羟基磷灰石/胶原矿化机理的研究进展

仿生合成的羟基磷灰石(HAp)/胶原复合材料的结构和成分与天然骨相似,具有很好的生物相容性、生物活性和生物可降解性,有望成为新一代的骨替代材料。羟基磷灰石/胶原矿化过程其实质是晶体在自组装的胶原纤维上形成的过程,但这一过程在体内是如何进行的至今仍然不清楚。对胶原矿化机理的研究能为制备具有更优越结构和功能的新型骨替代材料提供理论参考。本文概述了羟基磷灰石/胶原矿化机理的研究进展。     

生物降解高分子/羟基磷灰石复合材料研究进展

由于高分子/HA复合材料兼具HA优良的生物性能和高分子材料良好的力学性能而受到了广泛的重视.本文综述了近年来生物降解高分子/羟基磷灰石复合材料的研究进展,介绍了胶原及其衍生物、聚酯、甲壳素及其衍生物、淀粉等可降解高分子材料与羟基磷灰石复合作为骨修复材料的研究进展,并对此类材料存在的问题和发展前景进行了讨论.     

生物活性复合材料在生物矿化过程中的微观形貌与离子浓度变化

采用3-羟基丁酸酯-3-羟基戊酸酯的共聚物(PHBV)与磷酸三钙(TCP)、羟基磷灰石(HA)、生物活性玻璃(BG)等进行复合,获得了性能优良的生物活性骨组织工程支架材料和骨修复材料.研究和比较了3种复合材料在体外模拟生理环境中发生的生物矿化反应,对比了反应前后因矿化物的形成导致的表面微观形貌的变化,通过检测反应液离子浓度的变化对不同材料的矿化过程和生物活性进行了定量表征.研究结果表明,3种复合材料在模拟生理溶液中发生生物矿化的过程和程度不同,其中PHBV/BG的生物活性反应最为明显.     

庆大霉素对羟基磷灰石/壳聚糖复合材料性能的影响

羟基磷灰石/壳聚糖-庆大霉素(HA/CS-G)缓释材料为骨髓炎的定点缓释给药提供了一种有效的局部药物缓释体系。为了研究抗生素对羟基磷灰石/壳聚糖材料性能的影响,采用共沉淀法制备了HA/CS-G缓释材料。利用红外光谱(IR)、X射线衍射(XRD)和扫描电子显微镜(SEM)对材料进行了表征。以不载药的羟基磷灰石/壳聚糖(HA/CS)为对照,研究了庆大霉素对HA/CS复合材料抑菌性能、力学性能和降解性能等的影响。实验结果表明,HA/CS-G有良好的抑菌效果。负载庆大霉素后HA/CS的机械强度明显增强,而材料的降解速率有所下降。本文采用的二次成型技术显著增大了材料的机械强度。     

原位复合法制备层状结构的壳聚糖/羟基磷灰石纳米材料

用原位复合法制备了高性能的壳聚糖/羟基磷灰石(CS/HA)纳米复合材料.用预先沉积的壳聚糖膜将含有羟基磷灰石前驱体的壳聚糖溶液与凝固液隔离,同时控制壳聚糖沉积与羟基磷灰石前驱体转化为羟基磷灰石的过程,使其缓慢且有序地进行.当pH值改变时,质子化的壳聚糖分子链在负电层诱导下有序沉积并形成层状结构与羟基磷灰石原位生成CS/HA,并实现二者分子级复合.XRD和TEM测试证实原位生成的磷酸盐是羟基磷灰石,且其颗粒长约为100nm,宽30～50nm.SEM结果表明,用原位复合法制备的材料具有层状结构,CS/HA(质量比100/5)纳米复合材料弯曲强度高达86MPa,比松质骨的高3～4倍,相当于密质骨的1/2,有望用于可承重部位的组织修复材料.     

