聚己内酯-天然骨粉生物医用复合材料的制备和性能

采用熔融共混法制备了不同天然骨粉含量的聚己内酯-天然骨粉（PCL-BP）生物医用复合材料,并通过力学实验、表面亲水性分析、差示扫描量热分析和热重分析对复合材料的性能进行了表征。结果表明：随着天然骨粉含量的增加,复合材料的拉伸和弯曲强度先增加后降低,其表面亲水性得以改善。此外,复合材料的结晶温度升高,熔融焓降低,热稳定性...     

高氯酸锂对PEO结晶结构和结晶行为的影响

利用配备热台的偏光显微镜(POM)、红外光谱仪(FTIR)和示差扫描量热器(DSC)等实验方法研究了高氯酸锂(LiClO4)与聚氧化乙烯(PEO)之间的络合作用对PEO结晶行为和结晶形态的影响.DSC测试结果表明在LiClO4/PEO二元共混体系中,PEO的熔融温度、结晶温度随着锂盐含量的增加出现先增加后降低的现象;而结晶度则是先不变后降低.FTIR结果表明LiClO4影响聚合物结晶性能的原因是Li+能和PEO中的醚基的络合作用.POM观察结果发现LiClO4/PEO共混体系中存在聚合物的球晶,共混体系中聚合物的球晶生长速率都随着结晶温度的升高而下降,并且球晶生长速率还随着体系中随LiClO4含量的增加而减小.     

膨胀蛭石填充聚甲醛复合材料的制备与性能

采用经硅烷偶联剂和十六烷基三甲基溴化铵有机插层处理的膨胀蛭石微粉(EV)填充改性聚甲醛(POM),通过熔融共混制备POM/EV复合材料,并讨论了EV含量对复合材料的力学性能及热稳定性的影响.研究结果表明:当EV添加量为2%(w)时,复合材料的断裂伸长率为66.2%,较纯POM提高44.5%;弯曲强度和缺口冲击强度分别为77.7 MPa和6.15 kJ/m~2,分别较纯POM降低了7.9%和2.4%.此外,当EV的添加量为5%(w)时,复合材料的结晶点较纯POM提高了1.4℃;且随着EV添加量的增加,复合材料的热稳定性越好.     

聚环氧乙烷(PE0)与聚双酚A羟基醚(PBHE)共混体系的研究

用偏光显微镜(PLM)、扭辫(TBA)、IR及WAXD对PEO/PBHE共混体系结晶形态进行了研究。结果表明,PEO含量在50％以上的共混体系,几乎完全被PEO球晶充满,非晶态PBHE作为微区分散在大球晶之间或球晶之中。PEO含量为40％和30％的照片上呈现树枝晶。PEO含量为20％以下时照片中不再看到结晶出现,PEO与PBHE形成单一非晶相。PEO/PBHE共混体系的组分之间存在着氢键相互作用,这种作用强于PBHE分子间的氢键作用。共混体系的结晶度及T_g随PBHE组分含量的增加,前者减小后者增加并符合FOX方程揭示的规律。PEO与PBHE具有很好的相容性。     

聚环氧乙烷(PE0)与聚双酚A羟基醚(PBHE)共混体系的研究

 用偏光显微镜(PLM)、扭辫(TBA)、IR及WAXD对PEO/PBHE共混体系结晶形态进行了研究。结果表明,PEO含量在50％以上的共混体系,几乎完全被PEO球晶充满,非晶态PBHE作为微区分散在大球晶之间或球晶之中。PEO含量为40％和30％的照片上呈现树枝晶。PEO含量为20％以下时照片中不再看到结晶出现,PEO与PBHE形成单一非晶相。PEO/PBHE共混体系的组分之间存在着氢键相互作用,这种作用强于PBHE分子间的氢键作用。共混体系的结晶度及T_g随PBHE组分含量的增加,前者减小后者增加并符合FOX方程揭示的规律。PEO与PBHE具有很好的相容性。     

环氧树脂/聚氧化乙烯共混物及其与硫氰化钠络合物的结构研究(Ⅰ)

