Curing behavior and physical properties of epoxy nanocomposites comprising amine‐functionalized carbon nanofillers

Carbon nanofillers like nanotubes and nanofibers have been used to reinforce various epoxy systems. The incorporation of carbon nanofillers into a thermosetting epoxy system enhanced the thermal and mechanical properties of the epoxy system. The best performance of an epoxy nanocomposite system with carbon nanofillers would be resulted from the homogeneous dispersion of the nanofillers and strong interfacial adhesion between the epoxy matrix and the nanofillers. Therefore, amine‐functionalization of carbon nanofibers (CNFs) and multiwalled carbon nanotubes (MWNTs) was carried out via treating them with 4‐aminobenzoic acid in polyphosphoric acid. FTIR spectroscopy, XPS, TGA, and FE‐SEM analyses confirmed that the functionalization was successful. Curing behavior and thermo‐physical properties of the nanocomposites comprising the pristine or functionalized carbon nanofillers were investigated and compared with each other. Fractured surfaces of the nanocomposites were investigated by FE‐SEM. The functionalized MWNTs induced stronger interfacial adhesion than the functionalized CNFs and resulted in considerable improvement in the physical properties of the epoxy nanocomposites. POLYM. COMPOS., 31:1449–1456, 2010. © 2009 Society of Plastics Engineers     

Electrical conductivity and transparency of polymer hybrid nanocomposites based on poly(trimethylene terephthalate) containing single walled carbon nanotubes and expanded graphite

Single‐walled carbon nanotubes (SWCNT)/expanded graphite (EG)/poly(trimethylene terephthalate) (PTT) hybrid nanocomposites were prepared via in situ polymerization. Raman spectroscopy and scanning electron microscopy (SEM) were employed to determine both, purity and morphology of the nanofillers and the dispersion of nanotubes and nanosheets. The electrical and optical properties of thin polymer films based on both “single” nanocomposites and hybrid nanocomposites were studied. For PTT/SWCNT nanocomposites, results confirmed that films optical transmittance decreases as the concentration of SWCNT increases, attaining almost no optical transmittance for 0.3 wt % of nanofiller. Conversely, the electrical conductivity of nanocomposites was found to increase by increasing the nanofiller amount and the σ_dc values indicate that percolation occurs at a very low SWCNT content (around 0.05 wt %). In the case of PTT/SWCNT + EG nanocomposites, when the content of SWCNT is 0.05%, the hybrid system presents lower conductivity than that corresponding to the “single” nanocomposite. The incorporation of additional EG to the PTT/SWCNT nanocomposite has a small effect on the electrical conductivity but inhibits the transparency of the system. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44370.     

Synthesis and characterization of nanocomposites of thermoplastic polyurethane with both graphene and graphene nanoribbon fillers

Thermoplastic polyurethane (TPU) nanocomposites containing graphene and graphene nanoribbons were obtained by polymerizing 1,4-butanediol with two diisocyanates (namely, 1,6-hexane diisocyanate or isophorone diisocyanate), in which the nanofillers were previously dispersed. Raman spectroscopy and Transmission Electron Microscopy demonstrated the formation of few-layer graphene and graphene nanoribbons dispersed in the monomers. At variance to the methods commonly reported in literature, that used in this work consists of the direct exfoliation of graphite without any chemical manipulation. Apart from the obvious cost and ease advantages, the so-obtained graphene does not contain any carboxy or alkoxy groups formed during the exfoliation process, which, at variance, are typically present in the most commonly reported methods. This finding paves the way toward the large-scale production of graphene and its nanoribbons, which are considered even more interesting than graphene itself for many potential applications. The obtained nanocomposites show a peculiar thermal and rheological behavior due to the presence of the nanofillers and to their reinforcing or plasticizing effect exerted on the TPU matrices.     

