Role of the degree of acetalization on dynamic mechanical properties of polyvinyl butyral/carbon nanotube composites

In this work, polyvinyl butyral (PVB) nanocomposites reinforced with 0.1–1.0 wt % of pristine [carbon nanotube (CNT)] or oxidized (CNTO) multiwalled CNTs were synthesized via in situ polymerization. It was found that the presence of the reinforcement during the synthesis altered the degree of acetalization of PVB. Dynamic mechanical analyses showed that PVB nanocomposites containing 0.5 wt % of pristine CNT had the best adhesion factor, with increases of about 30% in the storage modulus. On the other hand, PVB/CNTO 1.0 wt % nanocomposites achieved the best reinforcement efficiency factor (“C” coefficient). It is concluded that the in situ polymerization improves dispersion and final properties of the nanocomposite only if the nanoparticles are able to form relevant interfacial interactions during the PVB synthesis. In addition, it was verified that the presence of CNT or CNTO altered the degree of acetalization of PVB, which strongly influences the final properties of the nanocomposites. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48146.     

Mechanical and thermal properties of hierarchical composites enhanced by pristine graphene and graphene oxide nanoinclusions

Epoxy resin nanocomposites incorporated with 0.5, 1, 2, and 4 wt % pristine graphene and modified graphene oxide (GO) nanoflakes were produced and used to fabricate carbon fiber‐reinforced and glass fiber‐reinforced composite panels via vacuum‐assisted resin transfer molding process. Mechanical and thermal properties of the composite panels—called hierarchical graphene composites—were determined according to ASTM standards. It was observed that the studied properties were improved consistently by increasing the amount of nanoinclusions. Particularly, in the presence of 4 wt % GO in the resin, tensile modulus, compressive strength, and flexural modulus of carbon fiber (glass fiber) composites were improved 15% (21%), 34% (84%), and 40% (68%), respectively. Likewise, with inclusion of 4 wt % pristine graphene in the resin, tensile modulus, compressive strength, and flexural modulus of carbon fiber (glass fiber) composites were improved 11% (7%), 30% (77%), and 34% (58%), respectively. Also, thermal conductivity of the carbon fiber (glass fiber) composites with 4% GO inclusion was improved 52% (89%). Similarly, thermal conductivity of the carbon fiber (glass fiber) composites with 4% pristine graphene inclusion was improved 45% (80%). The reported results indicate that both pristine graphene and modified GO nanoflakes are excellent options to enhance the mechanical and thermal properties of fiber‐reinforced polymeric composites and to make them viable replacement materials for metallic parts in different industries, such as wind energy, aerospace, marine, and automotive. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40826.     

Effect of crosslink density on thermal conductivity of epoxy/carbon nanotube nanocomposites

The effect of the polymeric crosslink density on the thermal conductivity of an epoxy nanocomposite was investigated by adding two different diamine‐functionalized multiwalled carbon nanotubes (diamine‐MWNTs) to the epoxy resin as co‐curing agents and conducting fillers. Tetramethylenediamine (TMDA)‐MWNTs resulted in an epoxy nanocomposite with a higher crosslink density than octamethylenediamine (OMDA)‐MWNTs. Interestingly, epoxy/TMDA‐MWNT nanocomposites under 1.5 wt % nanotube concentration, showed a higher thermal conductivity than an epoxy/OMDA‐MWNT nanocomposite with the same concentration of nanotubes. In contrast, for higher diamine‐MWNT concentrations (over 2.0 wt %), the thermal conductivity of the epoxy/OMDA‐MWNT nanocomposite was higher than that with TMDA‐MWNTs. We observed that for low MWNT concentrations, where a percolating network was not formed, a high crosslink density enhanced the thermal conductivity via phonon transport. However, for high MWNT concentrations, a high crosslink density hinders the formation of a percolating network and lowers the thermal conductivity. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44253.     

