改性羟基磷灰石/聚乳酸纳米复合材料的结晶行为

利用溶剂复合的方法制备了具有良好生物相容性的表面接枝聚(γ-苄基-L-谷氨酸)的改性羟基磷灰石/聚乳酸纳米复合材料, 并研究了其熔融与结晶行为. 结果表明, 聚乳酸的玻璃化转变温度为60.3 ℃, 而复合材料的玻璃化转变温度达到65.8 ℃, 不同样品在140 ℃等温结晶后, 改性羟基磷灰石/聚乳酸复合材料的球晶直径仅为聚乳酸(PLLA)球晶直径的16.7%~66.7%. 复合材料的熔点提高到184.4 ℃.     

微波辅助仿生矿化增强石墨烯与聚乳酸的界面相互作用

石墨烯纳米片在提高聚乳酸(PLA)复合材料力学性能和气体阻隔性能等方面具有良好的应用前景,但通常在不同程度上受限于较差的界面相互作用.本文通过高效且环境友好的微波辅助水相仿生矿化方法,在石墨烯纳米片表面直接生成高结晶度、高结构规整度的羟基磷灰石纳米晶须,获得了具有良好分散性和界面结合力的仿生矿化石墨烯(BMGr)纳米杂化体.将BMGr纳米杂化体均匀分布于聚乳酸纤维表面,通过受限成型(60℃,3 MPa)获得了具有强界面结合的复合薄膜,大幅提高了力学性能.值得强调的是,BMGr增强聚乳酸复合薄膜的拉伸强度、杨氏模量和拉伸韧性分别达到22.6 MPa,199 MPa和6.6 MJ/m³,是纯PLA纤维膜的6.46,3.75和8.25倍.本文不仅发展了有效修饰石墨烯纳米片的技术路线,更为制备高强度高韧性的聚乳酸复合材料并阐述其结构-性能关系提供了研究思路.     

钛基表面纳米羟基磷灰石涂层的电泳沉积

应用沉淀法合成纳米羟基磷灰石,并以电泳沉积法在粗糙化的钛表面制备纳米结构的羟基磷灰石涂层.纳米涂层有利于保持羟基磷灰石的化学组成和结构,制备的涂层均匀并且无裂缝,烧结后涂层仍保持纳米结构,其烧结温度也明显降低。钛表面经化学处理后,可形成很多微孔和TiO2薄层,增强了涂层和基体之间的结合.涂层的结合力为 18±2. 5MPa,硬度和杨式模量分别为 32. 0和 2. 4GPa.     

转铁蛋白修饰聚乳酸纳米微粒表面的99mTC标记及体内分布

以转铁蛋白溶液为外水相,聚乳酸丙酮溶液为油相,纳米沉淀法制备了表面结合转铁蛋白的聚乳酸纳米微粒,以二氯亚锡为还原剂,直接法和CDPTA螯合法对纳米微粒进行99mTc放射性标记,以C6胶质瘤细胞实验考察了标记对纳米微粒表面转铁蛋白活性的影响,结果表明直接法标记率较高,大于80.1%,对转铁蛋白活性有影响。CDPTA螯合法标记法较低(72.3%),对转铁蛋白活性影响较小。以脑部荷胶质瘤大鼠为动物模型,鼠尾静脉注射放射性标记纳米微粒,SPECT示踪和γ计数器检测显示:以转铁蛋白表面修饰的聚乳酸纳米微粒经静脉注射后主要分布于肝、脾,与正常鼠相比,荷胶质瘤大鼠对纳米微粒的摄取率有所提高。     