对不同分子量聚氧乙烯(PEO)以不同比例与双酚A二缩水甘油醚型环氧树脂(ER)制得的交联共混物ER/PEO,以及再与NaSCN络合后的产物用WAXD,SAXS,DSC和SEM等方法进行了研究,结果表明:随着ER含量的增加,ER/PEO共混物由晶态转为非晶态。ER/PEO属单斜晶系;与NaSCN络合后,体系结晶性变差。ER/PEO-NaSCN属三斜晶系,其长周期比相应ER/PEO交联共混物的长周期值大。EP的加入使非晶层增厚,结晶片层变薄,长周期值增加。     

静电纺丝法制备PAN/HNTs混杂纤维增强热塑性聚氨酯复合材料

静电纺丝方法制备了聚丙烯腈/埃洛石纳米管(PAN/HNTs)混杂纤维增强体,通过改变接收装置、热拉伸处理得到5种不同的PAN/HNTs混杂纤维增强体。采用浸渍法将5种增强体用于改性热塑性聚氨酯,得到PAN/HNTs/TPU复合材料。结果表明,PAN/HNTs混杂纤维增强体可显著提高复合材料的力学性能。将平板接收制备的PAN/HNTs混杂纤维增强体以及另外两种由1050r/m滚筒接收制备的PAN/HNTs混杂纤维增强体(前者不采用热拉伸,后者采用热拉伸),三者制成PAN/HNTs/TPU复合材料。与通过平板接收制备的复合材料相比,通过由1050r/m滚筒接收制备的两种复合材料性能要优于前者,相较于前者,其复合材料的拉伸强度分别增加了19%和43%,弹性模量分别增加了44%和122%,断裂伸长率分别增加了19%和24%。当定向接收的PAN/HNTs纤维膜的含量为5.6%时所得到的PAN/HNTs/TPU复合材料力学性能为最佳;通过热拉伸处理PAN/HNTs纤维膜,当含量为4.5%时,复合材料的力学性能为最佳。这种力学增强的主要原因是PAN/HNTs纤维与热塑性聚氨酯材料之间的相容性得到了改...     

铜离子配位下的聚氧乙烯受限结晶行为研究——缺陷引起的熔点下降

利用铜离子(Cu2+)对聚氧乙烯(PEO)的配位作用所形成的对分子链运动的束缚,研究了链段受限下PEO的结晶和熔融行为.首先利用宽频介电松弛谱(BDS)对受限条件下PEO的松弛行为进行表征,结果表明,加入铜离子后PEO的β-过程和γ-过程的特征松弛时间都变长,说明PEO的链段协同运动和主链扭转运动都变得更加困难;松弛时间为评价受限程度提供了定量的依据.DSC的测试结果表明,受限条件下PEO的玻璃化转变温度(Tg)升高,同时出现冷结晶现象,说明Cu2+配位作用确实对PEO的链段运动产生了束缚作用;同时PEO的结晶度和熔点都随着铜离子含量的提高而降低.WAXD结果表明,CuBr2在共混物中没有发生结晶,同时PEO的晶型没有发生改变.利用AFM进一步研究了PEO/CuBr2共混物薄膜的结晶形貌,发现在不同Cu2+含量的共混物中PEO都形成伸直链晶体,片晶厚度没有变化,说明熔点的降低并非是片晶厚度变化所导致.但是AFM的结果却显示螺位错晶体的数量随着Cu2+含量的提高明显增加.可以认为,在Cu2+配位受限下的PEO体系中,晶体缺陷应是引起熔点下降的主要原因,和金属等其它晶体材料的情况有着类似效应.     