蒙脱土/碳纳米管多维增强的聚乙烯复合材料的制备

引言聚烯烃是国民生活和现代国防不可或缺的基础原材料,但与ABS、PC等工程塑料相比,其刚性不足,低温脆性也较明显,因此很难作为结构材料使用。纳米技术的出现为聚烯烃材料性能的提高提供了广阔的空间[1],其中,纳米复合材料中存在纳米尺寸效应、超大的比表面积以及很强的界面相互作用,具有比强度高、可设计性强、抗疲劳性好等优点,因此,纳米复合聚乙烯中含少量纳米材料便能极大增强材料本身的性能,同时聚合物中纳米材料的低含量也大大减少了无机载体在聚合物中的灰分,有利于聚合物材料高性能的保持,这引起了研究工作者的广泛关注。     

Investigation of electrical,mechanical, and thermal properties of functionalized multiwalled carbon nanotubes‐reduced graphene Oxide/PMMA hybrid nanocomposites

Electrical, mechanical, and thermal properties of the poly(methyl methacrylate) (PMMA) composites containing functionalized multiwalled carbon nanotubes (f‐MWCNTs) and reduced graphene oxide (rGO) hybrid nanofillers have been investigated. The observed electrical percolation threshold of FHC is 0.8 wt% with maximum conductivity of 1.21 × 10^?3 S/cm at 4 wt% of f‐MWCNTs. The electrical transport mechanism and magneto resistance studied of hybrid composites have also been investigated. Progressive addition of f‐MWCNTs in rGO/PMMA composite results increase in mechanical (tensile strength and Young's modulus) and thermal (thermal stability) properties of f‐MWCNTs‐rGO/PMMA hybrid nanocomposites (FHC). The increased mechanical properties are due to the efficient load transfer from PMMA matrix to f‐MWCNTs and rGO through better chemical interaction. The strong interaction between PMMA and f‐MWCNTs‐rGO in FHC is the main cause for improved thermal stability. POLYM. ENG. SCI., 59:1075–1083, 2019. © 2019 Society of Plastics Engineers     

Microwave responsive epoxy nanocomposites reinforced by carbon nanomaterials of different dimensions

This study fabricated nanocomposites consisting of epoxy‐based shape memory polymer (ESMP) matrix and carbon nanofillers. The nanofillers include zero‐dimensional carbon black, one‐dimensional multiwalled carbon nanotubes, two‐dimensional (2D) graphene nanoplatelets, and three‐dimensional (3D) functionalized graphene sheets, which are all efficient microwave‐absorbing materials that can transform microwaves into heat energy. As a result, the temperatures of the nanocomposites increased more rapidly than pristine ESMP in microwaves. The functionalized graphene sheets were found to transform the microwaves into heat more efficiently than the other nanofillers. Possible microwave propagation paths in the nanocomposites were proposed. Moreover, the nanocomposites displayed significantly higher mechanical strengths than pristine ESMP. The low cost and strong nanocomposites with fast microwave responses may be applied as actuators or deployable devices in medical treatments. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45676.     

New polyurea MWCNTs nanocomposite films with enhanced mechanical properties

Polyurea nanocomposites represent a promising option in the development of advanced materials for applications that require high mechanical resistance. This article describes an optimized synthetic route for obtaining polyurea nanocomposites with enhanced mechanical properties by employing epoxy‐functionalized multiwalled carbon nanotubes (MWCNTs) as reinforcing agent. The experimental measurements revealed that these functionalized nanofillers have a positive effect on the properties of the composite only until they reach a certain concentration; therefore, the optimal composition was reported (the samples containing 0.2 weight % functionalized MWCNTs). The functionalization of the MWCNTs was confirmed through RAMAN, X‐ray photoelectron spectroscopy, scanning electron microscopy and thermogravimetric analysis, while the polyurea nanocomposites obtained have been characterized by thermal (differential scanning calorimetry and TGA) and mechanical (dynamic mechanical analysis and tensile tests) analyses. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45061.     

Electromagnetic interference shielding behavior of chemically and thermally reduced graphene based multifunctional polyurethane nanocomposites: A comparative study

This article presents the effect of exfoliation, dispersion, and electrical conductivity of graphene sheets onto the electrical, electromagnetic interference (EMI) shielding, and gas barrier properties of thermoplastic polyurethane (TPU) based nanocomposite films. The chemically reduced graphene (CRG) and thermally reduced/annealed graphene (TRG) having Brunauer–Emmett–Teller surface areas of 18.2 and 159.6 m²/g, respectively, when solution blended with TPU matrix using N,N-dimethylformamide as a solvent. Graphene sheets based TPU nanocomposites have been evaluated and compared for EMI shielding in Ku band, electrical conductivity, and gas barrier property. TRG/TPU nanocomposite films showed excellent gas barrier against N₂ gas as compared to CRG/TPU. The EMI shielding effectiveness for neat CRG and TRG graphene sheets is found to be −80, −45 dB, respectively, at 2 mm thickness. The EMI shielding data revealed that TRG/TPU nanocomposites showed better shielding at lower concentration (10 wt %), while CRG displayed better attenuation at higher concentrations. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47666.     

