不同石墨烯-碳纳米管杂化体系对热塑性聚氨酯复合材料力学和自修复性能的增强机制

采用溶液共混法,设计不同的杂化方案,制备了3种具有不同复合程度的石墨烯(G)和碳纳米管(CNT)三维空间结构材料,并对G-CNT填充的热塑性聚氨酯(TPU)复合材料的力学性能及在微波诱导下的裂纹自修复特性进行了研究.结果表明,G-CNT复合结构能改善增强相与基体间的界面结合及载荷传递,且复合程度越高其对TPU力学增强效果越显著.当采用预复合方法时G-CNT复合程度最高,此时TPU复合材料的拉伸强度比纯TPU提高了37.6%,比G/TPU提高了27.1%.TPU复合材料在微波场的诱导下可实现损伤裂纹的快速修复,然而其修复效率并未随着G-CNT复合程度的增加而升高,当采用超声复合时,G-CNT的复合程度低于预复合法的复合程度,但其修复率却达到最高值(138%).该自修复特性和G-CNT的空间构型及其异质界面与微波之间的耦合机制密切相关.     

氧化石墨烯纳米带-碳纳米管/TPU复合材料薄膜的制备及表征

将不同维度纳米填料同时复合,采用纵向氧化切割MWCNTs法制得不同含量比的氧化石墨烯纳米带-碳纳米管(GONRs-CNTs)2种维度纳米材料复合体,随后将上述填料加入到TPU基体中制得GONRsCNTs/TPU复合材料薄膜.采用FTIR、XRD、TG、XPS、TEM和FE-SEM研究了不同反应条件下所得GONRsCNTs复合体的结构及性能,并结合复合材料薄膜的氧气透过率和拉伸测试以及表面形貌观察,研究了GONRs与CNTs的协同作用、二者的含量比对TPU复合材料薄膜阻隔和力学性能的影响.研究表明,GONRs与CNTs的协同效应明显优于MWCNTs,同时当所加GONRs-CNTs复合体中GONRs与CNTs的含量比约为67∶33时,GONRs-CNTs/TPU复合材料薄膜的氧气透过率和拉伸强度相比纯TPU薄膜分别降低51.3%和提高29.3%,阻隔性能和力学性能均得到明显改善.     

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...     

基于非共价键制备高韧性可修复聚合物复合材料

以鞣花酸(ELA)改性氧化石墨烯(EGO)作为“砖”、聚氨酯(PU)作为“泥”，并引入非共价键，通过蒸发诱导自组装制备了可修复仿珍珠层复合材料(PU-EGO)。利用红外光谱、电位分析仪、X射线衍射仪等对EGO结构进行表征，通过万能试验机对PU-EGO的力学性能进行测试。结果表明：ELA吸附于GO表面，且当PU与EGO质量比为3∶1时，PU-EGO的拉伸强度和韧性分别达到111.2 MPa和81.5 MJ/m³(相比PU分别提高了9.6倍和1.8倍)。此外，所制备的材料还具备良好的自修复性和重复加工性能。     

同时添加碳纳米管及石墨烯对热致液晶聚酯形状记忆行为及拉伸性能的影响

利用溶液共混的方法将碳纳米管(CNT)及石墨烯(G)同时加入到热致液晶聚酯中制备纳米复合材料.通过透射电镜(TEM)研究纳米粒子的分散及形貌.采用荧光光谱及拉曼光谱研究碳纳米填料与热致液晶聚酯基体之间存在π-π相互作用.利用电子万能试验机(EUTM)研究了材料的拉伸性能,由于CNT与G与基材之间作用力强,且CNT与G间的协效作用能有效地实现应力转移,同时加入CNT及G有助于提升复合材料的拉伸强度.动态热机械分析(DMA)数据表明,同时添加CNT与G对于复合材料的固定率影响不大,但会降低回复率;同时复合材料的回复应力也得到显著的提升.     

