Preparation of porous hydroxyapatite scaffolds

In this work, the sintering and grain growth of hydroxyapatite green bodies are analyzed in order to identify the optimum heat treatments for the preparation of porous hydroxyapatite scaffolds. Sintering in air at temperatures ranging between 1100 and 1200 °C yields dense materials with narrow grain-size distributions. The scaffolds are formed by the infiltration of polymer foams with hydroxyapatite slurries or by robocasting, a novel rapid-prototyping technique. Examples of the microstructures achieved with each approach are presented. It is observed that both techniques can be used to fabricate scaffolds with adequate pore size to promote bone ingrowth.     

Electrochemistry assisted reacting deposition of hydroxyapatite in porous chitosan scaffolds

Electrochemistry assisted reacting deposition method was employed to prepare porous chitosan/hydroxyapatite (CS/HA) composite scaffold with a new design device using ion exchange membranes to separate calcium salt and phosphate solutions. The results determined from XRD and SEM indicates hydroxyapatite can be electrochemically deposited in the chitosan scaffold using the device. After electrochemistry assisted reacting deposition, the surface of the chitosan scaffold was coated with low crystalline HA, particularly at the frame edge of the scaffold. The pores in the scaffold still kept interconnected well and the deposited hydroxyapatite has a cluster microsphere shape whose size is about 3-5 μm.     

Preparation of highly interconnected porous hydroxyapatite scaffolds by chitin gel-casting

In this study, a simple and effective method for producing highly interconnected porous hydroxyapatite (HA) scaffolds was developed by combining gel-casting, particle-leaching and extrusion techniques. Chitin (CT) sol was used to disperse HA particles and wax spheres were introduced as porogens for their excellent deformability. In extrusion process, the accumulated wax spheres in point-to-point contact can transform into surface-to-surface contact by means of the extrusion pressure. Thus, the obtained porous HA scaffolds exhibited an interconnected channel network after leaching out of the porogens. The results showed that the scaffolds prepared by different size of wax spheres exhibited nearly the same volumetric porosity of about 86%, while the compressive strengths decreased as the pore size increased. Therefore, the method developed can be used to effectively tailor the pore size of HA scaffolds while maintaining a high porosity. The highly porous HA scaffolds with excellent interconnectivity are expected to be a promising bone substitute in clinical practice.     

羟基磷灰石基多孔复合支架的制备及其表征

研究利用造孔剂法制备高度贯通的多孔羟基磷灰石(HA)支架,孔隙率约为78%,并利用聚己内酯(PCL)分别复合纳米HA(nHA)或微纳米生物玻璃(nBG)粉末对其进行涂覆改性,粉末的添加量均为10%~40%(质量分数)。4种类型支架分别记为HA、PCL/HA、nHA-PCL/HA和nBG-PCL/HA。实验结果发现,nHA-PCL/HA和nBG-PCL/HA复合支架最大抗压强度分别为1.41~1.98 MPa和1.35~1.78MPa。4类支架矿化实验显示,浸泡21d后nBG-PCL/HA表面促进生成较多的磷灰石矿化物;细胞实验结果显示细胞在4类支架上均生长良好,说明支架具有良好的生物相容性。支架在实验犬背部肌肉组织内植入2个月的组织学检测显示,4种支架内均有新骨形成,尤其是nHA-PCL/HA和nBG-PCL/HA孔内有更多的新生骨组织,说明这两种支架表面复合涂层中的生物活性纳米颗粒对诱导新骨生成具有积极的促进作用。     

Fabrication and characterization of novel hydroxyapatite/porous carbon composite scaffolds

Novel hydroxyapatite (HA)/porous carbon composite scaffolds were prepared by applying sonoelectrodeposition and a subsequent hydrothermal treatment to previous carbonized phenolic resin coated polyurethane sponges. The interconnected pore network and morphology of HA/porous carbon composite scaffolds were determined by scanning electron microscope (SEM), and the whole surface of porous carbons were evenly coated with the deposited HA layer which was confirmed by EDS and XRD. The porosity (83.5 ± 0.3%) and the bulk density (0.297 ± 0.009 g·cm⁻³) of HA/porous carbon scaffolds were detected by the Archimedes method. The compressive and flexural strength of the scaffolds is 1.187 ± 0.064 MPa and 0.607 ± 0.268 MPa, respectively. Compared with the polymeric surface of 24-well cell culture plates, these novel scaffolds significantly promote the proliferation of human osteoblast-like MG-63 cells, indicating that this novel HA/porous carbon composite scaffold could be used for in vitro 3D culture of osteoblasts.     

