硅烷偶联剂对磷灰石/壳聚糖多孔材料改性

提出以硅烷偶联剂（KH-570）为改性剂,对磷灰石（HA-TCP）进行改性,通过真空冷冻干燥法制备HA-TCP／CS多孔生物材料,采用XRD、SEM、TEM、IR等手段对材料进行分析表征,研究了KH-570的用量对多孔生物材料抗压强度与孔隙率关系。结果表明：随着KH-570含量的增加,多孔生物材料的抗压强度先是逐渐降低而后升高,孔隙率先是逐渐升高而后降低的过程。当HA—TCP：CS=7：3时,KH-570加入量为1wt％时抗压强度为4．1MPa,孔隙率升至最高83．8％,此时多孔生物材料的抗压强度和孔隙率匹配较好,孔隙呈层错板条搭接,且分布均匀,HA—TCP颗粒均匀分散在CS模板上,材料的相结构变化不大,只是材料中各相对应的特征衍射峰的强度略有增强。硅烷偶联剂连接机理是KH-570分解后,结构中的-OH基能够与HA-TCP表面的-OH基之间产生牢固的键合作用,偶联剂另一端含有双键,使改性好的HA—TCP粉体可进一步参与CS的结合,起到连接磷灰石与CS的桥梁作用。     

环氧树脂复合泡沫材料的制备研究

以缩水甘油酯环氧树脂(EP)、酸酐固化剂和空心玻璃微珠为主要原料,通过添加一定的活性稀释剂,高温固化制备了EP复合泡沫材料。研究了空心玻璃微珠的表面改性对复合泡沫材料性能的影响。结果表明,复合泡沫材料性能与空心玻璃微珠的表面性能密切相关,当EP/固化剂/稀释剂的质量比为100/120/15、KH-560改性的空心玻璃微珠用量为30份时,所制备的复合泡沫材料密度为0.826 g/cm3,压缩强度达115.8 MPa,比强度为140.2。     

表面改性过程对空心玻璃微球性能的影响研究

空心玻璃微球是制备复合泡沫材料的关键原料,对其进行表面改性有利于改善复合材料的性能。但目前的研究甚少关注处理过程对微球性能的影响,不利于复合材料的进一步优化设计。因此,本文拟在制备空心玻璃微球的基础上,通过改变处理液组成、处理时间等条件,测试微球粒子密度、抗压强度等变化情况,研究改性过程对其性能的影响。实验结果表明,改性过程中水会侵蚀玻璃壳体,导致其粒子密度随处理时间的延长、酸度的增大而降低,抗压强度也随之下降。采用适当浓度的Al2(SO4)3水溶液处理微球可以在其表面形成新的膜层,改善抗压强度。     

不同偶联剂对环氧/玻璃微珠复合材料性能的影响

采用KH550、KH560、KH570三种硅烷偶联剂对空心玻璃微珠进行处理,进而使用熔融共混法制备了环氧/玻璃微珠复合材料。运用红外分析手段证实硅烷偶联剂均已成功接枝到空心玻璃微珠表面,借助DSC-TG和万能材料试验机研究了偶联剂种类对环氧/玻璃微珠复合材料固化反应、热稳定性和力学性能的影响。对测试结果的分析表明,空心玻璃微珠的表面处理并未改变环氧与氰酸酯间的固化反应速度。经偶联剂表面改性后,制得的环氧/玻璃微珠复合材料的弯曲和压缩强度显著提高,不同硅烷偶联剂的改性效果不同,其中KH-570改性的综合效果最优。     

磷灰石/硅灰石生物玻璃基骨水泥的溶胶-凝胶法制备及性能

为了获得高性能的玻璃基骨水泥,采用溶胶–凝胶法制备了磷灰石/硅灰石（apatite/wollastonite,AW）生物玻璃,将其作为固相粉末与柠檬酸固化液均匀混合制得了AW玻璃基骨水泥（glass-based bone cement,GBC）,探讨了溶胶–凝胶法制备的AW生物玻璃作为GBC固相粉末的可能性。用X射线衍射、红外光谱和强度测试仪对不同温度热处理的AW生物玻璃粉末的晶相转变以及骨水泥在人体模拟体液中浸泡不同时间后的晶相组成和抗压强度进行了研究。结果表明：AW生物玻璃粉末经700℃热处理后形成了硅灰石和羟基磷灰石晶相,且温度越高晶相越完整;以900℃热处理后的AW生物玻璃粉末作为固相所制备的GBC随着浸泡时间的增加,骨水泥固化体中生成了更多量的CaCO3晶体及少量的羟基磷灰石晶体,且此种GBC的抗压强度最大。     