Performance enhancement of polylactide by nanoblending with POSS and graphene oxide

We report the effect of filler modification on the properties of polylactide (PLA)‐based nanocomposites, where graphene oxide (GO) nanosheets and polyhedral oligomeric silsesquioxane (POSS) nanocages are employed as nanofillers. The organically treated nanofillers are termed as GO‐functionalized and POSS‐functionalized. The synthesis of the nanocomposites was carried out via in situ ring‐opening polymerization of lactic acid (LA). The following four naocomposite systems were prepared, characterized, and compared to achieve a better understanding of structure‐property relationship (1) PLA/GO‐functionalized, (2) PLA/POSS‐functionalized, (3) PLA/physical mixture of GO‐functionalized and POSS‐functionalized, and (4) PLA/GO‐graft‐POSS (with eight hydroxyl groups). As revealed by the thermal and mechanical (nanoindendation) characterization, that the nanocomposites having a combination of GO and POSS as nanofiller, either as physical mixture of GO‐functionalized and POSS‐functionalized or as GO‐graft‐POSS, is far more superior as compared with the nanocomposites having individually dispersed nanofillers in the PLA matrix. Observed enhancement is attributing to the synergistic effect of the nanofillers as well as better dispersion of the modified‐fillers in the matrix. POLYM. COMPOS., 35:118–126, 2014. © 2013 Society of Plastics Engineers     

Synergistic effects of cellulose nanocrystals-organic montmorillonite as hybrid nanofillers for enhancing mechanical,crystallization, and heat-resistant properties of three-dimensional printed poly(lactic acid) nanocomposites

Cellulose nanocrystals (CNC)-organic montmorillonite (OMMT) hybrid nanofillers were prepared, and their effects in reinforcing the performance of three-dimensional (3D) printed poly(lactic acid) (PLA) nanocomposites were studied. The results indicated that the hybrid CNC-OMMT nanofillers had a synergistic impact on enhancing the mechanical properties of PLA nanocomposites compared to either single nanofillers (CNC or OMMT). The dispersion of CNC-OMMT in the PLA matrix was not only significantly improved, but also the hybrid nanofillers did not form pore defects in the nanocomposites. In terms of the crystallization performance, the multidimensional hybrid nanofillers acted as efficient heterogeneous-nucleating agents and increased the PLA crystallization rate. Additionally, the incorporation of the hybrid nanofillers improved the heat resistance of the PLA nanocomposites when the printing platform temperature was adjusted to a temperature within the crystallization temperature range of PLA. The preparation of hybrid nanofillers based on existing nanomaterials and their incorporation into polymers creates a novel route for the development of high-performance polymer nanocomposites.     

EMI shielding effectiveness of carbon based nanostructured polymeric materials: A comparative study

The microstructure, electromagnetic interference (EMI) shielding effectiveness (SE), DC electrical conductivity, AC electrical conductivity and complex permittivity of nanostructured polymeric materials filled with three different carbon nanofillers of different structures and intrinsic electrical properties were investigated. The nanofillers were multiwall carbon nanotubes (MWCNT), carbon nanofibers (CNF) and high structure carbon black (HS-CB) nanoparticles and the polymer was acrylonitrile-butadiene-styrene (ABS). In addition, the EMI SE mechanisms and the relation between the AC electrical conductivity in the X-band frequency range and the DC electrical conductivity were studied. The nanocomposites were fabricated by solution mixing and characterized by uniform dispersion of the nanofillers within the polymer matrix. It was found that, at the same nanofiller loading, the EMI SE, permittivity and electrical conductivity of the nanocomposites decreased in the following order: MWCNT > CNF > CB. MWCNT based nanocomposites exhibited the lowest electrical percolation threshold and the highest EMI SE owning to the higher aspect ratio and electrical conductivity of MWCNT compared to CNF and HS-CB. The AC conductivity in the X-band frequency range was found to be independent of frequency.     

