The origin of the electric and dielectric behavior of expanded graphite–carbon nanotube/cyanate ester composites with very high dielectric constant and low dielectric loss

High performance expanded graphite (EG)–multiwalled carbon nanotube (MWCNT)/cyanate ester (CE) composites with very high dielectric constant, low dielectric loss and low percolation threshold were developed. In order to understand the electric and dielectric behavior of EG–MWCNT/CE composites, EG/CE and MWCNT/CE binary composites were also prepared for comparison. Results show that the ternary composites have greatly different electric and dielectric properties from the binary composites. The percolation threshold of the EG–MWCNT/CE composite is much lower than that of either the EG/CE or MWCNT/CE composite. With the same content of conductive fillers, the EG–MWCNT/CE composite shows a much higher dielectric constant than EG/CE and MWCNT/CE composites. In addition, to obtain the same dielectric constant, the dielectric loss of the EG–MWCNT/CE composite is lower than that of either binary composite. The difference is attributed to the synergistic effect between EG and MWCNT. The addition of EG not only improves the dispersion of MWCNTs in the resin matrix, but also helps to form conductive networks. An equivalent circuit model is proposed.     

Flammability and thermal degradation of intumescent flame‐retardant polypropylene composites

The flammability of polypropylene (PP) composites containing intumescent flame‐retardant additives, i.e., melamine pyrophosphate (MPP) and 1‐oxo‐4‐hydroxymethyl‐2,6,7‐trioxa‐1‐phosphabicyclo[2.2.2]octane (PEPA) was characterized by limiting oxygen index (LOI), UL 94 test, and cone calorimeter. In addition, the thermal degradation of the composites was studied using thermogravimetric analysis (TG) and real‐time Fourier transform infrared (RTFTIR). It has been found that the PP composite only containing MPP (or PEPA) does not show good flame retardancy even at 30% additive level. Compared with the PP/MPP binary composite, the LOI values of the PP/MPP/PEPA ternary composites at the same additive loading are all increased, and UL 94 rating of the ternary composite (PP3) studied is raised to V‐0 rating from no rating (PP/MPP). The cone calorimeter results show that the heat release rate of some ternary composites decreases in comparison with the binary composite. It is noted from the TG data that initial decomposition temperatures of ternary composites are lower than that of the binary composites. The RTFTIR study indicates that the PP/MPP/PEPA composites have higher thermal oxidative stability than the pure PP. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

High dispersion ability of fluorene‐based polyester as a polymer matrix for carbon nanotubes

The high compatibility of fluorene‐based polyester (FBP‐HX) as a polymer matrix for multiwalled carbon nanotubes (MWCNTs) is discussed. A low surface resistivity due to the fine dispersion of MWCNTs in FBP‐HX and polycarbonate (PC) is reported. With a solution‐casting method, a percolation threshold with the addition of between 0.5 and 1.0 wt % MWCNTs was observed in the MWCNT/PC and MWCNT/FBP‐HX composites. Because of the coverage of FBP‐HX on the MWCNTs, a higher surface resistivity and a higher percolation ratio of the MWCNT/FBP‐HX composites were achieved compared with the values for the MWCNT/PC composites. In the MWCNT/FBP‐HX composites, MWCNTs covered with FBP‐HX were observed by scanning electronic microscopy. Because of the coverage of FBP‐HX on the MWCNTs, FBP‐HX interfered with the electrical pathway between the MWCNTs. The MWCNTs in FBP‐HX were covered with a 5‐nm layer of FBP‐HX, but the MWCNTs in the MWCNT/PC composites were in their naked state. MWCNT/PC sheets demonstrated the specific Raman absorption of the MWCNTs only with the addition of MWCNTs of 1 wt % or above because of the coverage of the surface of the composite sheet by naked MWCNTs. In contrast, MWCNT/FBP‐HX retained the behavior of the matrix resin until a 3 wt % addition of MWCNTs was reached because of the coverage of MWCNTs by the FBP‐HX resin, induced by its high wettability. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Binary and ternary nanocomposites based on PVDF,PMMA, and PVDF/PMMA blends: polymorphism,thermal, and rheological properties

