Electrical,rheological and electromagnetic interference shielding properties of thermoplastic polyurethane/carbon nanotube composites

Electrically conducting rubbery composites based on thermoplastic polyurethane (TPU) and carbon nanotubes (CNTs) were prepared through melt blending using a torque rheometer equipped with a mixing chamber. The electrical conductivity, morphology, rheological properties and electromagnetic interference shielding effectiveness (EMI SE) of the TPU/CNT composites were evaluated and also compared with those of carbon black (CB)‐filled TPU composites prepared under the same processing conditions. For both polymer systems, the insulator–conductor transition was very sharp and the electrical percolation threshold at room temperature was at CNT and CB contents of about 1.0 and 1.7 wt%, respectively. The EMI SE over the X‐band frequency range (8–12 GHz) for TPU/CNT and TPU/CB composites was investigated as a function of filler content. EMI SE and electrical conductivity increased with increasing amount of conductive filler, due to the formation of conductive pathways in the TPU matrix. TPU/CNT composites displayed higher electrical conductivity and EMI SE than TPU/CB composites with similar conductive filler content. EMI SE values found for TPU/CNT and TPU/CB composites containing 10 and 15 wt% conductive fillers, respectively, were in the range ?22 to ?20 dB, indicating that these composites are promising candidates for shielding applications. © 2013 Society of Chemical Industry     

无卤阻燃PF/EP/GF布复合材料的固化性能和阻燃性能

采用环氧树脂(EP)作固化剂,2,4,6-三(二甲胺基甲基)-苯酚(DMP30)作固化促进剂改善酚醛树脂(PF)的固化性能,以氢氧化铝和有机磷阻燃剂协同改性其阻燃性能,将其涂覆于玻璃纤维(GF)布上,压制成无卤阻燃PF/EP/GF布复合材料.用傅立叶变换红外光谱(FTIR)仪和差示扫描量热(DSC)仪对无卤阻燃PF/EP/GF布复合材料的固化反应机理、固化反应动力学进行了分析研究,并测试了该复合材料的阻燃性能.结果表明,无卤阻燃PF/EP/GF布复合材料的固化反应表观活化能Ea=75.7 kJ/mol、反应级数n=0.91,起始固化温度、固化峰顶温度、固化终止温度分别为108.6、133.2、152.9℃;当氢氧化铝质量分数为14%、DMP30质量分数为1%、有机磷阻燃剂质量分数为4.8%时,无卤阻燃PF/EP/GF布复合材料的固化性能、阻燃性能均达到较佳状态.     

Hybrid composites of ABS with carbonaceous fillers for electromagnetic shielding applications

This work evaluates the influence of two types of carbonaceous fillers, carbon black (CB) and carbon nanotubes (CNTs), on the electrical, electromagnetic, and rheological properties of composites based on poly(acrylonitrile‐co‐butadiene‐co‐styrene) (ABS) prepared by the melt mixing. Electrical conductivity, electromagnetic shielding efficiency (EMI SE) in the X‐band frequency range (8–12.4 GHz), and melt flow index (MFI) results showed that ABS/CNT composites exhibit higher electrical conductivity and EMI SE, but lower MFI when compared to ABS/CB composites. The electrical conductivity of the binary composites showed an increase of around 16 orders of magnitude, when compared to neat ABS, for both fillers. Binary composites with 5 and 15 wt % of filler showed an EMI SE of, respectively, ?44 and ?83 dB for ABS/CNT, and ?9 and ?34 dB for ABS/CB. MFI for binary composites with 5 wt % were 15.45 and 0.55 g/10 min for CB and CNT, respectively. Hybrid composites ABS/CNT.CB with 3 wt % total filler and fraction 50:50 and 75:25 showed good correlation between EMI SE and MFI. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46546.     