聚乳酸/蒙脱土纳米复合材料的结构和热性能

聚乳酸/蒙脱土纳米复合材料的结构和热性能;聚乳酸;蒙脱土;纳米复合材料;插层     

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/凹凸棒土纳米复合材料的结构与性能

采用熔融复合方法制备了不同填料质量分数的聚乳酸/纳米凹凸棒土复合材料,纳米凹凸棒土的加入可以显著提高聚乳酸纳米复合材料的拉伸强度和断裂伸长率.扫描电镜结果表明,凹凸棒土粒子在复合材料中实现了均匀分散.DSC曲线在降温过程中出现明显结晶峰,说明纳米凹凸棒土对聚乳酸有一定的成核作用.当纳米凹凸棒填料含量>8%时,在聚合物基体中可形成完善的网络状结构.填料粒子作为体系中的物理缠结点使得复合材料熔体的应力松弛时间延长.红外谱图显示纳米凹凸棒土和聚乳酸分子间存在较强的相互作用.我们推测,纳米凹凸棒土的加入减少了PLA基体层的厚度,使其由三维应力转变为二维应变状态,导致最大切应力可以达到剪切屈服强度,产生剪切滑移形变带,使得呈现出韧性材料性质,有效提高了材料的断裂伸长率.     

多孔纳米羟基磷灰石/聚乙烯醇复合水凝胶的表征

本文通过采用溶盐致孔法,制备了多孔纳米羟基磷灰石／聚乙烯醇复合水凝胶材料。用透射电子显微镜、红外光谱、扫描电子显微镜和图像分析对材料进行了表征。结果表明纳米羟基磷灰石与聚乙烯醇之间有一定键合,并且多孔纳米羟基磷灰石／聚乙烯醇复合水凝胶中大孔呈均匀分布且相互贯通,复合水凝胶的含水率在80％左右。该种多孔复合水凝胶是可用于人工角膜支架,是一种很有开发前景的生物医用材料。     

PLLA/β-TCP杂化微纳米纤维的制备及其性能

将湿法工艺合成的β-磷酸钙纳米粒子与左旋聚乳酸(PLLA)的混合溶液通过电纺丝法制成杂化纳米纤维膜,以期制备一种新型纳米纤维骨组织修复材料。采用FT-IR,XRD,TEM,DSC等手段研究了β-磷酸钙(β-TCP)的结构和形态,采用SEM和直径分布探讨了优化PLLA/β-TCP纤维的电纺丝工艺。结果表明:采用湿法合成β-TCP的纳米粒子具有良好的晶型结构,直径在219~328 nm之间;采用双溶剂体系在优化条件下制备的PLLA/β-TCP杂化纳米纤维直径在500~700 nm之间,PLLA/β-TCP界面结合良好,β-TCP起到了增强作用。在湿态条件下,PLLA纤维膜的力学性能有所提高,而PLLA/β-TCP纤维膜的力学性能则呈现下降趋势。     

紫外光阻隔型低分子量聚乳酸的合成及结构性质研究

以源于可再生资源的芦荟大黄素(AE)为引发剂，引发丙交酯(LA)开环聚合，合成了具有阻隔紫外光功能的低分子量聚乳酸.系统研究了所合成聚乳酸PLA-En的结构，光学和热学性质.AE分子结构中的醇羟基引发LA聚合形成由En基团(AE分子结构中醇羟基反应后的结构)封端的聚乳酸PLA-En，调控LA与AE之间的摩尔比n (20～200)，可调控PLA-En数均分子质量M_n(0.29×10⁴～2.93×10⁴g/mol);En基团的引入可赋予PLA-En与AE相似的光吸收特征和荧光发射特征，且几乎不受分子量的影响，同时，产物聚乳酸的热稳定性得到提高，PLA-En的热分解温度(T_d)比由十六醇(CA)引发合成的相近分子量聚乳酸PLA-Cn(Cn为CA结构中醇羟基反应后的结构)高15℃以上，但熔点差别不大.T_d的提高赋予PLA-En比PLA-Cn更宽的熔融加工温度窗口，前者超过100℃，后者不超过90℃.将质量比3 mass%的PLA-En(n=20,M_n=0.29×1...     