Novel,simple and reproducible method for preparation of composite hierarchal porous structure scaffolds

Demand to develop a simple and adaptable method for preparation the hierarchical porous scaffolds for bone tissue regeneration is ever increasing. This study presents a novel and reproducible method for preparing the scaffolds with pores structure spanning from nano, micro to macro scale. A macroporous Sr-Hardystonite (Sr–Ca₂ZnSi₂O₇, Sr–HT) scaffold with the average pore size of ~ 1200 μm and porosity of ~ 95% was prepared using polymer sponge method. The struts of the scaffold were coated with a viscous paste consisted of salt (NaCl) particles and polycaprolactone (PCL) to provide a layer with thickness of ~ 300–800 μm. A hierarchical porous scaffold was obtained with macro, micro and nanopores in the range of 400–900 μm, 1–120 μm and 40–290 nm, after salt leaching process. These scales could be easily adjusted based on the starting foam physical characteristics, salt particle size, viscosity of the paste and salt/PCL weight ratio.     

采用聚醚酯制备多孔支架的条件控制

采用热致相分离(TIPS)结合冷冻干燥技术制备了聚醚酯(聚对苯二甲酸丁二醇酯-co-聚对苯二甲酸环己烷二甲醇酯-b-聚乙二醇)(PTCG)多孔支架,研究了聚合物质量浓度、粗化温度和溶剂组成等相分离参数对多孔支架形貌结构的影响.结果表明,制备出的多孔支架孔间相互贯通,支架表面(与空气接触面)的孔径大于底面(与玻璃接触面)的孔径;随着聚合物质量浓度的增大,支架的孔径和孔隙率减小.由于分相过程中热力学推动力增大和相区融合阻力增加的相互作用,孔径随着粗化温度的降低呈现先升后降的趋势,并在0℃时出现最大值.在DO中加入不良溶剂H2O,溶液分相温度的升高导致多孔支架孔径的增大.通过控制相分离参数可以制备不同形貌结构的PTCG多孔支架.     

半乳糖修饰大孔壳聚糖支架的制备及表征

生物人工肝反应器中肝细胞的数量和功能是能否有效替代已衰竭肝脏功能的关键,与此紧密相关的是细胞支架材料结构和性能的优化.采用冷冻干燥法,制备了大孔壳聚糖支架,孔隙率在90%以上,平均孔径在100～200μm之间.以肝细胞表面去唾液酸糖蛋白受体(asialoglycoprotein receptor,ASGPR)的特异性配体-半乳糖,对材料表面进行糖基化修饰,制备了半乳糖基修饰的大孔壳聚糖支架,肝细胞在其上生长状况良好,细胞培养密度高,为高密度培养肝细胞提供了一种性能优良的支架材料.     

Characterization and osteoblast-like cell compatibility of porous scaffolds: bovine hydroxyapatite and novel hydroxyapatite artificial bone

Three different porous scaffolds were tested. The first two were prepared by sintering bovine bone. The third scaffold was prepared using three-dimensional gel-lamination, a new rapid prototyping method, and was named as hydroxyapatite artificial bone. X-ray diffraction and Fourier transform infrared spectroscopy analysis confirmed that the samples were mainly highly crystalline hydroxyapatite ceramics. Scanning electron microscopy and mercury intrusion porosimetry measurement showed that the pores were interconnected and pore sizes ranged from several microns to hundreds of microns. Mouse osteoblast-like cells grown on the three scaffolds retained their characteristic morphology. Cell proliferation and differentiation, analyzed by methylthiazol tetrazolium (MTT) and alkaline phosphatase activity assays, were significantly higher on the hydroxyapatite artificial bone than on the other two scaffolds tested. All the scaffolds provided good attachment, proliferation and differentiation of bone cells. These results indicate that the scaffolds have a favorable interaction with cells, they support cell growth and functions, and therefore these scaffolds may have great potential as bone substitutes. The three-dimensional gel-lamination method is proven to be an attractive process to design and fabricate bone scaffolds with favorable properties, and therefore, has promising potential for bone repair applications.     

注射成型羟基磷灰石/聚酰胺6多孔支架的微观结构和力学性能

采用注射成型法制备了羟基磷灰石/聚酰胺6(HA/PA6)多孔支架,用SEM、XRD、DSC等手段表征了支架的组成结构和形貌,检测了其力学性能.研究表明,调节羟基磷灰石(HA)含量、偶氮二甲酰胺(AC)用量和预塑量能有效控制支架的力学性能、孔径大小和孔隙率.HA/PA6支架的孔径在100～500μm左右,孔隙率达到甚至超...     

Improvement of compressive strength of porous hydroxyapatite scaffolds by adding polystyrene to camphene-based slurries

The compressive strength of porous hydroxyapatite (HA) scaffolds was enhanced by adding polystyrene (PS) polymer as a binder to hydroxyapatite (HA)/camphene slurries. As the PS content was increased from 0 to 20 vol.% in relation to the HA content, the compressive strength was significantly increased from 1.1 ± 0.2 to 2.3 ± 0.5 MPa, while the pore size was decreased from 277 ± 47 to 170 ± 29 µm. The improvement in the compressive strength was mainly attributed to both the suppression of the cracking of the green sample during freeze drying and the mitigation of the formation of micro-pores in the HA walls.     

非均相悬浮法制备多孔羟基磷灰石微球

为了获得具有吸附和生物学功能的多孔羟基磷灰石(HA)微球,以自制的纳米羟基磷灰石(HA)粉体为原料,用非均相悬浮法制备了HA/明胶微球,将微球在1 250℃下焙烧,成功制备了直径100~500μm的多孔HA微球.采用光学显微镜、SEM分析、XRD分析和BET氮吸附法研究了微球形貌、尺寸、物相组成、比表面积和孔径,测定了微球对水中F-离子的吸附性能.结果表明:微球具有良好球形形貌和相互贯通的纳米微孔;尺寸比较均匀,分散性良好;微球的主要结晶相为羟基磷灰石;BET表面积为1.867 0~2.089 5 m~2/g,孔径6.53~6.85 nm;对氟离子的平衡吸附容量为1.909~1.940 mg/g.通过控制m(HA)/m(明胶)比例、油温、搅拌速度和搅拌时间,可以在一定范围内控制微球直径和比表面积.     

Highly porous hydroxyapatite scaffolds with elongated pores using stretched polymeric sponges as novel template

This study reports a simple way of improving the compressive strength of highly porous hydroxyapatite (HA) scaffolds by adopting elongated polymeric sponges as a novel template. In this method, as-received polymeric sponges with isotropic pores were stretched uniaxially to 50% elongation at 200 °C for 2 h, and then coated with a HA slurry. The HA-coated sponges were heat-treated at 800 °C for 3 h to remove the polymeric sponges and at 1250 °C for 3 h to sinter the HA walls. The fabricated samples showed a highly anisotropic pore structure with elongated pores parallel to the direction of the elongation of the polymeric sponge. This simple method allowed a highly porous scaffold to have a high compressive strength of 3.8 ± 0.1 MPa at a porosity of 76% when tested parallel to the direction of pore elongation.     

组织工程海藻酸钙多孔支架的制备和研究

采用浇铸/冷冻干燥的方法制备出一种可组装于神经导管内的组织工程海藻酸钙多孔支架.通过IR、SEM、不同浓度交联剂对凝胶化过程的平衡溶胀比、抗压强度以及多孔支架在SBF液中的含水率和体积膨胀度的分析,对7海藻酸钙多孔支架的性能进行了讨论.结果表明,海藻酸钠多孔支架在氯化钙溶液浸渍中能快速反应生成海藻酸钙,并在凝胶化反应过程中可保持原有呈一定方向排列、孔隙连通和层状的多孔结构;多孔支架随交联剂中Ca2+浓度的增加,形成的海藻酸钙多孔支架的抗压强度提高,使支架的稳定性增加;海藻酸钙多孔支架在SBF中的含水率>90%,体积的膨胀度与交联剂中Ca2+浓度成反比.     