Sr-HAP/CS复合凝胶的制备及生物矿化性能研究

采用化学沉淀法-冷冻干燥法制备含锶羟基磷灰石/壳聚糖（Sr-HAP/CS）复合凝胶,比较羟基磷灰石/壳聚糖（HAP/CS）凝胶,研究了它们的组成、结构和生物矿化性能。产物经IR、XRD和SEM分析证实：HAP/CS和Sr-HAP/CS中无新化学键生成,主要成分为HAP、Sr-HAP和CS;XRD中Sr-HAP的特征峰比HAP相应峰尖锐,晶体粒径减小;2种凝胶内部为网状孔隙结构,物相分布均匀。矿化实验结果表明,2种复合凝胶在模拟体液（SBF）中浸泡,表面发生钙的溶解和沉积现象;15 d后,凝胶表面有明显白色絮状物,主要为HAP类物质,且Sr-HAP/CS凝胶表面沉积物量较多;复合凝胶均具有诱导成骨性,Sr-HAP/CS对促进无机成骨物的生长作用较强。     

磷灰石/硅灰石生物玻璃基骨水泥的溶-凝胶法制备及性能

为了获得高性能的玻璃摹骨水泥,采用溶胶-凝胶法制备了磷灰石/硅灰石(apatite/wollastonite,AW)生物玻璃,将其作为固相粉末与柠檬酸固化液均匀混合制得了AW玻璃基骨水泥(glass-based bone cement,GBC),探讨了溶胶-凝胶法制备的AW生物玻璃作为GBC固相粉末的可能性.用X射线衍射、红外光谱和强度测试仪对不同温度热处理的AW生物玻璃粉末的晶相转变以及骨水泥在人体模拟体液中浸泡不同时间后的晶相组成和抗压强度进行了研究.结果表明:AW生物玻璃粉末经700℃热处理后形成了硅灰石和羟基磷灰石晶相,且温度越高晶相越完整;以900℃热处理后的AW生物玻璃粉末作为固相所制备的GBC随着浸泡时间的增加,骨水泥固化体中生成了更多量的CaC03晶体及少量的羟基磷灰石晶体,且此种GBC的抗压强度最大.     

玻璃鳞片表面改性及其在防腐涂料中的应用研究

采用表面接枝反应法,以六亚甲基二异氰酸酯(HDI)为改性介质,对无机玻璃鳞片进行表面活化改性,对接枝改性产物的化学结构进行了分析表征。以改性玻璃鳞片为填料,制备了改性玻璃鳞片防腐涂料,并对涂料的力学性能及防腐性能进行了测试评价。     

氧化石墨烯改性水泥的制备及力学性能研究

制备了氧化石墨烯改性水泥,并对其力学性能进行研究。以鳞片石墨、硝酸钠、浓硫酸等为原料,采用Hummers改性法制备氧化石墨烯,经过超声、剥离等方法,得到了最终的氧化石墨烯。然后在净浆搅拌锅内倒入均匀分散的氧化石墨烯胶体,并倒入水泥对其进行均匀搅拌,对获取的水泥浆体进行成型养护,并对氧化石墨烯改性水泥进行了力学性能测试,包括抗压强度与抗折强度实验。将水泥的抗压强度与抗折强度实验结果作为对比组,将氧化石墨烯改性水泥的抗压强度与抗折强度实验结果作为实验组。结果显示制备的氧化石墨烯改性水泥在氧化石墨烯掺量逐渐提升的情况下,实现了抗压强度与抗折强度的提升,在氧化石墨烯掺量为1.0%时达到最大抗压强度,掺量为0.06%时抗折强度达到最高。     