Multifunctional epoxy composites modified with a graphene nanoplatelet/carbon nanotube hybrid

Epoxies are a class of thermoset polymers which find use in high performance applications. However, epoxies are inherently brittle and are poor conductors of electricity, which limits their ability to be employed in functional applications. Carbon nanomaterials have attracted considerable attention as filler materials, due to their combination of outstanding properties. In the present work, an epoxy polymer was modified with a hybrid nanofiller, consisting of graphene nanoplatelets (GNPs) and carbon nanotubes (CNTs) at a mass ratio of 9:1, using three-roll milling. Addition of 1 wt% resulted in an increase of eight orders of magnitude in the electrical conductivity and a 182% increase in the fracture energy, G_IC, of the epoxy. CNTs contributed greatly in the reduction of the percolation threshold, which was 10 times lower than that of conventional GNP/epoxy composites, while the increase in toughness was entirely attributed to the GNPs, predominantly through the mechanism of crack deflection. The toughening contribution of the hybrid nanofiller was theoretically calculated using analytical modeling, which showed excellent agreement between the predicted and experimental values of G_IC.     

Preparation of biaxially oriented polyamide 6/polyketone/graphene oxide films with enhanced barrier and mechanical behaviors

In this study, biaxially oriented polyamide 6/polyketone/graphene oxide (PA6/PK/GO) films were prepared by melt blending then simultaneously biaxially stretched process, with the aim of obtaining high barrier properties films and improvements in their mechanical properties. The oxygen transmission rate of biaxially oriented PA6/PK/GO film significantly decreased with addition of polyketone and GO. It is surprising that the biaxially oriented process can excellently improve the barrier properties of biaxially oriented PA6/PK/GO film. For example, there was 94.7% OTR reduction of the film containing 20 wt% PK and 0.08 wt% GO compared with PA6 film at a stretching ratio of 3.3 × 3.3. It is due to more tortuous permeation path of oxygen molecule owing to molecular orientation during biaxially stretching, and higher relative crystallinity with addition of GO. The tensile strength of film was remarkablly improved by stretching orientation and increase GO concentration. However, the elongation at break of film was considerably reduced by increase of stretching ratio. Although addition of GO may slightly improve the elongation at break of film at low stretching ratio, there was dramatic decline of elongation at break with increasing the content of GO at a stretching ratio of 3.3 × 3.3.     

热塑性聚氨酯/石墨烯改性聚氨酯注浆材料的制备与性能研究

采用石墨烯、热塑性聚氨酯（TPU）复合改性聚氨酯注浆材料,并添加少量的粉煤灰、炉底渣及碱性激发剂制备一种低密度、高强度、快硬性的TPU/石墨烯改性聚氨酯注浆材料。借助聚氨酯弹性体材料密度测试仪、万能材料试验机、渗透系数测试仪、荧光显微镜对TPU/石墨烯改性聚氨酯注浆材料的密度、膨胀倍数、抗压强度、阻燃性能、渗透系数及微观形貌进行表征,深入分析了石墨烯和TPU的种类和含量对聚氨酯注浆材料基本物理性能、力学性能及微观结构的影响。结果表明,TPU/石墨烯改性聚氨酯注浆材料的密度为0.24~1.25 g/cm³,膨胀倍数最高可达38倍,抗压强度为15.0~43.8 MPa,相比普通聚氨酯注浆材料,改性聚氨酯注浆材料抗压强度提升1倍以上。酒精灯燃烧试验显示注浆材料无焰燃烧时间均小于20 s。石墨烯和TPU均可提高聚氨酯的强度和耐久性,改善TPU的微观形貌。TPU/石墨烯改性聚氨酯注浆材料表现出良好的强度、耐久性及弹性,是一种性能优异的注浆材料。     

Thermosetting polyurethane‐multiwalled carbon nanotube composites: Thermomechanical properties and nanoindentation