碳纳米管对羟基磷灰石基复合材料力学性能的影响

将力学性能优良的碳纳米管(CNTs)与羟基磷灰石(HA)生物陶瓷相复合,发展CNTs/HA复合材料来应用于骨组织修复领域,有望解决HA生物陶瓷力学性能的不足。通过3种不同的制备方法,即通过表面活性剂将CNTs分散在HA基体中、通过酸碱中和反应将CNTs与HA共沉淀以及通过体外浸泡在CNTs上矿化生长HA等方法来获得CNTs/HA复合材料。深入研究CNTs的表面结构和分散状态对CNTs/HA复合材料力学性能的影响。结果表明,CNTs的添加改变了HA的脆性,导致复合材料抗压力学性能得到提高。但是,由于复合材料制备方法的不同,导致CNTs在HA基体中的分散状态、表面结构的完整性以及与HA的界面结合情况不同,导致其抗压力学性能不同。其中,通过表面活性剂将CNTs分散在HA基体中而获得复合材料的抗压力学性能表现最好,而CNTs与HA通过共沉淀法所获得复合材料的抗压力学性能表现最差。     

衰减全反射-红外成像研究聚乳酸/生物活性玻璃复合材料的体外矿化过程

采用衰减全反射-红外成像技术(ATR-FTIR mapping)对多孔聚乳酸/生物活性玻璃(PLLA/BG)复合材料在PBS缓冲液中的矿化过程进行了研究。光谱分辨率为8 cm!1,累加扫描8次,基于A1044/A1755的吸光度比值生成红外图像。成像结果表明,随着矿化进行,材料表面产生的羟基磷灰石(HA)也逐渐增多,当矿化进行到84 d后,材料表面大部分已被HA覆盖。但随着矿化时间的继续延长,矿化不均匀性也逐渐加剧。矿化曲线显示矿化过程存在4个阶段:矿化初期(前21 d),产生的HA很少;矿化增长期(21~70 d),BG逐渐转变为HA;快速增长期(70~91 d),矿化加速,并在91 d时达到最大;矿化后期(91 d后),曲线先显示平稳然后又从105 d起出现下降。研究表明,红外成像技术有望成为骨组织工程支架材料的重要研究工具。     

碳纳米管对羟基磷灰石基复合材料力学性能的影响

将力学性能优良的碳纳米管(CNTs)与羟基磷灰石(HA)生物陶瓷相复合,发展CNTs/HA复合材料来应用于骨组织修复领域,有望解决HA生物陶瓷力学性能的不足.通过3种不同的制备方法,即通过表面活性剂将CNTs分散在HA基体中、通过酸碱中和反应将CNTs与HA共沉淀以及通过体外浸泡在CNTs上矿化生长HA等方法来获得CNTs/HA复合材料.深入研究CNTs的表面结构和分散状态对CNTs/HA复合材料力学性能的影响.结果表明,CNTs的添加改变了HA的脆性,导致复合材料抗压力学性能得到提高.但是,由于复合材料制备方法的不同,导致CNTs在HA基体中的分散状态、表面结构的完整性以及与HA的界面结合情况不同,导致其抗压力学性能不同.其中,通过表面活性剂将CNTs分散在HA基体中而获得复合材料的抗压力学性能表现最好,而CNTs与HA通过共沉淀法所获得复合材料的抗压力学性能表现最差.     

纳米羟基磷灰石/胶原复合材料制备方法比较研究

低温下,通过将水热合成的纳米羟基磷灰石浆料与中性胶原溶胶共混和在中性胶原中原位形成羟基磷灰石两种方法制备羟基磷灰石／胶原复合材料,采用XRD、FTIR、扫描电镜、透射电镜和力学性能测试等方法对两种复合材料的特性进行了表征。通过对两种方法制备的复合材料的特性进行比较,发现两种方法均制备得到了纳米羟基磷灰石／胶原复合材料,复合材料在晶相组成、化学组成、纳米羟基磷灰石晶体尺寸、胶原纤维的结构等方面都与天然骨相似。但原位合成纳米羟基磷灰石晶体的结晶度比水热合成的纳米羟基磷灰石更接近于自然骨,原位合成的羟基磷灰石／胶原复合材料的均匀性、界面结合紧密度、力学性能等方面均优于共混法。原位合成法是改善纳米羟基磷灰石／胶原复合材料均匀性和力学性能的有效方法。     

聚乳酸/羟基磷灰石多孔复合材料的制备及体外降解研究

采用溶剂浇铸-盐沥洗法制备了具有较高孔隙率的聚左旋乳酸/羟基磷灰石(PLLA/HA)多孔复合材料,用扫描电镜(SEM)和衰减全反射-傅立叶变换红外光谱(ATR-FTIR)研究了HA含量对制备样品的形貌以及体外降解行为的影响.结果表明,100/10、100/20、100/30、100/40和100/50的PLLA/HA复...     