兼具导热和自修复功能的聚合物复合材料

针对聚合物复合材料存在的结构受损导致导热和力学强度降低的问题,提出利用导热填料增强自修复聚合物,实现导热性能和力学强度的快速修复.通过对双(3-氨丙基)封端的聚二甲基硅氧烷(H2N-PDMS-NH2)进行端基改性,得到脲基嘧啶酮(UPy)双封端的聚二甲基硅氧烷(UPy-PDMS-UPy),于60℃下20 h后拉伸强度修复效率可达86.6%.进一步填充羟基化氮化硼(mBN)制备兼具自修复功能的导热复合材料,研究发现mBN的填充导致复合材料强度提高但韧性降低,对导热性能和自修复功能分别起积极和不利影响.当mBN含量为30 wt%时,热导率高达2.579 W·m^?1·K^?1,于60℃下40 h后拉伸强度修复效率达82.0%.红外热像仪显示,损伤处接触10 h后,mBN-30/UPy-PDMS-UPy上表面温度接近初始温度,展现出导热通路的修复特征,实现导热与自修复功能的兼备.     

GAP黏合剂体系交联网络结构研究

为改善聚叠氮缩水甘油醚(GAP)黏合剂体系的网络结构,分别考察了GAP与二官能度的甲苯二异氰酸酯(TDI)或异佛尔酮二异氰酸酯(IPDI)预聚、缩二脲多异氰酸酯(N-100)与二官能度固化剂的种类和配比对GAP弹性体力学性能、网络结构参数、网络结构完整性以及拉伸断面形貌的影响.结果表明,将GAP与TDI预聚可提高体系交联网络结构的完整性,同时提高弹性体的断裂延伸率和最大拉伸强度.适量加入二官能度异氰酸酯能改善体系的网络结构完整性,由于预聚体中TDI与IPDI结构和反应活性的差别,GAP/TDI/N-100弹性体在N-100与TDI质量比为7∶3时体系网络结构最完整,而GAP/IPDI/N-100弹性体在N-100与IPDI质量比为5∶5时体系网络结构最完整;在相同的N-100含量下GAP/IPDI/N-100体系比GAP/TDI/N-100体系强度高,延伸率略低.随着N-100含量的减少,GAP/TDI/N-100体系最大拉伸强度(δ_m)从0.66 MPa降低到0.32 MPa,断裂延伸率(ε_b)从104.6%提高到506.3%;GAP/IPDI/N-100体系强度在W(N-100)∶W(IPDI)=7∶3时达到最大值0.69 MPa,断裂延伸率从103.2%提高到391.4%.扫描电镜(SEM)结果表明,弹性体的拉伸断面形貌与弹性体的网络结构完整性和力学性能具有良好的对应关系.     

热解碳包覆的碳纳米管复合二氧化锰薄膜超级电容器

通过化学气相沉积(CVD)的方法,在碳纳米管(CNT)薄膜及其连接处沉积热解碳(PC)来限制CNTs之间的滑移。通过扫描电镜(SEM)观察发现,热解碳(PC)的沉积使得CNT表面更加平整,且表面的孔洞更加均匀。通过应力应变及亲疏水性测试发现,CNT/PC复合薄膜的拉伸强度增加了200%,水与薄膜的静态接触角由123°减小到78°。其后通过电化学沉积的方法,制备得到CNT/PC/MnO2薄膜电极材料,通过电化学测试得知,在1 mA/cm^2的电流下单电极的比电容为326 mF/cm^2,可以稳定循环10000圈,电容的保持率稳定在100%左右。     

TPU增韧MABS的研究

利用双螺杆挤出机制备聚氨酯和甲基丙烯酸甲酯—丙烯腈-丁二烯-苯乙烯树脂熔融共混物(合金)。研究TPU的类型以及含量对TPU/MABS合金的透光率、力学性能和缺口冲击强度影响。结果表明:TPU/MABS合金可以保持较好透明性,随TPU含量的增加,合金材料的拉伸强度和弯曲模量逐渐降低,但是合金材料的冲击强度得到明显提高。扫描电镜观察表明,随TPU含量的增加,TPU与MABS界面分离现象逐渐明显。同时发现聚醚型TPU与MABS相容性和增韧效果要优于聚酯型TPU。     