PEO分子量对POM/PEO晶/晶共混物溶液结晶的影响

以六氟异丙醇(HFIP)为聚甲醛(POM)与聚氧化乙烯(PEO)的共溶剂,通过溶液结晶研究了PEO分子量对POM/PEO 50/50晶/晶共混物结晶行为及结晶形态的影响。结果表明,PEO分子量越小,POM与PEO在结晶过程中相互干扰越大。当PEO分子量为4×103时,共混物中POM形成部分不完善晶体,出现明显的熔融双峰。SEM结果表明:含不同分子量PEO的共混晶体均无明显相分离,且低分子量PEO的共混物更易形成规整球晶,认为通过溶液结晶,POM/PEO 50/50共混物中POM与PEO形成了晶体相互穿插的结晶结构。     

聚磷腈微球的制备及其阻燃PET的研究

采用沉淀聚合法制备聚环三磷腈-co-(3,4-二羟基苯甲酸)(Poly(HCCP-co-PCA))微球,通过傅里叶变换红外光谱、扫描电镜和热重分析等测试手段对其进行表征,研究单体摩尔比对微球的结构、微观形貌以及热稳定性的影响,其中n(HCCP)/n(PCA)为1/0.5时,聚磷腈微球的粒径较为均一,分散均匀,直径为1.5μm左右,并且具有优异的热稳定性和成炭性能。采用熔融共混法制备PET/Poly(HCCP-co-PCA)复合材料,研究Poly(HCCP-co-PCA)的用量对复合材料阻燃性能的影响,并探究其阻燃机理。结果表明,随着Poly(HCCP-co-PCA)含量的增加,复合材料的阻燃性能明显提高。当Poly(HCCP-co-PCA)添加量为1.5(wt)%时,复合材料通过UL 94-V0等级测试,极限氧指数为28.8%,并且热释放速率峰值和总热释放量分别降低了75.26%和69.07%。其阻燃原理主要是燃烧时生成炭层较多,起到较好隔绝效果,同时产生不可燃气体,进一步提升阻燃效果。     

Investigating the mechanical,thermal and melt flow index properties of HNTs – LLDPE nano composites for the applications of rotational moulding

Linear low density polyethylene (LLDPE) is the one of the most popular polymer used for rotational moulding applications such as storage tanks. But, its inferior mechanical properties and thermal stability restrict the longer service. Hence, this study experimentally demonstrates the effect of Halloysite Nanotube (HNTs) concentration on LLDPE composites for enhancing the mechanical and thermal stability. HNTs were uniformly dispersed with LLDPE matrix through ultra-sonication, followed by compression moulding used to prepare the nano composites plates. The prepared composites are shown 19.2% improved tensile strength for 2 wt% HNTs, whereas 28.9% hike in flexural strength observed for 4 wt% HNTs composite, compare to neat LLDPE. Which shows that higher concentrations of HNTs is favourable in improving the flexural strength rather than tensile properties. In addition to that, higher concentrations of HNTs are also helping in improving the storage modulus of the LLDPE composites. The increase in mechanical properties mainly attributed due to effective load carriers (HNTs) in the composite. Besides, HNTs were also contributing for improving the melting point and residual char of the composites, which is indeed for storage tanks durability. The prepared composite was thermally stable at higher temperature up to 230 °C, because of HNTs chemical structure, the inner layer of HNTs constitute with Al₂O₃ and outermost layer constitute with SiO_2, both are thermally stable. Stated enhancement proves the potential effect of HNTs reinforcement in the LLDPE composite for rotational moulding applications.     

Polymer electrolyte for lithium batteries based on photochemically crosslinked poly(ethylene oxide) and ionic liquid

Polymer/ionic liquid composites were investigated as solvent-free electrolytes for lithium batteries. Ternary electrolytes based upon poly(ethylene oxide), an ionic liquid and a conducting salt were UV crosslinked with benzophenone as the photoinitiator. Crosslinking leads to an increase in mechanical stability of the PEO composites. This straight-forward process provides a way to increase the content of ionic liquid and thus to raise ionic conductivity without loss of mechanical stability. Impedance measurements showed that the ionic conductivity of the composites is not affected by the UV curing process. Moreover, the UV curing process causes a decrease in the degree of crystallinity in the PEO composites which contributes to an increase in ionic conductivity. The present work is related to safety issues of lithium batteries.     