The influence of the transparent layer thickness on the absorption capacity of epoxy/carbon nanotube buckypaper at X-band

Carbon nanotube films (BPs) as EMI shielding materials can be applied in electronic and communication devices due to their high electrical conductivity. Sandwich structures can offer excellent shielding effectiveness by introducing a wave-transmitting layer between conductive films. However, the optimization of the structure demands a deep investigation and plays a crucial role in the final shielding properties of the composites. In this work, BPs are incorporated into epoxy substrates with variable thicknesses (1–6 mm) to fabricate epoxy/BP sandwich structures. The morphology of the CNT films is analyzed by SEM, and the electrical conductivity of all prepared samples is measured by 4-point method. The electromagnetic tests are carried out in the X-band (8.2–12.4 GHz) through the scattering parameters. SEM images reveal a porous structure without visible agglomeration. The electrical conductivity of the BP reaches up to 996 S/m, whereas the values for epoxy/BP composites varies in the range of 8.51–3.13 S/m (1 to 3 mm). BP total shielding efficiency (SE_T) is approximately 14 dB along the X-band spectrum, with similar contributions of reflection and absorption losses. While, the composites show mainly absorbing behavior, especially in the thicker samples, with more significant SE_T values (23.4 dB–6 mm).     

RTM制备玻璃纤维增强环氧树脂复合材料的力学性能分析

以环氧树脂为基体,短切玻璃纤维和玻璃纤维布为增强材料,通过RTM工艺制备了玻璃纤维增强环氧树脂(GF/EP)复合材料,并研究了RTM工艺制备玻璃纤维布增强环氧树脂(L-GF/EP)和短切玻璃纤维增强环氧树脂(S-GF/EP)复合材料的拉伸和弯曲性能,分析了开孔对两种复合材料拉伸性能的影响。结果表明:在拉伸过程中,开孔试样因孔边产生的应力集中,导致其拉伸强度与无孔试样相比下降了30%左右;玻纤铺层类型的不同对复合材料的力学性能具有显著影响;L-GF/EP复合材料内部结构完整,在载荷作用下,复合材料的弯曲断裂呈现一定的假塑性断裂模式,达到弯曲极限挠度值后,出现一定程度的回弹现象,其力学性能优于S-GF/EP复合材料。     

连续玻纤增强聚丙烯混纤纱织物层压成型工艺研究

采用两种不同形式的混纤纱机织物为原料,利用层压成型的方法制备了连续玻璃纤维(GF)增强的聚丙烯(PP)板材。研究了层压温度、压力、保压时间和混纤纱机织物形式对层压板材的弯曲性能和层间剪切强度(ILSS)的影响。结果表明,当层压温度为230℃,层压压力为8.5 MPa,保压时间为30 min,降温过程冷却速度为0.5℃/min时,层压板材的力学性能最佳。弯曲强度和模量分别达到352.58 MPa、23.09 GPa,ILSS达到27.37 MPa。此时,纤维含量和空隙率分别为72.25%、2.03%。在最优工艺条件下制备的两种不同织物形式层压板材弯曲强度和弯曲模量以及ILSS:2/2斜纹织物平纹织物。两种织物层压板材的空隙率:2/2斜纹织物平纹织物。     

The effect of glass-resin interface strength on the impact strength of fiber reinforced plastics

The effect of glass-resin interface strength on the impact energy of glass fabric (style 181) reinforced epoxy and polyester laminates has been determined. The interface strength was altered by surface treatment of the fabrics with silane coupling agents and with a silicone fluid mold release and the interlaminar shear strength was determined as a means to evaluate the interface strength. An instrumented Charpy impact test was used on unnotehed specimens and thus both initiation and propagation energies could be determined as well as dynamic strength. It was found that the initiation energy for both polyester and epoxy laminates increased with increasing interlaminar shear strength, The propagation energy and thus the total energy for polyester laminates displays a minimum at a critical value of interlaminar shear strength (ILSS). Below this critical value, the total impact energy increases with decreasing shear strength and the dominant energy absorption mode appears to be delamination. Above the critical value, the impact energy increases with increasing values of ILSS and the fracture mode is predominantly one of fiber failure. In all cases, even with mold release applied, the shear strength of epoxy laminates was above this critical value and-thus the total impact energy increases with Increasing values of ILSS. The maximum energy absorbed for the epoxy laminate and the polyester laminate is nearly identical. However, the maximum for the epoxy laminate occurs when the shear strength is maximized while for the polyester laminate the shear strength must be minimized. For the polyester laminate when delamination is predominant, it was found that the glass surface treatment affects the amount of delamination as opposed to the specific value of delamination fracture work.     