Enhanced thermal conductivity of PLA‐based nanocomposites by incorporation of graphite nanoplatelets functionalized by tannic acid

Enhancing thermal conductivity of polymeric nanocomposites remains a great challenge because of the poor compatibility between nanofillers and the polymeric matrix and the aggregation effect of nanofillers. We report the enhanced thermal conductivity of poly(lactic acid) (PLA)‐based nanocomposites by incorporation of graphite nanoplatelets functionalized by tannic acid. Graphite nanoplatelets (GNPs) were noncovalently functionalized with tannic acid (TA) by van der Waals forces and π–π interaction without perturbing the conjugated sp² network, thus preserving the high thermal conductivity of GNPs. PLA‐based nanocomposites with different contents of TA‐functionalized GNPs (TA‐GNPs) were prepared and characterized, and the influences of TA‐GNPs content on the morphologies, mechanical properties, and thermal properties of the composites were investigated in detail. TA‐GNPs remarkably improved the thermal conductivity of PLA up to 0.77 W/(m K), showing its high potential as a thermally conductive filler for polymer‐based nanocomposites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46397.     

Thermal conductivity and stability of a three‐phase blend of carbon nanotubes,conductive polymer,and silver nanoparticles incorporated into polycarbonate nanocomposites

Metallic and non‐metallic nanofillers can be used together in the design of polycarbonate (PC) nanocomposites with improved electrical properties. Here, the preparation of three‐phase blend (carbon nanotubes (CNT), silver nanoparticles, and conductive polymer) in a two‐step process before incorporation in the PC is reported. First, ethylene diamine functionalized multiwall carbon nanotubes (MWCNT‐EDA) were decorated with Ag nanoparticles. Next, the Ag‐decorated CNTs were coated with poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate (PEDOT : PSS). Due to the high thermal conductivity instrinsic to both metallic and non‐metallic phases, it is expected that the thermal properties of the resulting nanocomposite would largely differ from those of pristine PC. We thus investigated in detail how this hybrid conductive blend affected properties such as the glass transition temperature, the thermal stability, and the thermal conductivity of the nanocomposite. It was found that this strategy results in improved thermal conductivity and thermal stability of the material. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42281.     

Morphology,thermal, and electrical properties of polypropylene hybrid composites co‐filled with multi‐walled carbon nanotubes and graphene nanoplatelets

In this study, nanocomposites of polypropylene (PP) with various loadings of multi‐wall carbon nanotubes (MWCNT) and graphene nanoplatelets (GnP) were formed by masterbatch dilution/mixing approach from individual masterbatches PP‐MWCNT and PP‐GnP. Melt mixing on a twin‐screw extruder at two different processing temperatures was followed by characterization of morphology by transmitted‐light microscopy including the statistical analysis of agglomeration behavior. The influence of processing temperature and weight fractions of both nanofillers on the dispersion quality is reported. Thermal properties of the nanocomposites investigated by DSC and TGA show sensitivity to the nanofillers weight fraction ratio and to processing conditions. Electrical conductivity is observed to increase up to an order of magnitude with the concentration of each nanofiller increasing from 0.5 wt % to 1.0 wt %. This is related with a decrease of electrical conductivity observed for unequal concentration of both nanofillers. This particular behavior shows the increase of electrical properties for higher MWCNT loadings and the increase of thermo‐mechanical properties for higher GnP loadings. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42793.     

Studies on electrical properties of nanoclay filled thermoplastic polyurethane/polypropylene blends

The electrical properties of ester/ether‐based thermoplastic polyurethane (TPU) and polypropylene (PP) blends are presented in this article. Special attention has been paid to analyze the effect of blend ratio, compatibilization, and effect of nanoclay on the electrical properties of TPU/PP blends. The electrical properties measured were dielectric constant (ε′), volume resistivity (ρ_υ), loss factor (ε″), and dissipation factor (tan δ). Addition of PP into TPU increases the volume resistivity and reduces the dissipation and loss factor due to the decrease in the overall polarity of the system. Further addition of compatibilizer and nanoclay to this system reduced the dissipation factor and loss factor with increased volume resistivity. Compared with the ether‐TPU based blend nanocomposites, the ester‐TPU blends show better compatibility as confirmed by analysis. POLYM. COMPOS., 35:1671–1682, 2014. © 2013 Society of Plastics Engineers     

Electrospun PVDF/MWCNT/OMMT hybrid nanocomposites: preparation and characterization