In this study, composites based on a thermoset polyurethane elastomer (PU) and multiwalled carbon nanotubes (MWCNT) in the case of a PU of high elastic modulus (>200 MPa) are analyzed for the first time. As‐grown and modified nanotubes with 4 wt % of oxygenated functions (MWCNT‐ox) were employed to compare their effect on composite properties and maxima mechanical properties (elastic modulus and tensile strength) were reached at 0.5 wt % of MWCNT‐ox. Furthermore, by examining the morphology using optical and electron microscopies better dispersion and interaction of the nanotube‐matrix was observed for this material. DMTA data supports the observation of an increase in the glass transition temperature of ～20°C in the nanocomposites compared with the thermoset PU, which is an important result because it shows extended reliability in extreme environments. Finally, nanoindentation tests allowed a comparison with the conventional mechanical tests by measuring the elastic modulus and hardness at the subsurface of PU and the nanocomposites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41207.     

The effect of temperature on fatigue strength of poly(ether-imide)/multiwalled carbon nanotube/carbon fibers composites for aeronautical application

This work concerns the fatigue behavior at three different temperature conditions (−40, 20, and 80°C) and the addition of multiwalled carbon nanotube (MWCNT) into a carbon-fiber reinforced poly(ether-imide) composite. The incorporation of MWCNT into the composite increased the tensile strength and Young's modulus by up 5 and 2%, respectively. At low temperature, the incorporation of the nanoparticles improved the fatigue strength of the laminates by 15%. The shear strength results obtained by interlaminar shear strength and compression shear test tests have shown an increase of about 16 and 58%, respectively, by the introduction of nanotubes into the laminates. Fractographic observations revealed that the surface of carbon nanotube laminate (PEI/MWCNT/CF) presented a ductile behavior, and differences in the fracture aspects of the material compared to the traditional PEI/CF laminate have been observed.     

Improving thermal conductivity and shear strength of carbon nanotubes/epoxy composites via thiol‐ene click reaction

This study investigates the effect of the thiol‐ene click reaction on thermal conductivity and shear strength of the epoxy composites reinforced by various silane‐functionalized hybrids of sulfhydryl‐grafted multi‐walled carbon nanotubes (SH‐MWCNTs) and vinyl‐grafted MWCNTs (CC‐MWCNTs). The results of Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, thermal gravimetric analysis (TGA), and transmission electron microscopy (TEM) show that the sulfhydryl groups and vinyl groups are successfully grafted onto the surface of MWCNTs, after treatment of MWCNT with triethoxyvinylsilane and 3‐mercaptopropyltrimethoxysilane, respectively. Scanning electron microscopy (SEM), HotDisk thermal constant analyzer (HotDisk), optical microscope, and differential scanning calorimetry (DSC) are used to characterize the resultant composites. It is demonstrated that the hybrid of 75 wt % SH‐MWCNTs and 25 wt % CC‐MWCNTs has better dispersion and stability in epoxy matrix, and shows a stronger synergistic effect in improving the thermal conductivity of epoxy composite via the thiol‐ene click reaction with 2,2′‐azobis(2‐methylpropionitrile) as thermal initiator. Furthermore, the tensile shear strength results of MWCNT/epoxy composites and the optical microscopy photographs of shear failure section indicate that the composite with the hybrid MWCNTs has higher shear strength than that with raw MWCNTs. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44579.     

Ductile/brittle PA6/PS system: Effect of carbon nanoplatelets-modified interface on performance

Addition of rigid PS to ductile PA6 can lead to higher toughness provided plastic deformation of PS is achieved. The current study deals with upgrading of this system by graphene, graphene oxide (GO), and GO with grafted polystyrene (GO-g-PS). Low amount of these carbon nanoplatelets can enhance performance of the PA/PS 90/10 system with the best-balanced properties achieved with GO-g-PS by unique combination of reinforcement with the favorable effect of the GO-g-PS-modified interface on plastic deformation of the PS phase causing higher impact resistance. Simultaneous linking of PA chains and hydrogen bonding causes “anchoring” of PS inclusions in the PA6 phase. This results in support of hydrostatic pressure evolution during loading and thus extensive yielding of PS. Another positive effect is reduction of pullout of in situ formed fibrous inclusions, which is different from rigid short-fiber composites. The study highlights high potential of GO modified with polymer chains to upgrade polymer systems via tailoring the interface.     