Effects of carbon fiber modification with multiwall CNT on the electrical conductivity and EMI shielding effectiveness of polycarbonate/carbon fiber/CNT composites

The effect of carbon fiber (CF) modification with multiwall carbon nanotube (CNT) on the electrical, mechanical, and rheological properties of the polycarbonate (PC)/CF/CNT composite was investigated. The CF and multiwall CNT (MWCNT) were treated with sulfuric acid and nitric acid (3:1 wt %) mixture, to modify the CF with the CNT. For the PC with acid-treated CNT (a-CNT) modified acid-treated CF (a-CF) (PC/a-CF/a-CNT) composite, the electrical conductivity, and the electromagnetic interference shielding effectiveness (EMI SE) showed the highest values, compared with those of the PC/a-CF and PC/a-CF/CNT composites. The EMI SE of the PC/a-CF (10 wt %)/a-CNT (0.5 wt %) composite was found to be 26 (dB at the frequency of 10.0 GHz, and the EMI SE was increased by 91.2%, compared to that of the PC/a-CF composite at the same amount of total filler content. Among the composites studied in this work, the PC/a-CF/a-CNT composite also showed the highest values of relative permittivity (ε_r) and dielectric loss factor. The above results suggest that the CF modification with the a-CNT significantly affected the electrical conductivity and EMI SE of the composite, and the hybrid fillers of the a-CNT and a-CF resulted in good electrical pathways in the PC/a-CF/a-CNT composite. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47302.     

The influence of single-walled carbon nanotube structure on the electromagnetic interference shielding efficiency of its epoxy composites

Three types of single-walled carbon nanotube (SWCNT) homogeneous epoxy composites with different SWCNT loadings (0.01-15%) have been evaluated for electromagnetic interference (EMI) shielding effectiveness (SE) in the X-band range (8.2-12.4 GHz). The effect of the SWCNT structure including both the SWCNT aspect ratio and wall integrity, on the EMI SE have been studied and are found to correlate well with the conductivity and percolation results for these composites. The composites show very low conductivity thresholds (e.g. 0.062%). A 20-30 dB EMI SE has been obtained in the X-band range for 15% SWCNT loading, indicating that the composites can be used as effective lightweight EMI shielding materials. Furthermore, their EMI performance to radio frequencies is found to correspond well with their permittivity data.     

Flexible poly(styrene-b-(ethylene-co-butylene)-b-styrene) nanocomposites for electromagnetic interference shielding

In this report, multiwalled carbon nanotubes (CNT) embedded poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS) microspheres (CNT/SEBS) were prepared by solvent evaporation method. Reduced graphene oxide (rGO) nanosheets were used to cover the surface of CNT/SEBS microspheres. The CNT/SEBS/rGO nanocomposites with special segregated conductive network were fabricated by hot pressing these as-prepared complex microspheres. The morphology, electrical percolation threshold, electrical conductivity, and electromagnetic interference (EMI) shielding effectiveness (SE) of CNT/SEBS/rGO composites were characterized. The shielding mechanisms were discussed in detail. Analysis of electrical conductive performance shows that the electrical percolation threshold of rGO is 0.22 vol %. Results of EMI shielding test confirmed the synergistic effect between CNT and rGO. The EMI SE of the composite filled by 2.1 vol % CNT and 3.35 vol % rGO can achieve 26 dB in 8.2− 12.4 GHz (X band), which exceeds the basic requirement for commercial application (20 dB). Its reflectance coefficient (19–41%) indicates that the most part of incident electromagnetic (EM) wave energy is attenuated through absorption mechanism. This kind of absorptive EMI shielding material can be applied without serious secondary EM radiation pollution problems. The effects of filler content, molding temperature on EMI SE, and shielding mechanism were also investigated. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48542.     

Improving delamination resistance of carbon fiber reinforced polymeric composite by interface engineering using carbonaceous nanofillers through electrophoretic deposition: An assessment at different in-service temperatures

In this article, modification of carbon fiber surface by carbon based nanofillers (multi-walled carbon nanotubes [CNT], carbon nanofibers, and multi-layered graphene) has been achieved by electrophoretic deposition technique to improve its interfacial bonding with epoxy matrix, with a target to improve the mechanical performance of carbon fiber reinforced polymer composites. Flexural and short beam shear properties of the composites were studied at extreme temperature conditions; in-situ cryo, room and elevated temperature (−196, 30, and 120°C respectively). Laminate reinforced with CNT grafted carbon fibers exhibited highest delamination resistance with maximum improvement in flexural strength as well as in inter-laminar shear strength (ILSS) among all the carbon fiber reinforced epoxy (CE) composites at all in-situ temperatures. CNT modified CE composite showed increment of 9% in flexural strength and 17.43% in ILSS when compared to that of unmodified CE composite at room temperature (30°C). Thermomechanical properties were investigated using dynamic mechanical analysis. Fractography was also carried out to study different modes of failure of the composites.     