PBT/空心玻璃微珠复合材料的性能研究

采用不同硅烷偶联剂对空心玻璃微珠(HGM)进行表面改性,制备了聚对苯二甲酸丁二醇酯(PBT)/改性HGM复合材料。结果表明:改性HGM的加入,提高了复合材料的弯曲强度和拉伸强度,并有效降低了其密度,同时复合材料的冲击强度下降;HGM表面经SG-700型硅烷偶联剂处理后对PBT填充改性的效果较好。     

Preparation and characterisation of HA/TCP biphasic porous ceramic scaffolds with pore-oriented structure

Porous hydroxyapatite/tricalcium phosphate (HA/TCP) ceramic scaffolds with a uniform unidirectional pore structure were successfully fabricated by an ice-templating method by using Ca-deficient HA whiskers and phosphate bioglass. HA whiskers showed good dispersibility in the slurry and favoured the formation of interconnected pores in the scaffolds. Addition of bioglass powders enhanced the material sintering process and the phase transformation of Ca-deficient HA to β-TCP. Calcium-phosphate-based scaffolds with a composition from HA to an HA/β-TCP complex could be obtained by controlling the freezing moulding system and slurry composition. The fabricated scaffolds had a porosity of 75–85%, compressive strength of 0.5–1.0 MPa, and a pore size range of 130–200 µm.     

基于三维打印骨支架制备及其性能

利用三维打印（3DP）成型技术制备了羟基磷灰石（HAP）支架与混合壳聚糖（CS）的HAP-CS复合支架,并用Ⅰ型胶原蛋白（Collagen TypeⅠ）对HAP-CS支架进行了改性处理;通过抗压强度实验、孔隙率测定、微观形貌观察、亲水性及碱性磷酸酶（ALP）活性检测实验研究了所制备支架性能。结果表明添加CS可提高HAP支架抗压强度74.5%,但未降低支架孔隙率;经Collagen Type I改性的HAP-CS支架的亲水性有显著提高,ALP活性检测结果显示Collagen Type Ⅰ可提高细胞骨化能力。综上,本研究所制备的HAP-CS改性支架具有良好的性能及生物活性,可用于骨缺损修复研究。     

仿生型壳聚糖-明胶/溶胶凝胶生物玻璃复合支架的制备及其矿化性能研究

利用冷冻干燥法制备出用于骨和软骨组织工程的壳聚糖-明胶/溶胶凝胶生物玻璃(CS-Gel/SGBG)仿生型复合多孔支架,并进行了孔隙率的测定和显微形貌的观察;探讨了各组分不同用量对CS-Gel/SGBG复合支架显微结构的影响以及复合支架在模拟生理体液中的仿生矿化性能。研究表明,通过调节各组分的不同用量,可以制备出三维连通的复合多孔支架,且孔隙率达到90%以上;在模拟生理体液中浸泡后发现CS-Gel/SGBG支架表面有大量结晶态类骨碳酸羟基磷灰石生成,表明复合支架有良好的生物矿化性能。     

Microstructural,mechanical properties and strengthening mechanism of DLP produced β-tricalcium phosphate scaffolds by incorporation of MgO/ZnO/58S bioglass

The inherent brittleness of bioceramics restricts their applications in load-bearing implant, although they possess good biocompatibility and bioactivity. ZnO, MgO and 58S bioglass (BG) were incorporated as additives to further improve the mechanical properties and biocompatibility of β-TCP and ZnO/MgO/BG-β-TCP composite scaffolds were manufactured via digital light processing (DLP). The composite with the best comprehensive performance was selected for degradation behavior and biocompatibility evaluation. The effects of different proportions of ZnO/MgO/BG on mechanical strength were analyzed and ZnO0·5/MgO1/BG2-β-TCP (ZMBT) samples exhibited superior mechanical strength. The improvement by 272% and 99% respectively was achieved in fracture toughness and compressive strength with the optimal recipe. The enhancement effect is realized through phase transition, alterative sliding actions and transgranular fracture to effectively prevent the load transfer combining the functions of bioglass and metal oxide. ZMBT scaffolds exhibited a more desirable pH environment and an enhanced ability of apatite-mineralization formation, meanwhile Si⁴⁺, Mg²⁺ and Zn²⁺ were gradually released from scaffolds. Furthermore, in vitro evaluation indicated that ZMBT scaffolds presented not only excellent cell attachment, proliferation, alkaline phosphatase (ALP) activity, but they up-regulated osteogenic gene (ALP, OCN, Runx2). These results suggest that the addition of ZnO/MgO/BG to DLP-printed β-TCP scaffolds offer a smart strategy to fabricate porous scaffolds with conspicuously better biological and physicochemical properties including compressive strength, bioactivity, osteogenesis and osteogenesis-related gene expression. Metal-oxide and BG synergistically enhanced the mechanical and biological properties which make the ZMBT scaffolds a strong candidate for bone repair applications.     