电纺丝法制备聚乳酸/多壁碳纳米管/羟基磷灰石杂化纳米纤维的研究

电纺丝是一种利用聚合物溶液或熔体在强电场中进行喷射纺丝的加工技术,所制得的纤维、直径一般在数十纳米至几微米之间,比传统方法制得的纤维直径小几个数量级,是获得纳米尺寸长纤维的有效方法之一．     

Effect of multiscale structure on the gas barrier properties of poly(lactic acid)/Ag nanocomposite films

Poly(lactic acid) (PLA) is the most suitable for biodegradable packaging film because of its excellent integrated property, but the poor gas barrier property is its weakness. In this study, a nanocomposite film based on PLA incorporated with 0‐, 1‐, 3‐, 5‐, 10‐, or 15‐wt% nano‐Ag was developed. Effect of multiscale structure on the barrier properties of PLA/nano‐Ag films was studied. The PLA nanocomposite film with 5‐wt% nano‐Ag had the lowest water vapor permeability (WVP) value. Oxygen transmission rate (OTR) value for PLA nanocomposites with 3‐wt% nano‐Ag was found to be the lowest among all the samples. Multiscale structure was demonstrated by the scanning electron microscopy, Fourier transform‐infrared spectroscopy, X‐ray diffraction measurement, and differential scanning calorimetry results. The crystallinity of the PLA phase increased with the content of nano‐Ag in the PLA composites. The evolution of the PLA phase crystallinity could improve the barrier properties of PLA/nano‐Ag composite films for food packaging applications. From the view of multiscale structure, it is better to achieve a balance among short‐range conformation in the amorphous region, long‐range‐ordered structure, and ordered aggregated structure to improve the barrier properties of PLA/nano‐Ag composite films.     

Enhanced properties of poly(lactic acid) with silica nanoparticles

The objective of this article is to fabricate poly(lactic acid) (PLA) and nano silica (SiO₂) composites and investigate effect of SiO₂ on the properties of PLA composites. Surface‐grafting modification was used in this study by grafting 3‐Glycidoxypropyltrimethoxysilane (KH‐560) onto the surface of silica nanoparticles. The surface‐grafting reaction was confirmed by Fourier transform infrared spectroscopy and thermogravimetric analysis. Then the hydrophilic silica nanoparticles became hydrophobic and dispersed homogeneously in PLA matrix. Scanning electron microscope and Dynamic thermomechanical analysis (DMA) results revealed that the compatibility between PLA and SiO₂ was improved. Differential scanning calorimetry and polarized optical microscope tests showed that nano‐silica had a good effect on crystallization of PLA. The transparency analysis showed an increase in transparency of PLA, which had great benefit for the application of PLA. The thermal stability, fire resistance, and mechanical properties were also enhanced because of the addition of nano silica particles. Copyright © 2016 John Wiley & Sons, Ltd.     

Construction of crosslinking network structures by adding ZnO and ADR in intumescent flame retardant PLA composites

Different proportion of nano zinc oxide (nano ZnO) and chain extender (ADR) were combined with the intumescent flame retardant and then added into the PLA matrix. The thermal stability, flame retardant performance, and mechanical properties were studied. The gel content results showed that crosslinking structures were obtained after the addition of nano ZnO and ADR, which were generated by the catalytic chain scission effect of nano ZnO and chain extension effect of ADR. With addition of 1% nano ZnO and 1.6% ADR, the gel content of flame retardant PLA composite reached the highest value (14.2%). Meanwhile, the corresponding flame retardant PLA composite with 1% nano ZnO and 1.6% ADR, named FRPLA/ZnO/ADR-1, exhibited an overall improved properties including the flame retardant properties and mechanical performance, which passed the UL94 V-0 level with a limiting oxygen index value of 40.1%. Compared to FRPLA (flame retardant PLA without ZnO and ADR), the peak heat release rate and the total smoke production of FRPLA/ZnO/ADR-1were reduced by 60% and 67% respectively, and the final mass improved from 12% to 38%. In addition, the tensile strength and elongation at break of FRPLA/ZnO/ADR-1 increased by 25%, 14% compared with that of FRPLA. The impact strength was 15.1 kJ/m², which is similar to the pure PLA (15.6 kJ/m²). It indicated that the addition of nano ZnO and ADR could balance the flame retardant performance and the mechanical properties of the flame retardant PLA.     