In situ polymerization of bio‐based thermosetting polyurethane/graphene oxide nanocomposites

Novel bio‐based polyurethane/graphene oxide (GO) nanocomposites have been successfully synthesized from biorenewable epoxidized soybean‐castor oil fatty acid‐based polyols with considerable improvement in mechanical and thermal properties. The GO was synthesized via a modified pressurized oxidation method, and was investigated using Raman spectra, AFM and XPS, respectively. The toughening mechanism of GO in the bio‐based polyurethane matrix was explored. The elongation at break and toughness of polyurethane were increased by 1.3 and 0.8 times with incorporation of 0.4 wt % GO, respectively. However, insignificant changes in both mechanical strength and modulus were observed by adding GO. The results from thermal analysis indicated that the GO acts as new secondary soft segments in the polyurethane which lead to a considerable decrease in the glass transition temperature and crosslink density. The SEM morphology of the fracture surface after tensile testing showed a considerable aggregation of graphene oxide at concentrations above 0.4 wt %. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41751.     

Preparation and properties of polyurethane/multiwalled carbon nanotube nanocomposites by a spray drying process

A spray drying approach has been used to prepare polyurethane/multiwalled carbon nanotube (PU/MWCNT) composites. By using this method, the MWCNTs can be dispersed homogeneously in the PU matrix in an attempt to improve the mechanical properties of the nanocomposites. The morphology of the resulting PU/MWCNT composites was investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). SEM and TEM observations illustrate that the MWCNTs are dispersed finely and uniformly in the PU matrix. X‐ray diffraction results indicate that the microphase separation structure of the PU is slightly affected by the presence of the MWCNTs. The mechanical properties such as tensile strength, tensile modulus, elongation at break, and hardness of the nanocomposites were studied. The electrical and the thermal conductivity of the nanocomposites were also evaluated. The results show that both the electrical and the thermal conductivity increase with the increase of MWCNT loading. In addition, the percolation threshold value of the PU composites is significantly reduced to about 5 wt % because of the high aspect ratio of carbon nanotubes and exclusive effect of latex particles of PU emulsion in dispersion. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Highly filled multilayer thermoplastic/graphene conducting composite structures with high strength and thermal stability for electromagnetic interference shielding applications

Polyvinyl chloride (PVC)/graphene and poly(methyl methacrylate) (PMMA)/graphene nanocomposites were made by solution casting technique with graphene weight fractions of 1, 5, 10, 15, and 20%. Multilayer structures of the composites were made by hot compression technique to study their electromagnetic interference shielding effectiveness (EMI SE). Tensile strength, hardness, and storage modulus of the nanocomposites were studied in relation with graphene weight fraction. There has been a substantial increase in the electrical conductivity and EMI SE of the composites with 15–20% filler loading. Differential thermal analysis of the composites shows improved thermal stability with an increase in graphene loading. PMMA/graphene composites have better thermal stability, whereas PVC/graphene composites have superior mechanical properties. About 2 mm thick multilayer structures of PMMA/graphene and PVC/graphene composites show a maximum EMI SE of 21 dB and 31 dB, respectively, in the X band at 20 wt % graphene loading. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47792.     