Phenolic prepreg waste as functional filler with antioxidant effect in polypropylene and polyamide-6

Milled phenol-formaldehyde glass-fibre scrap (prepreg) was mixed with polypropylene (PP) and polyamide-6 (PA6). The oxidation induction time (OIT) of PP/prepreg composite measured by both chemiluminescence (CL) and Differential Scanning Calorimetry (DSC) was significantly longer than the oxidation induction time of unstabilised base PP. In addition, mechanical testing showed that the prepreg filler stabilised both PP and PA6 towards oxidation during long-term accelerated ageing. Headspace-gas chromatography/mass spectrometry (HS-GC/MS) showed that PP/prepreg composites emit somewhat larger amounts of volatile compounds compared to the reference PP/glass fibre composites, while the amount of volatile components emitted from PA6/prepreg composites was similar to the reference PA6/glass fibre composites. The new prepreg composites could have potential in thermally demanding applications especially if a secondary phosphite stabiliser is added to further increase the oxidative stability through synergy effects.     

微纤形态结构对PP/PA66原位微纤复合材料流变性能的影响

利用三角形排列三螺杆挤出机(triangle arrayed triple-screw extruder,TTSE)低温原位拉伸直接挤出制备了聚丙烯/聚己二酰己二胺(PP/PA66)原位微纤复合材料.通过三螺杆挤出机内部高强度的剪切-拉伸流场,研究了不同工艺参数如PA66含量、加工温度和螺杆转速下原位微纤复合材料中纤维的直径和长径比,并分析微纤长径比对复合材料动态流变性能的影响,且着重探究微纤长径比对凝胶点形成的影响.形貌分析结果显示,工艺条件极大地影响了微纤形貌,且PA66微纤长径比随分散相含量和螺杆转速的提高逐渐增加;动态流变数据说明,随着微纤长径比的增加,复合材料低频下的储能模量明显提高且比纯PP要高,同时,低频下的损耗角正切值降低且变化趋于平缓,而Cole-Cole圆半径显著增大,此时微纤复合材料表现出类凝胶的流变行为;原位微纤自缠结形成凝胶网络,微纤长径比越大,形成临界凝胶网络所需的PA66微纤含量越低,当长径比为210时,形成凝胶点时微纤含量仅3.80 wt%.     

聚丙烯/尼龙6挤出原位成纤后的牵引作用

用挤出机共混挤出聚丙烯和尼龙6，加工中尼龙6作为分散相在聚丙烯中形成微纤。改变挤出物挤出模口后所受的牵引作用的速度会产生材料形态与力学性能的变化。发现随牵引速度的提高，尼龙6微纤的平均直径变小，尺寸分布更均匀，力学性能也随之提高。差热分析表明，随牵引速度的增加聚丙烯与尼龙6的相容性略有提高，X-射线衍射分析表明拉伸作用对尼龙纤维晶体中分子链的取向无影响。     

Complementary effects of multiwalled carbon nanotubes and conductive carbon black on polyamide 6

This article introduces a newly innovative idea for preparation of superconductive ternary polymeric composites of polyamide 6 (PA6), conductive carbon black (CCB), and multiwalled carbon nanotubes (MWCNTs) with different weight ratios by a melt‐mixing technique. The complementary effects of CCB and MWCNTs at different compositions on rheological, physical, morphological, thermal, and dynamic mechanical and electrical properties of the ternary composites have been examined systematically. We have used a novel formulation to produce high‐weight fraction ternary polymer composites that show extremely higher conductivity when compared with their corresponding binary polymer composites at the same carbon loading. For example, with an addition of 10 wt % MWCNTs into the CCB/PA6 composite preloaded with 10 wt % CCB, the electrical conductivity of these ternary composites was about 5 S/m, which was 10 times that of the CCB/PA6 binary composite (0.5 S/m) and 125 times that of the MWCNT/PA6 binary composite (0.04 S/m) at 20 wt % carbon loading. The incorporation of the MWCNTs effectively enhanced the thermal stability and crystallization of the PA6 matrix in the CCB/PA6 composites through heterogeneous nucleation. The MWCNTs appeared to significantly affect the mechanical and rheological properties of the PA6 in the CCB/PA6 composites, a way notably dependent on the MWCNT contents. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1203–1212, 2010     

