Biodegradability study of polylactic acid/ thermoplastic polyurethane blends

Blends with varied ratio of polylactic acid (PLA) and thermoplastic polyurethane (TPU) were prepared by melt blending. The PLA content in blends was 20, 40, 60 and 80 wt%. Samples of pure PLA and TPU that underwent the same thermal treatment were also prepared. Biodegradation was examined by respirometry. Pure TPU started to degrade immediately due to degradation of the low molecular weight plasticizer in the polymer. Pure PLA, on the other hand, exhibited an incubation period after which degradation progressed rapidly and was almost complete after 70 days. The degradation profile of the blends can be correlated to their morphology. Samples with a co-continuous morphology initially degrade at a higher rate than the rest of the samples due to the higher exposure of the TPU phase in these blends.     

Achieving Outstanding Mechanical Performance in Reinforced Elastomeric Composite Fibers Using Large Sheets of Graphene Oxide

A simple fiber spinning method used to fabricate elastomeric composite fibers with outstanding mechanical performance is demonstrated. By taking advantage of the large size of as‐prepared graphene oxide sheets (in the order of tens of micrometers) and their liquid crystalline behavior, elastomeric composite fibers with outstanding low strain properties have been fabricated without compromising their high strain properties. For example, the modulus and yield stress of the parent elastomer improved by 80‐ and 40‐fold, respectively, while maintaining the high extensibility of ～400% strain inherent to the parent elastomer. This outstanding mechanical performance was shown to be dependent upon the GO sheet size. Insights into how both the GO sheet size dimension and dispersion parameters influence the mechanical behavior at various applied strains are discussed.     

Design and characterization of bi-soft segmented polyurethane microparticles for biomedical application

Bi-soft segmented poly(ester urethane urea) microparticles were prepared and characterized aiming a biomedical application. Two different formulations were developed, using poly(propylene glycol), tolylene 2,4-diisocyanate terminated pre-polymer (TDI) and poly(propylene oxide)-based tri-isocyanated terminated pre-polymer (TI). A second soft segment was included due to poly(?-caprolactone) diol (PCL). Infrared spectroscopy, used to study the polymeric structure, namely its H-bonding properties, revealed a slightly higher degree of phase separation in TDI-microparticles. TI-microparticles presented slower rate of hydrolytic degradation, and, accordingly, fairly low toxic effect against macrophages. These new formulations are good candidates as non-biodegradable biomedical systems.     

Degradation studies on segmented polyurethanes prepared with poly (d, l-lactic acid) diol, hexamethylene diisocyanate and different chain extenders

In order to investigate the effect of different chain extenders on degradation properties of segmented polyurethanes (SPUs), three types of segmented polyurethanes (SPU-P, SPU-O and SPU-A) based on poly (d, l-lactic acid) diol, hexamethylene diisocyanate (HDI), were synthesized with three chain extenders: peperazine (PP), 1, 4-butanediol (BDO) and 1, 4-butanediamine (BDA), respectively. Thermogravimetric analysis, activation energy and in vitro degradation were used to characterize the obtained polymers, quantitatively. The results revealed that chain extender played an important role in thermal degradation and biodegradation of polyurethanes. Thermogravimetric analysis and activation energy demonstrated that SPU-O, SPU-P and SPU-A presented best, second and weakest thermostability, respectively, and the thermal degradation mechanism of three SPUs was the same and regarded as a two-stage degradation. Data of hydrolytic degradation of the polymers during 12 weeks indicated that the in vitro degradation stability of SPU-A and SPU-P was similar, but both were better than that of SPU-O. The reason for the differences among three types of SPUs was discussed in this paper.     

芳纶纤维/SMPU-SiO2复合材料的界面性能研究

选用形状记忆聚氨酯(SMPU)和正硅酸乙酯(TEOS)为前驱体,固体酸对甲基苯磺酸(PTSA)为催化剂,利用空气中的水分为水解水源,通过溶胶-凝胶法原位制备了形状记忆聚氨酯与二氧化硅( SMPU-SiO2)杂化材料,并将杂化材料应用于芳纶纤维增强的柔性复合材料中,以期改善芳纶纤维与基体的界面性能.同时,针对芳纶纤维表面...     

可膨胀石墨阻燃高回弹聚氨酯泡沫塑料的性能

在原料中添加可膨胀石墨(EG),采用一步法合成了阻燃型高回弹聚氨酯软泡,研究了EG对泡沫性能的影响.用扫描电镜和光学显微镜观察了EG粒子在泡沫内的固着状态及其对泡孔形貌和泡沫燃烧后的炭层形貌的影响.垂直-水平燃烧实验和极限氧指数实验检测了EG的添加量对于泡沫燃烧的抑制情况.考察了EG粒子的含量对泡沫密度、拉伸及压缩力学...     

Synthesis and thermal properties of antimony doped tin oxide/waterborne polyurethane nanocomposite films as heat insulating materials

The waterborne polyurethane (WPU) was synthesized from the polycondensation between isophorone diisocyanate (IPDI) and polyoxypropylene glycol (N‐210) and then dispersed into water. Subsequently, the WPU emulsion was modified with antimony doped tin oxide (ATO) nanoparticle by ultrasonic dispersion. The ATO/WPU emulsion was cast onto Teflon molds. After being dried, ATO/WPU films were prepared. TEM indicated that the ATO nanoparticles were homogeneously dispersed in the polymer matrix at the nanometer scale. DSC showed that the ATO/WPU nanocomposites displayed increased glass transition temperatures compared to the control WPU. The mechanical properties of the films were characterized by dynamic‐mechanical analysis (DMA). The higher glass transition temperature and storage modulus indicates the superior mechanical properties of WPU modified by ATO nanoparticles over the conventional unmodified WPU. The thermal behaviors of the films were evaluated by thermogravimetric analysis (TGA). It could be found that the incorporation of ATO into WPU can improve the thermal stability dramatically. The results from UV–visible–near infrared spectra indicated that the ATO/WPU films could decrease the infrared transmission effectively. The heat‐insulation measurements showed that glass coated with ATO/WPU films possessed better heat‐insulating effect than empty glass. Copyright © 2010 John Wiley & Sons, Ltd.     