Electrospinning technique was employed to prepare neat PVDF, nanoclay-PVDF and carbon nanotube (MWCNT)-PVDF nanocomposites, and nanoclay-carbon nanotube-PVDF hybrid nanocomposites. A mixture of dimethyl formamide/acetone (60/40) was used to fluidize the polymer and nanofillers. Electrospinning process was conducted under optimized conditions. Maximum modification was achieved at 0.15 wt% nanofiller. Rheological measurements on the prepared solutions revealed decreased material functions in the presence of nanoclay, whereas the rheological properties of MWCNT-PVDF solution did not show any significant reduction compared with those of neat PVDF solution. The behaviors of the hybrid nanocomposite solutions, though dependent on their composition and their material functions, increased with MWCNT concentration. These differences, together with variations in electrical properties of nanoclay and MWCNT, led to changes in morphology of the fiber during electrospinning process. Under electrospinning conditions designed for neat PVDF solution, mats with beads and with the highest fiber diameter were produced. Meanwhile, incorporation of both nanoclay and MWCNT into the solutions resulted in bead-free fibers with thinner diameter. Fourier transformed infrared spectrophotometry (FTIR) and X-ray diffractometry (XRD) were used to measure the β-phase crystalline content in electrospun mats. Complete agreement was found between the FTIR and XRD results. The lowest and highest β-phase contents were obtained for neat PVDF mat and hybrid nanocomposite mat containing 0.1 wt% clay, respectively. The mixing procedure of nanofillers and the PVDF solution was also found to be important. In case of hybrid nanocomposites, more β-crystals were formed when the nanoclay was first mixed in the absence of MWCNT.     

A strategy of fabricating exfoliated thermoplastic polyurethane/clay nanocomposites via introducing maleated polypropylene

By reducing the attraction between the platelets of octadecylammonium chloride modified montmorillonite (OMMT-C18) via pre-intercalation of maleated polypropylene (MAPP), OMMT-C18 was exfoliated in thermoplastic polyurethane (TPU) matrix during melt-mixing. Wide angle X-ray diffraction, transmission electron microscopy and thermogravimetric analysis were used to investigate the microstructure of TPU nanocomposites. Three factors (including introducing sequence, the kind and the content of MAPP) showed important effects on the dispersion degree of OMMT-C18 in TPU matrix. The results confirmed that the pre-intercalation of MAPP was necessary for the exfoliation of OMMT-C18; however, the role of MAPP in TPU nanocomposites was different from that in polypropylene nanocomposites. In addition, the investigation on the morphology evolution of TPU nanocomposites showed that shear force played a key role in the formation of exfoliated TPU nanocomposites. TPU nanocomposites with exfoliated structure showed better properties compared with TPU and its nanocomposites with intercalated structure.     

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     

Properties of ultrahigh‐molecular‐weight polyethylene nanocomposite films containing different functionalized multiwalled carbon nanotubes

We compared the thermomechanical properties, morphologies, gas permeabilities, and electrical conductivities of ultrahigh‐molecular‐weight polyethylene (UHMWPE) nanocomposite films containing two types of functionalized multiwalled carbon nanotubes (functionalized MWNTs). Both 2‐hydroxyethyl triphenyl phosphonium‐MWNT (Ph3P‐MWNT) and 1,1,1,3,3,3‐hexafluoro‐2‐phenyl‐2‐propanol‐MWNT (CF3‐MWNT) were used as reinforcing fillers in the fabrication of UHMWPE hybrid films. UHMWPE nanocomposites with various functionalized MWNT contents were solution‐cast to produce the films. The thermomechanical properties and morphologies of the UHMWPE hybrid films were then characterized using differential scanning calorimetry, thermogravimetric analysis, electron microscopy, and mechanical tensile analysis. Transmission electron microscopy studies showed that some of the MWNT particles were dispersed homogeneously within the polymer matrix (on the nanoscale), whereas others were agglomerated. We also found that the addition of only a small amount of functionalized MWNTs was sufficient to improve the thermomechanical properties and the gas barrier of the UHMWPE hybrid films. Even, those hybrid films with low functionalized MWNT contents (i.e., <1 wt%) were found to exhibit much better thermomechanical properties than the pure UHMWPE films. On the other hand, the values of the electrical conductivity remained constant, regardless of the amount of functionalized MWNTs. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers