Composite scaffolds of nano calcium deficient hydroxyapatite/multi-(amino acid) copolymer for bone tissue regeneration

In this study, nano calcium deficient hydroxyapatite (n-DA)/multi-(amino acid) copolymer composite scaffolds were prepared by injection molding foaming method using calcium sulphate dihydrate as a foaming agent. The composite scaffolds showed well interconnected macropores with the pore size of ranging from 100 to 600 μm, porosity of 81 % and compressive strength of 12 MPa, and the compressive strength obviously affected by the porosity. The composite scaffolds could be slowly degraded in phosphate buffered solution (PBS), which lost its initial weight of 61 w % after immersion into PBS for 12 weeks, and the porosity significantly affected the degradability of the scaffolds. Moreover, it was found that the composite scaffolds could promote the MG-63 cells growth and proliferation, and enhance its alkaline phosphatase activity. The implantation of the scaffolds into the femoral bone of rabbits confirmed that the composite scaffolds were biocompatibitive, degradable, and osteoconductive in vivo.     

海藻酸钙水凝胶/聚乳酸复合材料的制备与性能

通过化学发泡-冷冻干燥-粒子滤出复合法制备聚乳酸(PLLA)大孔支架, 然后在大孔内以海藻酸钠(SA)、碳酸钙、葡萄糖酸内酯(GDL)为原料, 通过原位相转变制备海藻酸钙水凝胶/聚乳酸复合材料(CA/PLLA); 分别利用SEM、压缩强度测试和细胞培养对CA/PLLA支架的形貌、力学性能及生物相容性进行了研究。结果表明: PLLA具有直径小于2 mm、孔道相互连通的孔洞, 且在大孔中能够形成均匀的CA。CA/PLLA复合材料的压缩强度(2.74 MPa)远大于单一的海藻酸钙水凝胶的压缩强度(0.10 MPa)。在CA/PLLA复合支架中, 软骨细胞呈簇状圆形生长状态, 与其在天然软骨陷窝里生长状态一致。这种软硬结合、天然与合成高分子杂化的CA/PLLA复合材料的力学强度和生物相容性同时得到提高, 可进一步作为骨和软骨修复材料研究。     

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.     

Fabrication of porous low crystalline calcite block by carbonation of calcium hydroxide compact

Calcium carbonate (CaCO₃) has been widely used as a bone substitute material because of its excellent tissue response and good resorbability. In this experimental study, we propose a new method obtaining porous CaCO₃ monolith for an artificial bone substitute. In the method, calcium hydroxide compacts were exposed to carbon dioxide saturated with water vapor at room temperature. Carbonation completed within 3 days and calcite was the only product. The mechanical strength of CaCO₃ monolith increased with carbonation period and molding pressure. Development of mechanical strength proceeded through two steps; the first rapid increase by bonding with calcite layer formed at the surface of calcium hydroxide particles and the latter increase by the full conversion of calcium hydroxide to calcite. The latter process was thought to be controlled by the diffusion of CO₂ through micropores in the surface calcite layer. Porosity of calcite blocks thus prepared had 36.8–48.1% depending on molding pressure between 1 MPa and 5 MPa. We concluded that the present method may be useful for the preparation of bone substitutes or the preparation of source material for bone substitutes since this method succeeded in fabricating a low-crystalline, and thus a highly reactive, porous calcite block.     

Synthesis and characterization of porous κ-carrageenan/calcium phosphate nanocomposite scaffolds

The polysaccharide κ-carrageenan was used in the production of macroporous composites containing nanosized hydroxyapatite, with potential application in bone tissue engineering. Biodegradable composite scaffolds were prepared combining in situ co-precipitation of calcium phosphates with a freeze-drying technique. The effect of the Ca/P molar ratio and total ceramic content on the chemical composition, microstructure and mechanical performance of the scaffolds were investigated by thermal analysis, X-ray diffraction, FTIR, transmission electron microscopy, scanning electron microscopy, He porosimetry and compressive tests. A mixture of amorphous calcium phosphates and/or nanosized calcium-deficient hydroxyapatite was obtained in most of the composites. The formation of hydroxyapatite was induced by higher Ca/P ratios, probably due to competing reticulation of the biopolymer with calcium cations. The composite scaffolds presented interconnected pores (50–400 μm) and porosity around 97% and calcium phosphates were uniformly dispersed in the κ-carrageenan matrix. Both microstructure and compressive mechanical properties of the scaffolds were affected by the ceramic content and, for a Ca/P molar ratio of 1.67, maximum compressive strength was achieved for a ceramic content of ca. 25 wt%. Above this value the structural integrity of the composite was damaged and a dramatic decrease in mechanical strength was verified. Compressive mechanical properties of the composites were improved by increasing Ca/P atom ratio.     

Effect of internal water content on carbonation progress in cement-treated sand and effect of carbonation on compressive strength

This study investigates the effect of internal water content in cement-treated sand on carbonation progress and the effect of carbonation on compressive strength. To alter the internal water content, specimens were cured under three conditions: sealed, drying, and water sprayed. The carbonation coefficient, which was determined by a phenolphthalein spray test, decreased as the internal water content increased because of water sprayed. However, a thermal analysis revealed that the amounts of portlandite consumed and calcium carbonate generated by carbonation exhibited dissimilar trends: the amount of generated calcium carbonate was the maximum when there was a small increase in water content by water sprayed. Further increments in water content significantly lowered the amount of generated calcium carbonate. The measured compressive strength increased linearly with the amount of calcium carbonate. This implies that the amount of calcium carbonate is a good indicator of the effect of carbonation on the strength development of cement-treated sand and that both these quantities are affected by the internal water content.     

添加成孔剂法制备孔径、气孔率可控的多孔玻璃陶瓷

研究了采用添加成孔剂法制备具有相互贯通气孔的多孔生物玻璃陶瓷的方法及其性能.多孔玻璃陶瓷主晶相为氟磷灰石和β-硅灰石,气孔率在49％-82％间连续可控,气孔由成孔剂热解排除形成的球形宏观孔(孔径200-850μm)和玻璃粉体烧结形成的微观孔(孔径2-4μm)组成,宏观孔孔径取决于成孔剂粒径并通过孔壁上的孔洞(孔径50-300μm)相互连通.塑性成孔剂硬脂酸受压产生塑性变形,添加硬脂酸的素坯强度高、可加工,烧结产物强度较高、气孔为扁球状;刚性成孔剂聚苯乙烯受压产生弹性变形,添加聚苯乙烯的素坯疏松、不可加工,烧结产物强度较低、气孔呈圆球状.成形压力对添加塑性成孔剂的样品性能影响显著,而对添加刚性成孔剂的样品性能无显著影响.气孔率与成孔剂的含量成良好的线性关系,通过控制成孔剂粒径和加入量可达到气孔率、孔径可控的目的.孔径一定时抗压强度与总气孔率成良好的二次曲线关系.     

Supercritical carbonation of calcareous composites: Influence of curing

This paper reports the effect of curing on the susceptibility of cementitious composites to carbonation using supercritical carbon dioxide. Samples made using a compression moulding technique were cured in water before and/or after carbonation and the effect on porosity, microstructure, solid phase assemblage and flexural strength was determined. In terms of development of mechanical strength, no benefit was gained from any period of pre- or post-carbonation curing regime. Yet samples cured prior to carbonation underwent minimal chemical reaction between supercritical carbon dioxide and calcium hydroxide, unhydrated cement or C–S–H. Thus there was no correlation between chemical degree of reaction and strength development. The effects responsible for the marked strength gain in supercritically carbonated samples must involve subtle changes in the microstructure of the C–S–H gel, not simple pore filling by calcium carbonate as is often postulated.     

Mechanical characterization of dense calcium phosphate bioceramics with interconnected porosity

Porous hydroxyapatite/tricalcium phosphate (HA/TCP) bioceramics were fabricated by a novel technique of vacuum impregnation of reticulated polymeric foams with ceramic slip. The samples had approximately 5–10% interconnected porosity and controlled pore sizes appropriate to allow bone ingrowth, combined with good mechanical properties. A range of polyurethane foams with 20, 30 and 45 pores per inch (ppi) were used as templates to produce samples for testing. The foams were inpregnated with solid loadings in the range of 60–140 wt%. The results indicated that the average apparent density of the HA/TCP samples was 2.48 g/cm³, the four-point bending strength averaged 16.98 MPa, the work of fracture averaged 15.46 J/m² and the average compressive strength was 105.56 MPa. A range of mechanical properties resulted from the various combinations of different grades of PU foam and the solid loading of slips. The results indicated that it is possible to manufacture open pore HA/TCP bioceramics, with compressive strengths comparable to human bone, which could be of significant clinical interest.     

Carbonation of calcium sulfoaluminate mortars

This study investigated potential physical and chemical parameters that could govern the carbonation rate of calcium sulfoaluminate (CSA) mortars and endeavored to elucidate the microstructural and chemical factors that govern CSA cement's carbonation rate. Experiments included: water absorption, oxygen diffusion, mercury intrusion porosimetry, quantitative X-ray diffraction, thermogravimetric analysis, accelerated carbonation, compression and flexure tests. Additionally, the carbonation process was investigated using thermodynamic modeling. The results show that CSA mortars carbonate much faster than Portland cement mortars and at approximately the same rate as calcium aluminate cement mortars. Additionally, CSA mortars carbonate slower with decreasing w/c, and the anhydrite content of the CSA mortars strongly affects the ye'elimite reaction kinetics which plays an important role in imparting carbonation resistance in CSA mortars. Finally, calcium sulfate additions to CSA clinker to produce CSA cement dilutes the clinker content and reduces the amount of CO₂ that the CSA cement can ultimately bind.     

酚醛树脂/TiC/石墨复合材料双极板的性能分析

以改性酚醛树脂(PF)、TiC和石墨粉(EG)作为原料,通过一次模压成型工艺制备一种质子交换膜燃料电池复合材料双极板,并借助扫描电镜表征了复合材料的微观结构。研究了酚醛树脂的含量、成型压力以及TiC的含量对复合材料导电性能、力学性能的影响。实验结果表明:随酚醛树脂含量的增加,导电性能降低,力学性能升高;随成型压力的增大,导电性能和力学性能都呈升高趋势;随TiC含量的增加,力学性能增强,导电性能呈先增大后减小的趋势。当酚醛树脂和TiC质量分数各为10%,成型压力为60MPa时,所得复合材料弯曲强度>36MPa,抗压强度分别>30MPa,体积电导率>150S/cm。     

多孔 n2 HA/ PA26复合材料的制备及性能

采用注塑方法制备了多孔纳米磷灰石/聚酰胺26 (n2 HA/ PA26) 复合材料 , 采用 SEM、XRD、IR、 力学性能测试考察了多孔材料的性能。结果发现 : 多孔纳米磷灰石/聚酰胺26复合材料的孔隙分布均匀 , 贯通性良好 , 孔的尺寸约为 100～700μm , 平均孔径约 300～500μm , 大孔壁上有丰富的微孔 ; 所得多孔复合材料的孔隙率可控 , 总孔隙率最高可达 881 6 %; 多孔材料的总孔隙率降低 , 则开孔率随之降低 ; 多孔纳米磷灰石/聚酰胺26 复合材料的抗压强度为 1. 1～15. 6 MPa , 压缩模量为 0. 4～1. 4 GPa ; 在总孔隙率相近的条件下 , 多孔材料的抗压强度随 n2 HA质量分数增加而升高; 发泡剂和发泡过程对组成纳米磷灰石/聚酰胺26复合材料的两组元材料的性质和结构无影响。这种多孔材料可望作为人体非承重部位的植入骨修复体和组织工程支架使用。     

磷酸钙骨水泥/明胶复合组织工程支架材料的制备及其结构与性能

磷酸钙骨水泥组织工程支架材料具有良好的生物相容性和骨传导性,是一种良好的骨组织工程支架材料,但是这种材料存在力学性能差的缺点,限制了它的应用.本文采用生物相容性良好的可降解明胶材料与磷酸钙骨水泥支架进行复合,制备出的明胶/磷酸钙骨水泥复合支架材料,其压缩强度可达3.7MPa,比复合前磷酸钙支架材料的强度提高了37倍,而且材料具有良好的柔韧性,适合用作为非承重部位骨组织缺损修复用组织工程支架材料.     

A model predicting carbonation depth of concrete containing silica fume

Silica fume (SF) has been used since long as a mineral admixture to improve durability and produce high strength and high performance concrete. Due to the pozzolanic reaction between calcium hydroxide and silica fume, compared with ordinary Portland cement, the carbonation of concrete containing silica fume is much more complex. In this paper, based on a multi-component concept, a numerical model is built which can predict the carbonation of concrete containing silica fume. The proposed model starts with the mix proportions of concrete and considers both Portland cement hydration reaction and pozzolanic reaction. The amount of hydration products which are susceptible to carbonate, such as calcium hydroxide (CH) and calcium silicate hydrate (CSH), as well as porosity can be obtained as associated results of the proposed model during the hydration period. The influence of water-binder ratio and silica fume content on carbonation is considered. The predicted results agree well with experimental results.     

废旧线路板粉料/玻璃纤维增强复合材料研制

以废旧线路板回收处理过程中得到的塑料粉料与玻璃纤维作为增强材料,采用模压成型的方法制备成不饱和聚酯复合材料。研究了模压工艺参数以及废弃物粉末填料配比等对复合材料力学性能的影响规律,并初步展望了废弃物复合材料的应用。结果表明,随着模压温度、压强、模压时间和填料含量的增加,复合材料的弯曲强度先升高后降低;在优化的模压工艺参数条件下,用废弃粉体与短切玻璃纤维作为组合增强体,制得的不饱和聚酯复合材料的力学性能远大于仅用废弃粉体作为增强体的力学性能,其弯曲强度和冲击强度可达150MPa、18kJ/m2。     

Fabrication of three dimensional polymeric scaffolds with spherical pores

This paper reports polymeric scaffolds with spherical internal macropores and relatively large external dimension. Paraffin spheres with the diameter of several hundred microns were prepared by a suspension technique. Particulate leaching technique based on this kind of spherical porogens was combined with room-temperature compression molding technique to fabricate biodegradable poly(D,L-lactic-co-glycolic acid) (PLGA) porous scaffolds potentially for tissue engineering or in situ tissue induction. The scaffolds exhibited ordered macropores with good pore interconnectivity. The porosity ranged from 80 to 97% adjusted simply by varying porogen content. The foams with porosity around 90% have compressive modulus over 3 MPa and compressive strength over 0.2 MPa. As preliminary cell experiments with 3T3 fibroblasts cultured on the porous scaffolds indicate, the processing procedure of the scaffolds has not brought with problem in cytotoxicity.     

3D spatial distribution of the calcium carbonate caused by carbonation of cement paste

Carbonation of cement-based materials is one area of concern for the durability of concrete structures. The calcium carbonate caused by carbonation is an important indicator of carbonation degrees. The present paper, using 3D tomography data, proposes a nondestructive method to characterize the 3D spatial distributions of calcium carbonate. It allows monitoring of 3D carbonation evolutions. The evolution of the calcium carbonate distributions in a specimen of cement paste with different carbonation degrees is given using the current method. The results are compared with the average quantity of calcium carbonate determined by thermal analysis. From the sharp edge of the calcium carbonate distribution, we conclude that the accelerated carbonation in this experimental condition is a diffusion controlling process.     

Optimization of calcium chloride content on bioactivity and mechanical properties of white Portland cement

This research investigates the optimization of calcium chloride content on the bioactivity and mechanical properties of white Portland cement. Calcium chloride was used as an addition of White Portland cement at 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10% by weight. Calcium chloride was dissolved in sterile distilled water and blended with White Portland cement using a water to cement ratio of 0.5. Analysis of the bioactivity and pH of white Portland cement pastes with calcium chloride added at various amounts was carried out in simulated body fluid. Setting time, density, compressive strength and volume of permeable voids were also investigated. The characteristics of cement pastes were examined by X-ray diffractometer and scanning electron microscope linked to an energy-dispersive X-ray analyzer. The result indicated that the addition of calcium chloride could accelerate the hydration of white Portland cement, resulting in a decrease in setting time and an increase in early strength of the pastes. The compressive strength of all cement pastes with added calcium chloride was higher than that of the pure cement paste, and the addition of calcium chloride at 8 wt.% led to achieving the highest strength. Furthermore, white Portland cement pastes both with and without calcium chloride showed well-established bioactivity with respect to the formation of a hydroxyapatite layer on the material within 7 days following immersion in simulated body fluid; white Portland cement paste with added 3%CaCl₂ exhibited the best bioactivity.     

Studies on the porous scaffold made of the nano-HA/PA66 composite

Porous scaffolds made of n-HA/PA66 composite were fabricated through porogen-leaching technique. The structure, phase and morphology of the scaffolds were investigated by using IR, XRD and SEM, and the physical properties were also studied. The results indicated that the two phases in the composite dispersed uniformly and chemical bonding existed between the two phases. The porosity was proportional to the content of the porogen, and macropores and micropores coexisted and interconnected in the scaffolds. When the porosity was up to 80%, the porosity and the mechanical strength of the scaffolds prepared can meet the demands of tissue engineering simultaneously.