Graphene/polypropylene nanocomposites with improved thermal and mechanical properties

Small amount of large surface area graphene (G) is expected to significantly alter functional properties of polymers. The property enhancement is a function of degree of exfoliation and dispersion of G as well as its compatibility with base polymer. However, nonpolar nature of polyolefins such as polypropylene (PP) restricts homogeneous dispersion of G, leading to significant agglomeration and properties reduction. In this work, two compatibilizers, poly (ethylene-co-butyl acrylate) (EBA) (new compatibilizer) and PP-grafted-maleic anhydride (MA-PP) (conventional compatibilizer) were compared to enhance the dispersion efficacy of G in PP. The EBA-compatibilized nanocomposites exhibited 44% increase in the Young's modulus compared to 32% increment in MA-PP-compatibilized nanocomposites. Higher elongation at break for EBA-compatibilized nanocomposites is attributed to lower degree of crystallinity in these nanocomposites. On the other hand, EBA-compatibilized nanocomposites showed significantly improved thermal stability compared to MA-PP-compatibilized nanocomposites. The results indicate that EBA may act as a potential compatibilizer for G/PP nanocomposites.     

Effects of substitution for carbon black with graphene oxide or graphene on the morphology and performance of natural rubber/carbon black composites

In this study, nanosheets including graphene oxide (GO) and reduced graphene oxide (rGO), were incorporated into natural rubber (NR), to study the effects of substituting GO or rGO for carbon black (CB) on the structure and performance of NR/CB composites. The morphological observations revealed the dispersion of CB was improved by partially substituting nanosheets for CB. The improvements in static and dynamic mechanical properties were achieved at small substitution content of GO or rGO nanosheets. With substitution of rGO nanosheets, significant improvement in flex cracking resistance was achieved. NR/CB/rGO (NRG) composites has a much lower heat build‐up value compared with NR/CB/GO (NG) composites at a high load of nanosheets. However, both GO and rGO tended to aggregate at a high concentration, which led to the poor efficiency on enhancing the dynamic properties, or even deteriorate the performance of rubber composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41832.     

Mechanical and thermal transmission properties of carbon nanofiber‐dispersed carbon/phenolic multiscale composites

The present article reports the development and characterization of carbon nanofiber (CNF)‐incorporated carbon/phenolic multiscale composites. Vapor‐grown CNFs were dispersed homogeneously in to phenolic resin using an effective dispersion route, and carbon fabrics were subsequently impregnated with the CNF‐dispersed resin to develop carbon fiber/CNF/phenolic resin multiscale composites. Mechanical and thermal transmission properties of multiscale composites were characterized. Elastic modulus and thermal conductivity of neat carbon/phenolic and multiscale composites were predicted and compared with the experimental results. It was observed that incorporation of only 1.5 wt % CNF resulted in 10% improvement in Young's modulus, 12% increase in tensile strength, and 36% increase in thermal conductivity of carbon/phenolic composites. Fracture surface of composite samples revealed the formation of stronger fiber/matrix interface in case of multiscale composites than neat carbon/phenolic composites. Enhancement of above properties through CNF addition has been explained, and the difference between the predicted values and experimental results has been discussed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Flame‐retardant cyanate ester resin with suppressed toxic volatiles based on environmentally friendly halloysite nanotube/graphene oxide hybrid

Development of high‐performance thermosetting resins by adding environmentally friendly flame retardant to heat‐resistant resins without deteriorating their outstanding thermal stability is an important research direction. Here, a unique hybrid (GHNT) consisting of graphene oxide (GO) and halloysite nanotubes (HNT) was synthesized, and then a series of composites based on cyanate ester (CE) resin were fabricated. The effects of GHNT on the heat resistance, flame retardancy, and smoke suppression of GHNT/CE composites were intensively investigated. The GHNT/CE composite with 5.0 wt % GHNT not only has about 15.1 °C higher initial degradation temperature, but also shows 54.6% or 37.9% lower peak heat release rate or maximum smoke density than CE resin. These results clearly demonstrate that GHNT is not the simple combination of GO and HNT; instead, it obviously shows positive synergistic effects in simultaneously improving the flame retardancy and thermal resistance of CE resin. The improved flame retardancy could be attributed to condensed‐phase mechanisms, including increasing char yield, building a dense char layer, and free radical scavenging. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46587.     