Fabrication and characterization of porous hydroxyapatite microspheres by spray-drying method

In the present paper, porous hydroxyapatite (HA) microspheres were fabricated using gelatin as a pore-forming agent by spray-drying method. The mean particle size of the microspheres is about 7 μm and the surface area is about 53.4 m²/g. The experimental results showed that the porosity of the prepared microspheres is higher and the pores are more interconnected compared with the microspheres obtained without any additives.     

Fabrication and characterization of porous hydroxyapatite microspheres by spray-drying method

In the present paper, porous hydroxyapatite (HA) microspheres were fabricated using gelatin as a pore-forming agent by spray-drying method. The mean particle size of the microspheres is about 7 ?m and the surface area is about 53.4 m²/g. The experimental results showed that the porosity of the prepared microspheres is higher and the pores are more interconnected compared with the microspheres obtained without any additives.     

Preparation of porous hydroxyapatite

The aim of the paper was to obtain a porous hydroxyapatite (HA) biomaterials relating to the manufacture of artificial implants. The technique of impregnating a body of porous polyurethane foam with slurry containing HA powder, water and additives was applied and proved to be more successful. The process of preparations was discussed and the porous HA with desired properties was obtained at last.     

Characterization of porous hydroxyapatite

Hydroxyapatite has been considered for use in the repair of osseous defects for the last 20 years. Recent developments have led to interest in the potential of porous hydroxyapatite as a synthetic bone graft. However, despite considerable activity in this field, regarding assessment of the biological response to such materials, the basic materials characterization is often inadequate. This paper documents the characterization of the chemical composition, mechanical integrity, macro- and microstructure of a porous hydroxyapatite, Endobon ® (E. Merck GmbH), intended for the bone-graft market. Specimens possesed a range of apparent densities from 0.35 to 1.44 g cm^-3. Chemical analysis demonstrated that the natural apatite precursor of Endobon® was not converted to pure hydroxyapatite, but retained many of the ionic substituents found in bone mineral, notably carbonate, sodium and magnesium ions. Investigation of the microstructure illustrated that the struts of the material were not fully dense, but had retained some traces of the network of osteocyte lacunae. Macrostructural analysis demonstrated the complex inter-relationship between the structural features of an open pore structure. Both pore size and connectivity were found to be inversely dependent on apparent density. Furthermore, measurement of pore aspect ratio and orientation demonstrated a relationship between apparent density and the degree of macrostructural anisotropy within the specimens, while, it was also noted that pore connectivity was sensitive to anisotropy. Compression testing demonstrated the effect of apparent density and macrostructural anisotropy on the mechanical properties. An increase in apparent density from 0.38 to 1.25 g cm^-3 resulted in increases in ultimate compressive stress and compressive modulus of 1 to 11 MPa and 0.2 to 3.1 GPa, respectively. Furthermore, anisotropic high density (> 0.9 g cm^-3) specimens were found to possess lower compressive moduli than isotropic specimens with equivalent apparent densities. These results underline the importance of full structural and mechanical characterization of porous ceramic implant materials. ©1999 Kluwer Academic Publishers     

注射参数和组分对羟基磷灰石／聚酰胺66多孔支架结构和性能的影响

采用注射成型法制备了羟基磷灰石／聚酰胺66（HA／PA66）多孔支架,用SEM、XRD和DSC等手段表征了支架的形貌和结构,测试了其力学性能。研究表明,调节注射参数（发泡剂和储料量）能控制支架的力学性能、孔径大小和孔隙率。HA能提高支架的刚性,但使孔径和孔隙率下降。在HA／PA66（30／70,质量比）中添加乙烯一醋酸...