Synthesis and properties of castor oil-based polyurethane containing short fluorinated segment

This study successfully incorporated a short-segment fluorine-containing chain extender (2,2,3,3-tetrafluoro-1,4-butanediol [TF]) into castor oil-based polyurethane (COPU) to synthesize TF/COPUs. The interactions between TF and COPU components were identified by Fourier transform infrared and X-ray photoelectron spectroscopies, the results revealed that the increase in the TF content increased the van der Waals forces in C F…CO and the hydrogen bonding force in C F…H N. Atomic force microscopy indicated that the addition of more TF contributed to a higher level of microphase separation in the TF/COPUs. Thermogravimetric analysis showed that the TF component can enhance the thermal resistance of TF/COPUs. Differential scanning calorimetry and dynamic mechanical analysis indicated that the glass transition temperature (T_g) of TF/COPUs increased with the TF content. The stress–strain testing showed that the tensile strength and elongation at break values decreased with the TF content. This tensile behavior may be due to the molecular weight of a TF/COPU decreased with the TF content as evidenced by the gel permeation chromatography results. The hydrolytic degradation tests of dipping TF/COPUs in 3 wt% NaOH solution indicated that TF could lower the surface free energy and enhance the degradation stability of TF/COPUs.     

线性富磷化阻燃剂在聚氨酯泡沫中的应用研究

通过界面聚合法合成了一种线性富磷化阻燃剂（LPRFR），将LPRFR与可膨胀石墨（EG）复配制备了阻燃聚氨酯泡沫（RPUF），使用红外光谱分析仪、核磁共振分析仪对阻燃剂LPRFR的化学结构进行了表征，并通过极限氧指数仪、锥形量热仪、扫描电子显微镜和红外光谱分析仪对RPUF的燃烧性能、微观形貌和化学结构进行了分析。结果表明，仅10 %（质量分数，下同）的LPRFR 与8 %EG复配后，RPUF的极限氧指数（LOI）便达到26.1 %；LPRFR和EG能大幅降低RPUF的热释放速率，并提高基体的成炭能力； LPRFR参与了燃烧过程中的成炭反应，形成了含P—O—C及P=O结构的高质量炭层，有效隔绝了氧气和热量；LPRFR是一种对于聚氨酯泡沫阻燃性能优异的新型阻燃剂。     

Enhanced airborne sound absorption effect in poly(vinylidene fluoride)/(K0.5Na0.5)NbO3-nanofiber composite foams

Introducing electrical conductive function to discharge local piezoelectric effect is found effective for improving airborne sound absorption performance. In this work, instead of conductive fillers, a composite with two piezoelectric materials with opposite piezoelectric responses was explored aiming at enhanced sound absorption effect. Open-cell poly(vinylidene fluoride)/(K_0.5Na_0.5)NbO₃ (PVDF/KNN)-nanofiber composite foams were proposed and investigated for airborne sound absorption purpose. Structural and thermal analyses showed that the KNN nanofibers were well dispersed in the PVDF matrix and enhanced the degree of crystallinity of polar phase of PVDF. Significantly enhanced airborne sound absorption over a broad frequency range was observed in the PVDF/KNN-nanofiber composite foams, with increasing KNN nanofibers. One possible mechanism for the improved sound absorption with the piezoelectric KNN nanofibers with positive piezoelectric coefficient added in the PVDF matrix with negative piezoelectric coefficient is that electrical discharge could be facilitated for energy dissipation with the opposite charges generated through the piezoelectric effects in the two phases with opposite polarity. The experimental results show that the open-cell PVDF/KNN-nanofiber composite foams are promising for broadband airborne sound absorption application, and our analysis shed a light on the strategy in designing piezoelectric composite foam with high sound absorption performance.     

聚酯类增塑剂的合成与应用研究进展

综述了国内外聚酯增塑剂的合成及应用的最新研究进展，重点介绍了超支化、生物基、石油基聚酯增塑剂的合成与制备方法以及不同类型聚酯增塑剂在聚氯乙烯(PVC)、淀粉、聚乳酸、聚氨酯弹性体与橡胶制品中的最新应用研究进展；并对聚酯增塑剂未来发展方向做了展望。     

Shear and mode II fracture of PUR foams

Polyurethane (PUR) foam materials are widely used as cores in sandwich composites, for packing and cushioning. They are made of interconnected networks of solid struts and cell walls incorporating voids with entrapped gas. The main characteristics of foams are lightweight, high porosity, high crushability, and good energy absorption capacity. Fracture toughness in mixed mode loading is of particular interest because foam cracking weakens the structure’s capacity for carrying loads.Present paper assesses the shear elastic (shear modulus) and mechanical (shear strength) properties of polyurethane foams. Also, three different types of specimens were used to determine mode I and mode II fracture toughness. The shear modulus, shear strength and fracture toughness increases with increasing foam density. Also the effect of loading direction and loading speed is investigated. The authors propose a micromechanical model to estimate fracture toughness based on the tensile strength of the solid material and the topology of the cellular structure.     