Influence of thermal aging on tensile and creep behavior of thermoplastic polyurethane

Changes in mechanical and physical properties of polyurethane thermoplastic during aging at 70 °C and 90 °C were investigated. The loss weight response was analyzed by gravimetric measurements under these temperatures. Changes in appearance and morphology of TPU after thermal aging were revealed by optical microscopy. The prolongation of the thermal exposure time, up to 270 days, leads to a progressive increase in tensile strength. In fact, elastic modulus and stress at 200% of strain were increased with thermal exposure time. These results can be explained by the increase of thermal stability due to the increase of material rigidity and the decrease in chain mobility. The evolution of the mechanical properties from tensile tests seems to be well correlated to the creep behavior. Finally, Scanning Electron Microscopy (SEM) revealed the modification of TPU morphology fracture surface after thermal aging.     

基于光谱学分析的聚氨酯弹性体/聚磷酸铵/氢氧化铝复合材料阻燃机理研究

采用熔融共混技术,将聚磷酸铵(APP)和氢氧化铝(ATH)引入到聚氨酯弹性体(TPU)中,制备了一系列热塑性聚氨酯/聚磷酸铵/氢氧化铝(TPU/APP/ATH)复合材料。采用傅里叶红外光谱(FTIR)、X-射线光电子能谱(XPS)、扫描电镜(SEM)、激光拉曼光谱研究了TPU和阻燃TPU(FR-TPU)复合材料燃烧后炭渣的微观形貌、表面结构、元素组成、键合状态和石墨化程度,结合阻燃性能测试,揭示APP和ATH的协同阻燃机制。SEM分析表明相较于APP与ATH单独使用,TPU/APP/ATH炭层的空洞结构更少,炭渣的致密性更高。XPS分析表明FR-TPU的炭渣中C元素含量相比于纯TPU有所降低,O元素的含量有所上升,其中TPU/APP10/ATH10的C元素含量从88.2%降至69.24%,O元素的含量从8.07%升至17.78%,P和Al元素含量相较于单独添加分别从11.74%和16.36%下降至3.91%和3.31%。在此基础上,通过对C元素的分峰拟合发现TPU炭渣中C—C/C—H,C—O/C—N和CO/CN含量分别为61.05%,35.65%和3.30%;TPU/APP10/ATH10炭渣中三种结构含量分别为45.38%,45.00%和9.63%,说明ATH和APP复配使用有利于C元素形成酯、醚、羰基、羧酸（盐）、酯基等结构。通过对O元素的分峰拟合发现,TPU炭渣中O₂/H₂O,—O—,O三种结构含量分别为28.75%,44.36%和26.89%;TPU/APP10/ATH10炭渣中O₂/H₂O,—O—,O三种结构含量分别为44.33%,32.78%和22.89%,说明APP和ATH的加入有利于炭渣中O元素形成O₂/H₂O结构。通过对N元素的分峰拟合发现,TPU炭渣中—NH—,N结构的N元素含量分别为40.93%和59.07%;TPU/APP10/ATH10中—NH—,N结构的N元素含量分别47.17%和52.83%,说明ATH与APP复配使用促进了—NH—结构的形成。拉曼测试表明,相比于单独使用,APP和ATH复配使用,炭层的石墨化程度更好,致密性更高。以上分析结合阻燃测试可以得出TPU/APP/ATH复合材料阻燃机制：ATH受热分解生成氧化铝,吸收热量并释放大量水蒸气,有效促进APP降解,生成不燃性的氨气和聚磷酸,氨气和水蒸气稀释可燃性气体的浓度。随着温度继续升高,氧化铝可继续与聚磷酸反应生成偏磷酸铝[Al(PO₃)₃],同步催化聚氨酯基体成炭,形成高度石墨化炭层,石墨化炭层与偏磷酸铝一起覆盖在基体表面,有效抑制燃烧区域物质以及能量的输运,从而达到阻燃目的。     

Improving the adhesion between a aqueous PU and a polyamide fibre with silane

Glycidoxypropyltrimethoxysilane (GPS) and γ-aminopropyltrimethoxysilane (APS) were used to modify the surface chemistry of polyamide fibre. The surface chemistry was characterised using X-ray photoelectron spectroscopy. The silanol functional group was designed to be introduced on the surface of polyamide fibre to increase its chemical activity by N-alkylation of GPS and hydrolysis of APS, and to improve the poor interfacial adhesion between a polyamide 66 fibre and an aqueous polyurethane polymer adhesive. The microbond test was used to measure the interfacial shear strength between the waterborne PU adhesive and the polyamide fibre. It has been found that APS hydrolysis and GPS-alkylated fibre surface can be used to improve the interfacial adhesion of polyamide fibre to PU. The IFSS can be improved by N-alkylation of GPS from 5.0 to 8.4?MPa. After water immersion at 50?°C for 48?h, then drying, the IFSS increased to 8.8?MPa due to the plasticisation of PU in water. Better interfacial adhesion was also observed by the hydrolysis of APS, but not significantly improved by this method due to the relatively weak hydrogen bond at the interface between APS and polyamide fibre.