PP/EPDM/CaCO_3三元复合材料的相结构及力学性能研究

采用以化学键合方式在CaCO3表面包覆上聚丙烯蜡和将改性后的CaCO3先与EPDM复合、再与PP复合的工艺,制备PP/EPDM/CaCO3三元复合材料,以期在PP基体材料中得到EPDM包裹CaCO3的相结构.通过测量三元复合体系中各组分的表面张力,计算各可能组分对之间的界面张力和黏结功,分析三元复合体系中可能的相结构.热力学计算结果表明,三元复合体系中既存在以EPDM为壳、CaCO3为核的"核壳结构",又存在CaCO3与EPDM各自独立分散在PP基体中的结构.电镜照片进一步揭示,在PP/EPDM/改性CaCO3三元复合体系与PP/EPDM/未改性CaCO3三元复合体系中,这两种相结构的比例是不同的,在前者中以核壳结构为主.CaCO3表面性质的不同是产生这一差别的原因.由于这一结构差别的存在,PP/EPDM/改性CaCO3三元复合体系比PP/EPDM/未改性CaCO3三元复合体系具有更好的力学性能.当EPDM用量为8 phr、改性CaCO3用量为15 phr时,三元复合体系的冲击强度达14.25 kJ/m2,是纯PP的3.17倍.     

Maleic Anhydride Polyethylene Octene Elastomer Toughened Polyamide 6/Polypropylene Nanocomposites: Mechanical and Morphological Properties

A series of polyamide 6/polypropylene (PA6/PP) blends and nanocomposites containing 4 wt% of organophilic modified montmorillonite (MMT) were designed and prepared by melt compounding followed by injection molding. Maleic anhydride polyethylene octene elastomer (POEgMAH) was used as impact modifier as well as compatibilizer in the blend system. Three weight ratios of PA6/PP blends were prepared i.e. 80:20, 70:30, and 60:40. The mechanical properties of PA6/PP blends and nanocomposite were studied through flexural and impact properties. Scanning electron microscopy (SEM) was used to study the microstructure. The incorporation of 10 wt% POEgMAH into PA6/PP blends significantly increased the toughness with a corresponding reduction in strength and stiffness. However, on further addition of 4 wt% organoclay, the strength and modulus increased but with a sacrifice in impact strength. It was also found that the mechanical properties are a function of blend ratio with 70:30 PA6/PP having the highest impact strength, both for blends and nanocomposites. The morphological study revealed that within the blend ratio studied, the higher the PA6 content, the finer were the POEgMAH particles.     

The addition of clay on the mechanical properties of surface‐treated CF‐filled PA66 composites

Polyamide 66 (PA66) composites filled with clay and carbon fiber (CF) were prepared by twin‐screw extruder in order to study the influence of nanoparticle reinforcing effect on the mechanical behavior of the PA66 composites (CF/PA66). The mechanical property tests of the composites with and without clay were performed, and the fracture surface morphology was analyzed. The results show that the fracture surface area of the clay‐filled CF/PA66 composite was far smoother than that of the CF/PA66 composite, and there formed a tense interface on the CF surface after the addition of clay. The tensile and flexural strength of CF/PA66 composites with clay was improved. The impact strength decreased because of the high interfacial adhesion. In conclusion, the addition of clay favored the improvement of the higher interface strength and so had good effect on improving the tensile and flexural properties of the composites. Copyright © 2017 John Wiley & Sons, Ltd.     

聚丙烯/聚(丙烯-g-马来酸酐)/蒙脱土纳米复合材料结晶动力学研究

非等温结晶动力学;聚丙烯/聚(丙烯-g-马来酸酐)/蒙脱土纳米复合材料结晶动力学研究