Chemical modification of carbon fiber with diethylenetriaminepentaacetic acid/halloysite nanotube as a multifunctional interfacial reinforcement for silicone resin composites

In the present research, a multifunctional hierarchical reinforcement was prepared by chemical modification of carbon fibers (CFs) with halloysite nanotubes (HNTs) by the bridging diethylenetriaminepentaacetic acid (DTPA) for improving interfacial microstructures and properties of composites. Surface structures and groups of modified HNTs and CFs were characterized systematically. The uniform distributions of the introduced DTPA and HNTs helped to increase fiber polarity, surface energy, and wettability. As a consequence, significant enhancements of interfacial properties and hydrothermal aging resistance of composites were achieved, and interfacial reinforcing mechanisms have also been studied. Moreover, the storage modulus showed a 17.95% improvement, and the glass transition temperature was enhanced by 17°C by dynamic mechanical analysis testing.     

Thermal stability and flame retardant effects of halloysite nanotubes on poly(propylene)

Naturally occurred halloysite nanotubes (HNTs) with hollow nanotubular structures were used as a new type filler for poly(propylene) (PP). Nanocomposites based on PP and HNTs were prepared by melt blending. Scanning electronic microscopy (SEM) results suggested HNTs were dispersed in PP matrix evenly at nanoscale after facile modification. Thermal stability of the nanocomposites was found remarkably enhanced by the incorporation of HNTs. Cone calorimetric data also showed the decrease of flammability of the nanocomposites. Entrapment mechanism of the decomposition products in HNTs was proposed to explain the enhancement of thermal stability of the nanocomposites. The barriers for heat and mass transport, the presence of iron in HNTs, are all responsible for the improvement in thermal stability and decrease in flammability. Those results suggested potential promising flame retardant application of HNTs in PP.     

Effects of halloysite nanotube orientation on crystallization and thermal stability of polypropylene nanocomposites

The polypropylene/halloysite nanotubes (PP/HNTs) nanocomposites were prepared via water-assisted injection molding (WAIM) and compression molding (CM). HNTs were highly oriented in WAIM parts due to the strong shear effect; whereas HNTs were randomly oriented in the CM one. The orientation of HNTs had little influence on their nucleating efficiency for the PP. However, the HNTs selectively induced α-form crystal at high cooling rates; whereas they showed β-nucleating activity at low cooling rates. Thermal analyses revealed that the HNTs delayed thermal degradation onset in the initial degradation stage, whereas they sped up the thermal degradation in the main volatilization stage at the contents of 5 and 8 wt%. The simultaneous thermogravimetric analyses and differential scanning calorimetry measurements revealed that, at a low content, the direct stabilizing effect of HNTs on PP contributed largely to the increased thermal stability of the WAIM PP/HNTs nanocomposites rather than their barrier and entrapment effect on the volatile products.     

Comparative properties of cellulose nano-crystals from native and mercerized cotton fibers

Stable aqueous suspensions of cellulose nano-crystals (CNCs) were fabricated from both native and mercerized cotton fibers by sulfuric acid hydrolysis, followed by high-pressure homogenization. Fourier transform infrared spectrometry and wide-angle X-ray diffraction data showed that the fibers had been transformed from cellulose I (native) to cellulose II (mercerized) crystal structure, and these polymorphs were retained in the nanocrystals, giving CNC-I and CNC-II. Transmission electron microscopy showed rod-like crystal morphology for both types of crystals under the given processing conditions with CNC-II having similar width but reduced length. Freeze-dried agglomerates of CNC-II had a much higher bulk density than that of CNC-I. Thermo-gravimetric analysis showed that CNC-II had better thermal stability. The storage moduli of CNC-II suspensions at all temperatures were substantially larger than those of CNC-I suspensions at the same concentration level. CNC-II suspensions and gels were more stable in response to temperature increases. Films of CNC and Poly(ethylene oxide) were tested. Both CNC-I/PEO and CNC-II/PEO composites showed increased tensile strength and elongation at break compared to pure PEO. However, composites with CNC-II had higher strength and elongation than composites with CNC-I.     