Bioactive monetite‐containing whisker‐like fibers reinforced chitosan scaffolds

The aim of this work was to develop bioactive chitosan scaffolds reinforced with monetite‐containing whisker‐like fibers. The fibers synthesized by homogeneous precipitation were characterized as monetite/hydroxyapatite short fibers (MAFs), using XRD, FTIR and SEM. The pure chitosan and MAFs/chitosan composite scaffolds were produced by freeze‐drying, and characterized with respect to porosity, pore size, swelling behavior, compressive strength and modulus, and in vitro bioactivity. The incorporation of MAFs in chitosan matrices led to increase the pore size, according to the evaluation by FE‐SEM, and decrease the porosity of composite scaffolds. The swelling ratio decreased as MAFs content of scaffolds increased. The compressive strength and modulus of scaffolds were improved by an increase in MAFs content. The noncross‐linked scaffolds with a chitosan: MAFs weight ratio of 1:1 (CW3) showed a porosity of 75.5%, and the strength and modulus of 259 kPa and 2.8 MPa in dry state, respectively. The crosslinking by glutaraldehyde resulted in improved mechanical properties. The strength and modulus of cross‐linked CW3 scaffolds in wet state reached to 345 kPa and 1.8 MPa, respectively. The in vitro bioactivity of the reinforced scaffolds, evaluated by FE‐SEM/EDS, XRD, and ATR‐FTIR, was confirmed by the formation of a carbonated apatite layer on their surfaces when they soaked in simulated body fluid (SBF). The results of this initial study indicate that the monetite‐containing whisker‐like fibers may be an appropriate reinforcement of chitosan scaffolds.     

Characterization of chitosan/citrate and chitosan/acetate films and applications for wound healing

In this work, we aimed to develop a scaffold of chitosan (CS) with a porous sponge structure for an artificial skin. The scaffolds were prepared from both CS/citric and CS/acetic solutions. In addition, the cast films were also prepared from the same solutions to compare some of their properties. They were characterized using WAXD, FTIR, DSC, tensile measurements, and SEM observation. It was found that CS/acetate had low crystallinity but CS/citrate was in an amorphous state, resulting in a large ductility with rubbery softness. Despite the different morphologies of CS/citrate and CS/acetate scaffolds, both scaffolds exhibited the wound healing effect available for tissue engineering. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Novel Fe2O3-doped glass /chitosan scaffolds for bone tissue replacement

In this study quaternary bioglass system (BG) SiO₂–CaO–Na₂O–P₂O₅ doped with Fe₂O₃ was prepared by the sol–gel method. Furthermore, 3D scaffolds were designed through blending Fe₂O₃ -doped bioglass with chitosan to obtain various compositions of scaffolds by the freeze-drying technique. The thermal behavior, morphological properties, porosity (%), mechanical properties and physicochemical properties of BG and scaffolds were evaluated by DSC/TGA, TEM, SEM, liquid displacement method, universal testing machine, XRD and FTIR. In addition, the in vitro bioactivity of the prepared scaffolds was studied in phosphate buffer saline (PBS) through the determination of PBS ions concentrations, as well as the degradation and the observation of precipitated calcium phosphate layer by SEM coupled with EDX and FTIR behavior. The cell viability of the prepared scaffolds was conducted against Baby Hamster Kidney fibroblasts (BHK-21) cell line. The presence of Fe₂O₃ decreased the T_g (from 513 to 390?°C) and the size decreased (from 20.89 to 50.81–13.92–27.87?nm). The scaffolds porosity (%) decreased upon Fe₂O₃ doping but the mechanical strength increased. Cell viability results for the designed scaffolds demonstrated acceptable cell viability compared with normal cells. Therefore, the designed scaffolds are promoted as regenerated materials that can be used for bone tissue replacement.     