基于配位键交联的自修复弹性体的合成及表征

通过八甲基环四硅氧烷(D_4)的开环平衡反应合成了端氨基聚二甲基硅氧烷(APTPDMS),随后将APT-PDMS与二异氰酸酯反应生成预聚体,以2,6-二氨基吡啶(2,6-DAP)为扩链剂,合成得到有机硅弹性体(PDMS-PU),最后以Fe~(3+)进行配位交联,制备了一系列自修复有机硅弹性体(PDMS-PU/M)。通过核磁共振、红外和紫外-可见光谱、万能试验机、激光共聚焦显微镜分析表征了产物结构和材料的力学性能、自修复性能。结果表明:PDMS-PU/M具有优异的力学和自修复性能,拉伸强度可达1.96 MPa,自修复效率可达82.7%;通过控制Fe~(3+)的含量,改变交联密度,可以实现材料强度和柔性之间的调节。     

Thermal,mechanical and electroactive shape memory properties of polyurethane (PU)/poly (lactic acid) (PLA)/CNT nanocomposites

Polymer blend nanocomposites based on thermoplastic polyurethane (PU) elastomer, polylactide (PLA) and surface modified carbon nanotubes were prepared via simple melt mixing process and investigated for its mechanical, dynamic mechanical and electroactive shape memory properties. Chemical and structural characterization of the polymer blend nanocomposites were investigated by Fourier Transform infrared (FT-IR) and wide angle X-ray diffraction (WAXD). Loading of the surface modified carbon nanotube in the PU/PLA polymer blends resulted in the significant improvement on the mechanical properties such as tensile strength, when compared to the pure and pristine CNT loaded polymer blends. Dynamic mechanical analysis showed that the glass transition temperature (T_g) of the PU/PLA blend slightly increases on loading of pristine CNT and this effect is more pronounced on loading surface modified CNTs. Thermal and electrical properties of the polymer blend composites increases significantly on loading pristine or surface modified CNTs. Finally, shape memory studies of the PU/PLA/modified CNT composites exhibit a remarkable recoverability of its shape at lower applied dc voltages, when compared to pure or pristine CNT loaded system.     

In Situ Reduction of Graphene Oxide in Waterborne Polyurethane Matrix and the Healing Behavior of Nanocomposites by Multiple Ways

Smart polymers are advanced materials that continue to attract scientific community. In this work, self‐healing waterborne polyurethane/reduced graphene oxide (SHWPU/rGO) nanocomposites were prepared by in situ chemical reduction of graphene oxide in a waterborne polyurethane matrix. The chemical structure, morphology, thermal stability, mechanical property, and electrical conductivity of the SHWPU/rGO nanocomposites were characterized. The prepared SHWPU/rGO nanocomposites were further treated under heating, microwave radiating, and electrifying conditions to investigate their healing property. The results showed that chemical reduction of graphene oxide was achieved using hydrazine hydrate as a reducing agent and the rGO was well dispersed in the SHWPU matrix. The thermal stability and mechanical properties of SHWPU/rGO nanocomposites were significantly increased. The SHWPU/rGO nanocomposites can be healed via different methods including heating, microwave radiating, and electrifying. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 202–209     

Preparation and properties of natural rubber composites reinforced with pretreated carbon nanotubes

In order to achieve dramatic improvements in the performance of rubber materials, the development of carbon nanotube (CNT)‐reinforced rubber composites was attempted. The CNT/natural rubber (NR) nanocomposite was prepared through solvent mixing on the basis of pretreatment of CNTs. Thermal properties, vulcanization characteristics, and physical and mechanical properties of the CNT/NR nanocomposites were characterized in contrast to the carbon black (CB)/NR composite. Through the addition of the CNTs treated using acid bath followed by ball milling with HRH (hydrated silica, resorcinol, and hexamethylene tetramine) bonding systems, the crystallization melting peak in differential scanning calorimetry (DSC) curves of NR weakened and the curing rate of NR slightly decreased. Meanwhile, the over‐curing reversion of CNT/NR nanocomposites was alleviated. The dispersion of the treated CNTs in the rubber matrix and interfacial bonding between them were rather good. The mechanical properties of the CNT‐reinforced NR showed a considerable increase compared to the neat NR and traditional CB/NR composite. At the same time, the CNT/NR nanocomposites exhibited better rebound resilience and dynamic compression properties. The storage modulus of the CNT/NR nanocomposites greatly exceeds that of neat NR and CB/NR composites under all temperature regions. The thermal stability of NR was also obviously improved with the addition of the treated CNTs. Copyright © 2008 John Wiley & Sons, Ltd.     