Nanofibrous poly(lactic acid)/hydroxyapatite composite scaffolds for guided tissue regeneration

The production of nanofibrous PLA/HA composite scaffolds is described. The morphological, mechanical, surface, and thermal properties of the composites were extensively investigated. The results show that the mixture of PLA and HA formed smooth nanofibers without lumps. The incorporation of HA increased the mechanical strength of the nanofibers and changed the morphology, increasing the mean fiber diameter and pore size. Surface and internal properties confirmed that HA was homogeneously distributed inside the nanofibers and oriented towards their surface. The nanofiber composites allowed the adhesion and proliferation of pre-osteoblasts for up to 3 weeks.     

Design and preparation of poly(lactic acid) hydroxyapatite nanocomposites reinforced with phosphorus‐based organic additive: Thermal,combustion, and mechanical properties studies

A new phosphorus‐based organic additive (PDA) was designed and successfully synthesized using a three‐component reaction for improvement of the thermal and combustion resistance of polylactic acid (PLA). For compensate for mechanical properties of PLA, hydroxyapatite nanoparticles was modified via in situ surface modification with PDA and was used for preparation of PLA nanocomposites. The structure and morphology as well as thermal, combustion, and mechanical properties of the all PLA systems were investigated. The X‐ray diffraction (XRD) and field‐emission scanning electron microscopy (FE‐SEM) results indicated that the presence of PDA as surface modifier has been necessary for a desirable dispersion of hydroxyapatite (HA) nanoparticles in the PLA matrix. The thermal, combustion, and mechanical properties of the PLA system films were investigated using thermogravimetric analysis (TGA), microscale combustion calorimeter (MCC), and tensile test, respectively. The initial decomposition temperature and char residue of PLA containing 6 mass% of PDA along with 2 mass% HA nanoparticles were increased 20°C and 12% respectively, compared with that of the neat PLA. The peak of heat release rate was decreased from 566 W/g for the neat PLA to 412 W/g for PLA containing 2 mass% of PDA along with 6 mass% HA nanoparticles. By incorporation of only 2 mass% HA nanoparticles and 6 mass% of PDA, the tensile strength was obtained 51 MPa higher than that of the neat PLA.     

Modified PLA nano in situ gel: a potential ophthalmic drug delivery system

A novel nano in situ gel forming system of 5-Fluorouracil (5-FU) was investigated for its potential use for conjunctival/corneal squamous cell carcinoma (CCSC). The study was conducted in two steps, in the first step PLA nanoparticles were prepared and characterized; in the second step the drug loaded PLA nanoparticles were dispersed in sodium alginate solution yielding the modified nano in situ system, which were evaluated in rabbit eye. Size and morphology of prepared PLA particles were verified by using dynamic light scattering (DLS), atomic force microscope (AFM) and scanning electron microscope (SEM). In vitro and in vivo study of free 5-FU, PLA nanoparticles and modified nano in situ system were conducted in simulated tear fluid and in rabbit eye respectively. PLA nanoparticles were in size range of 128-194 nm with spherical shape and smooth surface with narrow size distribution. No polymer drug interaction was found as confirmed by FTIR, NMR and DSC. XRD of PLA nanoparticles confirmed that 5-FU was present in the crystalline state. In vitro experiments indicated a diffusion controlled release of 5-FU from both PLA nanoparticles and modified nano in situ system with high burst effect. Modified nano in situ gel system (MNS) significantly increased the Cmax and AUC0-8 in aqueous humor as compared to 5-FU solution and PLA nanoparticles. Higher 5-FU level in aqueous humor was possibly because of increased retention time of gel matrix-embedded drug loaded nanoparticles. Overall results showed the potential of MNS for ophthalmic delivery in the therapy of CCSC.     

