线+矩形"复合填充模式可以得到更高致密度和更优力学性能的陶瓷(抗弯强度达到637.8 MPa, Weibull模数达到9.10)。研究了不同气孔率多孔氧化锆陶瓷的压缩力学行为,结果表明陶瓷的抗压强度和气孔率之间存在复合指数规律,低气孔率时异面压缩的应力–应变曲线只呈现弹性阶段,高气孔率时出现弹性阶段和坍塌阶段,均未出现密实阶段。