Self assembled graphene/carbon nanotube/polystyrene hybrid nanocomposite by in situ microemulsion polymerization

Self-assembled graphene/carbon nanotube (CNT)/polystyrene hybrid nanocomposites were prepared by water-based in situ microemulsion polymerization. The resulting nanocomposites were used as filler in a host polystyrene matrix to form composite films. An admixture of the two types of carbon fillers provided better improvement in the thermal and mechanical properties compared to the neat polymer. The sheet resistance decreased progressively due to the formation of an extended conjugation network with the CNT bridging the gap between the graphene sheets coated with polymer nanoparticles. The details of the analysis are presented.     

A facile rheological approach for the evaluation of “super toughness point” of compatibilized HDPE / MWCNT nanocomposites

Fast and efficient determination of the optimal mechanical property of a polymer/CNT nanocomposite is crucial to develop polymer conductive nanocomposites. This work establishes a rheological approach to evaluate the super-toughness point of compatibilized high density polyethylene (HDPE)/multi-walled carbon nanotube (MWCNT) nanocomposites. Results illustrate that three types of HDPE/MWCNT nanocomposites exhibit obvious gel plateaus in the dynamic rheological curves and the gel points of nanocomposites with compatibilizer shift to the low MWCNTs loading. The super-toughness points of HDPE/MWCNT nanocomposites with compatibilizers show the correspondence with the gel points acquired from the rheological data, indicating that dynamic rheology is an effective way to determine the super-toughness points of HDPE/MWCNT nanocomposites with compatibilizers. Furthermore, unique network structure at the gel points is directly observed and the new mechanism of toughness is proposed. This study provides new insights for effective control of the structures and properties of polymer/CNT nanocomposites.     

Microstructural design for enhanced mechanical property and shape memory behavior of polyurethane nanocomposites: Role of carbon nanotube,montmorillonite, and their hybrid fillers

The recent rapid development of technology has demanded smart materials with tailoring a bridge between macro properties and sophisticated micro and nano characteristic. Principally, shape memory polymers (SMPs) will come to play as an indispensable part of numerous aspects of human activity. Nevertheless, the low mechanical strength and thermal conductivity of SMPs have primarily restricted their applications. To impart shape memory behaviour and mechanical properties, we fabricated a series of composites by a feasible and commercial melt-mixing method. Thus, a series of fast heat-actuated shape memory polymer composite with greatly enhanced stretch-ability, mechanical stiffness, dynamic-modulus, rheological qualities, recovery and fixity ratio was prepared by incorporating multi-walled carbon nanotubes (CNT), montmorillonite (MMT) and CNT:MMT hybrid into thermoplastic polyurethane (TPU). Noteworthy, CNT-based specimens exhibited superior mechanical properties than those of MMT-based samples, and interestingly, the hybrid composites featured a synergistic effect due to the sacrificial role of MMT nanoplatelets for adjusting the dispersion of CNT nanotubes. Microstructural observations indicated that the crystallization percentages of the composites were generally higher than that of pristine TPU; therefore, the shape-memory performance of the specimens improved notably in the case of the hybrid composites owing to creating more interfacial zone with CNT:MMT nanoparticles as compared to other simple composites. This study proved that the simultaneous incorporation of CNT and MMT nanoparticles not only granted outstanding mechanical properties, but also improved the overall shape memory behaviour of the composites by systematical localization of the nanoparticles without any functionalization or modification.     

Experimental and modeling investigation of shape memory behavior of polyurethane/carbon nanotube nanocomposite

In the current study, mechanical, thermal, thermo‐mechanical, and shape memory behavior of polyurethane/carbon nanotube nanocomposites were investigated, and also a modified Halpin‐Tsai equation was used for the first time to model shape recovery stress of these smart composites. Results showed that strength enhanced with the addition of MWCNTs and improved to a maximum value of 130% for PU‐1wt%CNTs. SEM micrographs were also used to prove the presence of agglomerates at higher CNT contents. By investigating thermogravimetry curves, it was concluded that the incorporation of carbon nanotubes transferred thermal degradation to a higher temperature. Storage modulus improved for nanocomposite samples which showed the reinforcing effect of CNTs on polyurethane. Memory behavior showed that recovery stress was increased for PU‐CNTs samples to a maximum value of 100% and not any harmful effect on shape recoveries observed. Finally, modified Halpin‐Tsai equation was obtained with the correction factor of K = exp(−1.79‐152V_f).     