不同硬度PTMG型CPUE与硫化橡胶的性能对比研究

通过改变硬段含量、扩链系数等制备了几种不同硬度的四氢呋喃均聚醚(PTMG)浇注型聚氨酯弹性体(CPUE),讨论了PTMG型CPUE与硫化橡胶(VR)的物理机械性能、拉伸应力应变行为以及动态力学性能的区别。结果表明,随CPUE硬度的提高,材料的刚性增强,力学性能是低硬度VR的数倍。通过对CPUE硬度的调节,可以使之兼具聚氨酯和橡胶的优良性能。在玻璃态温度下CPUE的储能模量随硬度的减小而降低,但都高于VR,而且CPUE的硬度越大,二者相差越大,温度越低,相差也越大;在室温以上温度范围内,CPUE具有比VR更小的力学损耗。     

Transparent and flexible films of new segmented polyurethane nanocomposites incorporated by NH2-functionalized TiO2 nanoparticles

In this work, TiO₂ nanoparticles are surface modified by NH₂-terminated organic moieties arised from 4,4′-methylene diphenyl diisocyanate (MDI). These nanoparticles are incorporated into ether-based segmented polyurethane (SPU) matrix. MDI is utilized as monomer together with poly(tetramethylene oxide) (PTMO) comonomer for preparing the final polymer as well. The NH₂-functionalized TiO₂ nanoparticles are covalently linked to the NCO terminals of the resulting SPU macromolecules during film preparation stage. Therefore, in addition to butylene glycol, these surface modified nanoparticles with enhanced organophilicity could play the role of the second chain extender of NCO-capped SPU macromolecules through formation of urea linkages. Optical and thermal behaviors of the transparent and flexible film (SPU/TiO₂–MDI) is compared with those of unmodified TiO₂ (SPU/TiO₂) and TiO₂-unloaded SPU films. Though the particle loading is only 5 wt.%, incorporation of TiO₂ and TiO₂–MDI nanoparticles into the SPU polymer enhances significantly the light absorption in UV region at 300–400 nm. SEM images of the prepared films clearly show a considerable decrease in particle aggregation for TiO₂–MDI into SPU matrix compared to that of unmodified TiO₂. TG analyses indicate a one-step decomposition pattern with onset temperatures of about 360 and 380 °C for neat SPU and SPU/TiO₂–MDI, respectively. Moreover, DTA thermograms of both nanocomposites show obviously two exothermic phase transitions in the thermal range of 330–440 °C.     

An effective approach to reinforced closed-cell Al-alloy foams with multiwalled carbon nanotubes

Exploring the reinforcing role of carbon nanotubes to obtain materials (polymers, metals, ceramics) with enhanced properties has been often attempted, but the success is strongly limited by the dispersing degree of carbon nanotubes. Here we report on an innovative colloidal approach to disperse the carbon nanotubes in the powders mixture of the precursor materials in order to profit from their reinforcing potential and obtain a new class of closed-cell metal foams. The feasibility of the proposed approach was demonstrated for aluminium foams reinforced with multi-walled carbon nanotubes. These nanocomposite metal foams synergistically combine the remarkable properties of both metal foams and carbon nanotubes. The results indicate that the tubular structure of carbon nanotubes is preserved throughout the entire the process. The carbon nanotubes are individually dispersed, stretched and randomly aligned in the aluminium-matrix of these closed-cell foams, thus potentiating their homogeneous 3D reinforcing role. Accordingly, the Vickers micro-hardness of the closed-cell foams was greatly enhanced.     

Optimizing the lignin based synthesis of flexible polyurethane foams employing reactive liquefying agents

The present work is focused on the optimization of a green process based on the employment of by‐products obtained from wood treatments as raw materials for producing flexible polyurethane foams. More specifically, lignin was employed in flexible polyurethane foams in order to partially replace the usual fossil polyols; therefore glycerol (GLY) and glycerin polyglycidyl ether (EJ 300) were used as the polyol fraction for lignin liquefaction. Polypropylene glycol triol was used as a chain extender in different ratios with liquefaction solvents, and polymeric diphenylmethane diisocyanate as an isocyanate fraction. Liquefaction of lignin was performed by microwave irradiation, thus reducing the processing time and energy required compared to present industrial production processes. All the foams were produced in controlled expansion through the adoption of a ‘one‐shot’ approach, using water as a blowing agent and with an isocyanate index (NCO/OH) of less than 100 to improve the flexibility of the foam. This approach allowed for the substitution of up to 12% of common petro derived polyol with commercial soda lignin. Finally, the foams were characterized, presenting properties that could be modulated as a function of lignin content, GLY/EJ 300 ratio and isocyanate index. The qualities of the foams were compatible with existing materials used for furniture and for the interiors of car seats and couches. © 2015 Society of Chemical Industry     

压电精密驱动柔性微夹钳设计

为了实现对微纳尺度下物件的精密夹持,建立了柔性微夹钳系统。并对该系统柔性夹钳设计、运动学、动力学和控制方法等进行研究。首先,利用柔性铰链设计方法设计了柔性微夹钳,利用伪刚体法建立了机械的伪刚体模型。接着,以伪刚体模型法建立了系统的运动学模型,即机械放大比和输入刚度等数学模型。然后,利用拉格朗日方法建立了系统的动力学方程,得出系统的自然振动频率。最后,通过ANSYS有限元方法对系统建立的模型进行了仿真分析和验证,此外,利用PID控制算法对微夹钳系统进行实验控制。实验结果表明:跟踪控制结果误差为2.4%;放大比为9.12倍。基本满足微纳尺度下的微夹持工作,其工作精度可达微米级别甚至纳米级别,符合设计要求。