聚氧化乙烯/高岭石聚合物电解质的制备与表征

通过尿素对高岭石的插层及随后的超声脱除处理,制备了一种片层剥离的高岭石粉体,并将这种剥离高岭石与聚氧化乙烯/高氯酸锂(PEO/LiClO_4)体系复合,制备出PEO/高岭石复合物.采用X射线衍射仪、红外光谱仪、扫描电子显微镜、透射电子显微镜、扫描量热仪、电化学工作站和万能材料试验机进行结构表征和性能测试.结果表明,尿素在高岭石层间的插层和脱除引起了高岭石片层的剥离,片层厚度小于50 nm.剥离高岭石在PEO/LiClO_4体系中与PEO形成了强烈的氢键作用,促进了PEO结晶度的降低,进而提高复合物的离子电导率.含有20 wt%剥离高岭石填料的PEO/高岭石复合物的离子电导率达到6.0×10~(-5) S/cm,与未复合的PEO/LiClO_4相比,提高了一个数量级.复合物制备过程中的烘干温度对PEO的结晶度会产生一定的影响,95°C下的烘干处理能得到结晶度较低,离子电导率较高的复合物.此外,剥离高岭石的添加显著提高了聚合物的杨氏模量和拉伸强度,与未复合的PEO/LiClO_4相比,杨氏模量和拉伸强度最大提高了256%和121%.     

Understanding the effect of filler shape induced immobilized rubber on the interfacial and mechanical strength of rubber composites

Styrene butadiene rubber (SBR) composites with silica, halloysite nanotubes (HNTs) and montmorillonite (MMT) were prepared and the interfacial and mechanical properties were compared to understand the reinforcing behaviours of these fillers based on the results of SEM, DSC, DMA, etc. Due to the formation of interparticle domain, HNTs immobilized more rubber approaching their surface than silica and MMT. Interestingly, only tightly immobilized rubber chains made contribution to the enhancement of interfacial and mechanical strength of SBR composites. This was because the tightly immobilized rubber acted as a bridge in the filler-rubber interface and induced the formation of stretched rubber chains linked filler network when the composites were loaded in tension, while loosely immobilized rubber were easy to slip off from filler surface, causing the separation between filler and bulk rubber. Therefore, silica with more tightly immobilized rubber approaching its surface showed better reinforcing effect on rubber than HNTs and MMT.     

聚氧乙烯-粘土-碱金属离子插层复合物作用机理研究

测量了聚氧乙烯(PEO)-粘土-K^＋/Na^＋插层复合物在不同相对湿度环境中的相对吸水量, 研究了相对吸水量与粘土层间距d₀₀₁之间的关系, 并结合X射线光电子能谱的研究结果, 探讨了复合物中PEO、粘土与碱金属离子三者之间的相互作用. 在K-MMT-PEO复合物中, K^＋与PEO和粘土表面都存在配合作用, 形成稳定的三元配合物, 在不同相对湿度下, K-MMT-PEO配合物吸水能力较低, 层间距基本不变. 在Na-MMT-PEO复合物中, Na^＋与PEO形成配合物, 水分子能破坏Na^＋-PEO之间的配合作用, 使PEO和Na^＋各自形成水化层, 因此随着相对湿度的增加Na-MMT-PEO复合物的相对吸水量和层间距都增大.     

固体高分辨核磁共振研究聚氧乙烯/纳米二氧化硅复合物的界面相互作用

采用固体高分辨核磁共振碳谱对聚氧乙烯(PEO)/纳米二氧化硅(Nano-SiO₂)复合物体系的相态结构、分子间相互作用和分子运动进行了研究,发现随着复合物中SiO₂含量增加,PEO结晶度明显降低,且PEO非晶区的分子运动受到明显约束,基于对PEO非晶区及SiO₂颗粒表面羟基质子的自旋-自旋弛豫行为的分析,提出了复合物的界面模型以及SiO₂与PEO之间的界面相互作用机制.