Preparation,mechanical properties,and in vitro biocompatibility of novel nanocomposites based on polyhexamethylene carbonate fumarate and nanohydroxyapatite

In the current study a new biodegradable nanocomposite based on poly hexamethylene carbonate fumarate (PHMCF) and nano‐sized hydroxyapatite (nano‐HA) has been developed. A silane coupling agent γ‐methacryloxypropyltrimethoxy silane, was used to achieve a good interfacial adhesion between nano‐HA and PHMCF matrix. PHMCF with different nano‐HA contents were characterized using dynamical mechanical thermal analysis (DMTA) and hardness test. The effect of frequency on storage modulus, glass transition temperature (T_g) and the damping were investigated. In vitro cytotoxicity and proliferation were performed using G292 cell lines by MTT assay. The addition of nano‐HA resulted in an increment on the storage modulus and decrement on the damping. Along with improvement in mechanical properties of composites, the addition of nano‐HA resulted in enhanced cell proliferation. Following these results, the newly developed nano‐PHMCF composite scaffold may be considered for bone tissue engineering applications. Copyright © 2009 John Wiley & Sons, Ltd.     

PLA/MWNTs/HA复合材料的制备和性能研究

采用超声辅助原位湿法合成多壁碳纳米管／羟基磷灰石纳米复合材料(MWNTs／HA),并通过溶液浇铸法制备了PLA／MWNTs／HA复合材料薄膜。考察了MWNTs／HA纳米粒子含量对复合膜性能的影响,并通过力学性能、SEM、FTIR、以及DMTA对复合膜性能进行了表征,结果表明：随着纳米粒子质量分数的增加,复合膜的拉伸强度呈下降趋势;拉伸模量和储能模量呈现先下降后上升的趋势;玻璃化转变温度则呈现不断上升趋势。     

Preparation and characterization of phosphorylated graphene oxide grafted with poly(L‐lactide) and its effect on the crystallization,rheological behavior,and performance of poly (lactic acid)

Phosphorylated graphene oxide (PGO) was prepared by using phosphoric acid as functional reagent, and PGO was grafted with poly(L‐lactide) (PGO‐PLLA) by ring‐opening polymerization of L‐lactide as monomer under nano‐ZnO catalyst. The results of the orthogonal analysis showed the optimum reaction conditions to be as follows: the reaction temperature of 170°C, reaction time of 14 hours, the mass ratio of PGO of 10 wt%, and the mass of nano‐ZnO of 1 wt%. PGO‐PLLA was characterized by fourier transform infrared spectroscopy, gel permeation chromatography, and X‐ray photoelectron spectroscopy, which demonstrated that the PLLA molecular chains were successfully grafted onto the surface of PGO. Poly (lactic acid)/PGO‐PLLA nanocomposites (PLA/PGO‐PLLA) were prepared by melt intercalation. Mechanical test and fracture scanning electron microscopy showed that PGO‐PLLA (0.3 wt%) improved impact strength of PLA by 52.19%, which resulted in ductile fractures surface of PLA/PGO‐PLLA. Microcalorimetry and thermal degradation kinetics proved that PGO‐PLLA improved the thermal stability of PLA. Polarized optical microscopy and differential scanning calorimetry confirmed that PGO‐PLLA increased crystallization rate and spherulite kernel density of PLA, and crystallinity of PLA/PGO‐PLLA reached to 22.05%. Rheological behavior proved that PGO‐PLLA increased the self‐lubricity of PLA. Enzymatic degradation results illustrated that PGO‐PLLA had some inhibition for the biodegradability of PLA based nanocomposites.