Effect of modified carbon nanotube on physical properties of thermotropic liquid crystal polyester nanocomposites

Polymer nanocomposites based on a very small quantity of carbon nanotube (CNT) and thermotropic liquid crystal polymer (TLCP) were prepared by simple melt blending using a twin-screw extruder. Morphological observations revealed that modified CNT was uniformly dispersed in the TLCP matrix and increased interfacial adhesion between the nanotubes and the polymer matrix. The enhancement of the storage and loss moduli of the TLCP nanocomposites with the introduction of CNT was more pronounced at low frequency region, and non-terminal behavior observed in the TLCP nanocomposites resulted from the nanotube-nanotube and polymer-nanotubes interactions. There is significant dependence of the mechanical, rheological, and thermal properties of the TLCP nanocomposites on the uniform dispersion of CNT and the interfacial adhesion between CNT and TLCP matrix, and their synergistic effect was more effective at low CNT content than at high CNT content. The key to improve the overall properties of the TLCP nanocomposites depends on the optimization of the unique geometry and dispersion state of CNT and the interfacial interactions in the TLCP nanocomposites during melt processing. This study demonstrate that a very small quantity of CNT substantially improved thermal stability and mechanical properties of the TLCP nanocomposites, providing a design guide of CNT-filled TLCP composites with as great potential for industrial use.     

Strong,Supertough and Self-Healing Biomimetic Layered Nanocomposites Enabled by Reversible Interfacial Polymer Chain Sliding

Despite the remarkable progress in ultrastrong mechanical laminate materials, the simultaneous achievement of toughness, stretchability and self-healing properties in biomimetic layered nanocomposites remains a great challenge due to the intrinsic limitations of their hard essences and lack of effective stress transfer at the organic-inorganic fragile boundary. Here, an ultratough nanocomposite laminate is prepared by constructing chain-sliding cross-linking at the interface between sulfonated graphene nanosheets and polyurethane layers based on the ring molecules sliding on the linear polymer chains to release stresses. Unlike traditional supramolecular bonding toughening with limited sliding spacing, our strategy enables interfacial molecular chains reversible slippage when the inorganic nanosheets bear stretching force, providing sufficient interlayer spatial distance for relative sliding to dissipate more energy. The resulting laminates exhibit strong strength (22.33 MPa), supertoughness (219.08 MJ m⁻³), ultrahigh stretchability (>1900 %) and self-healing ability (99.7 %), which far surpass most of reported synthetic and natural laminate materials. Moreover, the fabricated proof-of-concept electronic skin shows excellent flexibility, sensitivity and healability for human physiological signals monitoring. This strategy breaks through the challenge that traditional layered nanocomposites are intrinsically stiff and opens up the functional application of layered nanocomposites in flexible devices.     

Poly(vinylidene fluoride)/polycarbonate blend-based nanocomposites with enhanced rigidity — Selective localization of carbon nanofillers and organoclay

Carbon nanotube (CNT), graphene nanoplatelet (GnP) and organo-montmorillonite (15 A) individually and simultaneously served as reinforcing fillers to prepare poly (vinylidene fluoride) (PVDF)/polycarbonate (PC) blend-based multicomponent nanocomposites. Scanning electron microscopy and transmission electron microscopy results confirmed the selective localization of individual and hybrid fillers within the PC domains. Some 15 A was located at the interface of PVDF/PC phases to modify the blend morphology. Addition of CNT led to the development of a quasi co-continuous PVDF-PC morphology. Differential scanning calorimetry results showed that 15 A, not CNT/GnP, facilitated PVDF crystallization in the composites. Among the fillers, 15 A alone induced β-form PVDF crystals, as revealed by the X-ray diffraction results, and consequently caused the complex crystallization and melting of PVDF. The rigidity (Young's and flexural moduli) of the PVDF/PC blend increased after the formation of various blend-based nanocomposites. The hybrid filler of CNT/15 A increased the Young's modulus by approximately 90% compared with that of the blend. Rheological property measurements confirmed the formation of a pseudo-network structure in the composites. Adding CNT increased the complex viscosity of the samples to a higher extent than did adding GnP, and the viscosity further increased with the co-existence of carbon nanofiller(s) and 15 A.