铺层结构对EP/GF复合材料沉头螺栓连接失效的影响

以环氧树脂(EP)为基体,单层玻璃纤维(GF)布为增强体,利用真空辅助树脂传递模塑工艺制备了具有[0°]_(_(6s)),[45°/–45°]_(_(3s)),[0°/90°]_(_(3s)),[90°]_(_(6s))铺层结构的EP/GF复合材料层合板,通过拉伸失效实验研究了铺层结构对复合材料层合板沉头螺栓连接承载能力的影响,并进一步分析了4种铺层结构的沉头螺栓连接层合板在拉伸时的失效行为。结果表明,[45°/–45°]_(_(3s))与[0°/90°]_(_(3s))铺层结构的层合板均发生了承载失效,具有较高的螺栓连接承载能力,其中[0°/90°]_(3s)铺层结构的层合板最大拉伸载荷最高,为6.7 k N,[45°/–45°]_(3s)铺层结构的层合板具有最大的失效位移,为14.17 mm;[0°]_(6s)铺层结构的层合板发生了剪切开裂失效,其螺栓连接承载能力低于上述两种铺层结构;[90°]_(6s)铺层结构的层合板发生了净张力失效,其螺栓连接承载能力最低。     

Effect of processing conditions on physical properties of 3‐aminophenoxyphthalonitrile/epoxy laminates

To develop high performances of polymer composite laminates, differential scanning calorimetry and dynamic rheological analysis studies were conducted to show curing behaviors of 3‐aminophenoxyphthalonitrile/epoxy resin (3‐APN/EP) matrix and define cure parameters of manufacturing processes. Glass fiber reinforced 3‐APN/EP (GF/3‐APN/EP) composite laminates were successfully prepared through different processing conditions with three parameters such as pressures, temperatures, and time. Based on flexure tests, dynamic mechanical analysis, thermal gravimetric analysis, and scanning electron microscope, the complementary catalytic effect of the three processing parameters is investigated by studying mechanical behavior, thermomechanical behavior, thermal behavior, and fracture morphology of GF/3‐APN/EP laminates. The 50/50 GF/3‐APN/EP laminates showed a significant improvement in flexural strength, glass transition temperature (T_g), and thermal stability with favorable processing parameters. It was also found that the T_g and thermal stability were significantly improved by the postheated treatment method. The effect of manufacturing process provides a new and simple route for the polymer–matrix composites application, which indicates that the composites can be manufactured at low temperatures. But, they can be used in a high temperature environment. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39746.     

燃气流作用时间对玻璃钢层间剪切强度的影响

研究了不同燃气流作用时间对玻璃钢层间剪切强度的影响。研究结果表明:随着燃气流作用时间的延长,玻璃钢表面碳化失效层数呈增加趋势;未烧蚀部分复合材料层间剪切强度虽有降低,但是降低幅度不大,说明表面的玻璃布层碳化失效对深层复合材料层间剪切强度影响不大;烧蚀后复合材料断裂模式由韧性转变为脆性。该研究结果为玻璃钢在燃气流环境中的应用提供了重要的数据支撑。     

Improved Electromagnetic Interference Shielding Properties of MWCNT–PMMA Composites Using Layered Structures

Electromagnetic interference (EMI) shielding effectiveness (SE) of multi-walled carbon nanotubes–polymethyl methacrylate (MWCNT–PMMA) composites prepared by two different techniques was measured. EMI SE up to 40 dB in the frequency range 8.2–12.4 GHz (X-band) was achieved by stacking seven layers of 0.3-mm thick MWCNT–PMMA composite films compared with 30 dB achieved by stacking two layers of 1.1-mm thick MWCNT–PMMA bulk composite. The characteristic EMI SE graphs of the composites and the mechanism of shielding have been discussed. SE in this frequency range is found to be dominated by absorption. The mechanical properties (tensile, flexural strength and modulus) of the composites were found to be comparable or better than the pure polymer. The studies therefore show that the composite can be used as structurally strong EMI shielding material.     