Fabrication and characterization of chitosan/PVA with hydroxyapatite biocomposite nanoscaffolds

Nanofibrous biocomposite scaffolds of chitosan (CS), PVA, and hydroxyapatite (HA) were prepared by electrospinning. The scaffolds were characterized by FTIR, SEM, TEM, and XRD techniques. Tensile testing was used for the characterization of mechanical properties. Mouse fibroblasts (L929) attachment and proliferation on the nanofibrous scaffold were investigated by MTT assay and SEM observation. FTIR, TEM, and XRD results showed the presence of nanoHA in the scaffolds. The scaffolds have porous nanofibrous morphology with random fibers in the range of 100–700 nm diameters. The CS/PVA (90/10) fibrous matrix (without HA) showed a tensile strength of 3.1 ± 0.2 MPa and a tensile modulus 10 ± 1 MPa with a strain at failure of 21.1 ± 0.6%. Increase the content of HA up to 2% increased the ultimate tensile strength and tensile modulus, but further increase HA up to 5–10% caused the decrease of tensile strength and tensile modulus. The attachment and growth of mouse fibroblast was on the surface of nanofibrous structure, and cells' morphology characteristics and viability were unaffected. A combination of nanofibrous CS/PVA and HA that mimics the nanoscale features of the extra cellular matrix could be promising for application as scaffolds for tissue regeneration, especially in low or nonload bearing areas. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Physical and mechanical properties of the fully interconnected chitosan ice‐templated scaffolds

Porous chitosan scaffolds were prepared with a freeze‐casting technique with different concentrations, 1.5 and 3 wt %, and also different cooling rates, 1 and 4°C/min. The pore morphology, porosity, pore size, mechanical properties, and water absorption characteristics of the scaffolds were studied. Scanning electron microscopy images showed that the freeze‐cast scaffolds were fully interconnected because of the existence of pores on the chitosan walls in addition to many unidirectionally elongated pores. Increases in the chitosan concentration and freezing rate led to elevations in the thickness of the chitosan walls and reductions in the pores size, respectively. These two results led to the enhancement of the compressive strength from 34 to 110 kPa for the scaffolds that had 96–98% porosity. Also, augmentation of the chitosan concentration and decreases in the freezing rate led to the reduction of the number of pores on the chitosan walls. Furthermore, the volume of water absorption increased with a reduction in the chitosan concentration and cooling rate from 690 to 1020%. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41476.     

Effect of SiO2 in situ cross-linked CS/PVA on SrFe12O19 scaffolds prepared by 3D gel printing for targeting

The design of magnetic composite scaffolds with superior properties has the potential to construct a targeted delivery platform with hyperthermia. In this study, strontium hexaferrite (SrFe₁₂O₁₉, SrM) magnetic nanoparticles (MNPs) were obtained by the chemical precipitation method. Non-toxic cross-linked biogels were prepared for adhesive ceramic scaffolds, and chitosan/polyvinylalcohol (CS/PVA)-bonded SrM magnetic nanoscaffolds were successfully prepared by 3D gel printing (3DGP) method. The effects of PVA physical cross-linking and in situ formed SiO₂ on the properties of CS-bonded scaffolds were evaluated, and the compressive strengths were increased from 6.13 ± 2.45 MPa to 8.80 ± 2.02 MPa and 17.18 ± 2.15 MPa, respectively. The results showed that the saturation magnetization of SiO₂/CS/PVA/SrM composite scaffolds was 59.96 emu/g. In vitro immersion experiments showed that the degradation rates of SiO₂/CS/PVA/SrM scaffolds were 4.90% after 28 days, and the in situ SiO₂ improved the deposition of calcium salts on the scaffolds. The experiments showed that the SrM magnetic scaffolds could not only concentrate magnetic fields to improve the efficiency of targeting deposition but also achieve a weak targeting process without external magnetic field assistance. In vitro cell proliferation test showed that MC3T3-E1 cells had good adhesion and proliferation on the surface of SiO₂/CS/PVA/SrM scaffolds, which indicated that the scaffolds may be used for bone repairing.