Thermal and electrical conductivity of melt mixed polycarbonate hybrid composites co‐filled with multi‐walled carbon nanotubes and graphene nanoplatelets

In this work, we present thermoplastic nanocomposites of polycarbonate (PC) matrix with hybrid nanofillers system formed by a melt‐mixing approach. Various concentrations of multi‐walled carbon nanotubes (MWCNT) and graphene nanoplatelets (GnP) were mixed in to PC and the melt was homogenized. The nanocomposites were compression molded and characterized by different techniques. Torque dependence on the nanofiller composition increased with the presence of carbon nanotubes. The synergy of carbon nanotubes and GnP showed exponential increase of thermal conductivity, which was compared to logarithmic increase for nanocomposite with no MWCNT. Decrease of Shore A hardness at elevated loads present for all investigated nanocomposites was correlated with the expected low homogeneity caused by a low shear during melt‐mixing. Mathematical model was used to calculate elastic modulus from Shore A tests results. Vicat softening temperature (VST) showed opposite pattern for hybrid nanocomposites and for PC‐MWCNT increasing in the latter case. Electrical conductivity boost was explained by the collective effect of high nanofiller loads and synergy of MWCNT and GnP. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42536.     

Morphological and physical properties of a thermoplastic polyurethane reinforced with functionalized graphene sheet

BACKGROUND: Functionalized graphene sheet (FGS) was recently introduced as a new nano‐sized conductive filler, but little work has yet examined the possibility of using FGS as a nanofiller in the preparation of polymer nanocomposites. In particular, there are currently no published papers that evaluate polyurethane/FGS nanocomposites. The purpose of this study was to prepare a polyurethane/FGS nanocomposite and examine the morphological and physical properties of the material. RESULTS: A cast nanocomposite film was prepared from a mixture of thermoplastic polyurethane (TPU) solution and FGS suspended in methyl ethyl ketone. The FGS dispersed on the nanoscale throughout the TPU matrix and effectively enhanced the conductivity. A nanocomposite containing 2 parts of FGS per 100 parts of TPU had an electrical conductivity of 10^?4 S cm^?1, a 10⁷ times increase over that of pristine TPU. The dynamic mechanical properties showed that the FGS efficiently reinforced the TPU matrix, particularly in the temperature region above the soft segment melt. CONCLUSION: Our results show that FGS has a high affinity for TPU, and it could therefore be used effectively in the preparation of TPU/FGS nanocomposites without any further chemical surface treatment. This indicates that FGS is an effective and convenient new material that could be used for the modification of polyurethane. It could also be used in place of other nano‐sized conductive fillers, such as carbon nanotubes. Copyright © 2009 Society of Chemical Industry     

Synthesis and characterization of multiwall carbon nanotube/waterborne polyurethane nanocomposites

The preparation of thermoplastic nanocomposites of waterborne polyurethane (WBPU) and multiwall carbon nanotubes (MWCNTs) via an in situ polymerization approach is presented. The effects of the presence and content of MWCNTs on the morphology and thermal, mechanical and electrical properties of the nanocomposites were investigated. Carbon nanotubes were modified with amide groups in order to enhance their chemical affinity towards WBPU. Thermogravimetric studies show enhanced thermal stability of the nanocomposites. Scanning and transmission electronic microscopy images prove that functionalized carbon nanotubes can be effectively dispersed in WBPU matrix. Mechanical properties reveal that Young's modulus and tensile strength tend to increase when appropriate amounts of MWCNTs are loaded due to the reinforcing effect of the functionalized carbon nanotubes. Thermal properties show an increase in the glass transition temperature and storage modulus with an increase in MWCNT content. X‐ray diffraction reveals better crystallization of the WBPU in the presence of MWCNTs. The WBPU/MWCNT nanocomposite film containing 1 wt% of MWCNTs exhibits a conductivity nearly five orders of magnitude higher than that of WBPU film. © 2017 Society of Chemical Industry