Improving the interlaminar shear strength and thermal conductivity of carbon fiber/epoxy laminates by utilizing the graphene-coated carbon fiber

The poor interlaminar properties restrict the application of carbon fiber reinforced polymer (CFRP) composites. In this work, a novel method for fabricating a graded interface structure is developed to improve the through-thickness thermal conductivity of CFRP composites. High-strength graphene nano-plates (GnP) and phenolic resin (PF) were selected to deposit on the surface of carbon fiber to design a novel CF/Epoxy laminates, where a simultaneous improvement of interlaminar shear strength (ILSS) and through-thickness thermal conductivity was observed. With addition of 1 wt % of GnP-PF in CF, 37.04% increase of the ILSS, and 16.67% enhancement of thermal conductivity compared to the original CFRP. The mechanism for improvement of both ILSS and thermal conductivity was studied by scanning electron microscopy and nano-indentation, where a better interface formed by GnP-PF has been clearly observed. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47061.     

Enhanced interlaminar shear and impact performance of woven carbon/epoxy composites interleaved with needle punched high performance polyethylene fiber nonwoven

In this study, high-performance polyethylene (HPPE) fiber-based needle punched nonwovens were interleaved in cross-plied woven carbon fabric/epoxy composite laminates to enhance their interlaminar and impact properties. The placement of needle punched nonwoven interleaves exhibited considerable enhancement in interlaminar shear strength (ILSS), impact damage tolerance, and compression after impact (CAI) strength of laminates as evidenced by higher interlaminar strength, less absorbed energy, higher elastic energy, reduced damage degree, reduced out-of-plane deformation, higher load-bearing capacity, and higher residual compressive strength as compared to control sample. In particular, the composite laminate with placement of interleaves in alternating sequence between carbon plies resulted in 205.76% increase in ILSS and 129, 103 and 85% increase in CAI at 10, 25, and 40 J impact energy, respectively. Moreover, damaged surface area and out-of-plane deformation reduced to 38.75% and 62.5%, respectively for the same specimen impacted at 40 J energy. These results suggest that the HPPE fiber-based needle punched nonwoven interleaving can be adopted as a simple and low-cost approach compared with other interleaving techniques, to enhance the resistance to delamination, impact performance, and damage tolerance of traditional structural laminates.     

Interfacial microstructure and properties of carbon fiber-reinforced unsaturated polyester composites modified with carbon nanotubes

To improve the interfacial properties in carbon fiber (CF)-reinforced unsaturated polyester (UP) composites, we directly introduced functionalized carbon nanotubes dispersed in the fiber sizing onto the fiber surface. For comparing the influence of polymer type on sizing effect, two different polymers (UP MR13006 and water-soluble epoxy (EP)) were used to prepare sizing agent. Morphology and surface energy of CFs were examined by scanning electron microscopy and dynamic contact angle analysis test. Tensile strength was investigated in accordance with ASTM standards. Mechanical properties of the composites were investigated by interlaminar shear strength (ILSS) and impact toughness. Test results indicate that TS, ILSS, and impact toughness were enhanced simultaneously. For UP matrix, the sizing agent containing UP has better reinforcing and toughening effect than the sizing agent containing water-soluble EP.     

Resin modification on interlaminar shear property of carbon fiber/epoxy/nano‐CaCO3 hybrid composites

Epoxy resin was modified by adding a silane coupling agent/nano‐calcium carbonate master batch. Then, samples of binary carbon fiber/epoxy composites and ternary fiber/nano‐CaCO₃/epoxy were prepared by hot press process. The interlaminar shear strength (ILSS) of the carbon fiber/epoxy composites was investigated and the results indicate that introduction of the treated nano‐CaCO₃ enhances ILSS obviously. In particular, the addition of 4 wt% nano‐CaCO₃ leads to 36.6% increase in the ILSS for the composite. The fracture surfaces of the carbon fiber/epoxy composites and the mechanical properties of epoxy resin cast are examined and both of them are employed to explain the change of ILSS. The results show that the change of ILSS is primarily due to an increase of the epoxy matrix strength and an increase of the fiber/epoxy interface. The bifurcation of propagating cracks, stress transfer, and cavitation are deduced for the reasons of strengthening and toughening effect of nano‐CaCO₃ particles. POLYM. COMPOS., 38:2035–2042, 2017. © 2015 Society of Plastics Engineers