Binary and ternary nanocomposites based on poly(vinylidene fluoride) (PVDF), poly(methyl methacrylate) (PMMA), and PVDF/PMMA blends were successfully prepared through a melt-mixing process, using a commercial organoclay (15A) as the nanofiller. The 15A was more finely dispersed (intercalated/partially exfoliated) within the PVDF matrix compared with the PMMA matrix. A higher PVDF content in the ternary composite essentially led to a superior degree of 15A dispersion. The 15A addition induced the polar β-form PVDF crystals, whereas the presence of PMMA in ternary composites reduced the efficiency in promoting β-form formation by 15A. Adding 15A also enhanced the nucleation of PVDF, but the enhancement was inferior while PMMA was present. Conversely, the crystal growth of PVDF was retarded with the existence of 15A, and the PVDF/15A binary composite exhibited the greatest retardation. The equilibrium melting temperature (T_m°) of PVDF in the neat state and in the blends increased after 15A addition. The PVDF/15A binary composite possessed an evidently higher β-form T_m° than the α-form T_m° of neat PVDF (~20.1 °C rise). Similar effects on the individual components, 15A declined the thermal stability of PVDF but increased that of PMMA in the ternary composites. Rheological property measurements revealed that the ternary composites performed in-between that of individual PVDF/15A and PMMA/15A binary composites. A percolation of 15A (pseudo)network structure was developed in the composites, and a more elastic behavior was observed with increasing PVDF content in the composites.     

Binary [Cu2O/MWCNT] and ternary [Cu2O/ZnO/MWCNT] nanocomposites: formation, characterization and catalytic performance in partial ethanol oxidation

Cuprous oxide agglomerates composed of 4-10 nm Cu2O nanoparticles were deposited on multiwalled carbon nanotubes (MWCNTs) and on ZnO/MWCNTs to give binary [Cu2O/MWCNT] and ternary [Cu2O/ZnO/MWCNT] composites. Di-aqua-bis[2-(methoxyimino)propanoato]copper Cu[O2CCCH3NOMe](2)·2H2O 1 in DMF was used as single source precursor for the deposition of nanoscaled Cu2O. The precursor decomposes either in air or under argon to yield CuO2 by in situ redox reaction. Thermogravimetric coupled mass spectroscopic analysis (TG-MS) of 1 revealed that methanol formed during the decomposition of 1 acts as a potential in situ reducing agent. Scanning electron microscopy (SEM) of the binary [Cu2O/MWCNT] nano-composite shows an increase of cuprous oxide loading depending on the precursor amount, along the periphery of the MWCNTs as well as formation of larger particle agglomerates. Transmission electron microscopy (TEM) of the sample shows crystalline domains of size 4-10 nm surrounded by an amorphous region within the larger particles. SEM and TEM of ternary [Cu2O/ZnO/MWCNT] clearly reveal that Cu2O nanoparticles are primarily deposited on ZnO rather than on MWCNTs. The catalytic activities of the [Cu2O/MWCNT] and [Cu2O/ZnO/MWCNT] binary and ternary composites were studied for the selective partial oxidation of ethanol to acetaldehyde with molecular oxygen. While using binary [Cu2O/MWCNT] (13.8 wt% Cu) as catalyst, acetaldehyde was obtained with a yield of 87% at 355 °C (selectivity 96% and conversion 91%). When nanoscale ZnO is present, the resulting [Cu2O/ZnO/MWCNT] composite shows preferential hydrogen and CO2 formation due to the fact that the dehydrogenation and total oxidation pathway is more favoured compared to the binary composite. Significant morphological changes of the catalyst during the catalytic process were observed.     

Dynamic crystallization of polypropylene and wood‐based composites

Thermoplastic composites made of an isotactic polypropylene (iPP) matrix and woodflour (WF) were prepared by melt‐blending, using twin‐screw extrusion and injection molding. Up to 20 wt % of the composite was composed of WF. The incorporation of an interfacial agent made of an ethylene/methacrylic acid copolymer to iPP and WF, PP/WF, binary blends causes a compatibilization effect that becomes evident due to a reduction in the crystallization temperature of PP. In both the binary composites and the compatibilized or ternary composites, the PP adopts an α or monoclinic structure when crystallization occurs from the melt under dynamic conditions at cooling rates between 1 and 20°C min^?1. On the other hand, X‐ray diffraction analysis using synchrotron radiation of the injection‐molded samples demonstrates the existence of a β or trigonal form in the binary as well as the ternary PP/WF composites. They reach k_β levels between 0.18 and 0.25, which can be interpreted as the co‐operation between a reduction of the crystallization rate and the shear effect induced during the injection. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 6028–6036, 2006     

Indentation and scratch behavior of functionalized MWCNT–PMMA composites at the micro/nanoscale

Polymethylmethacrylate (PMMA) and functionalized multiwalled carbon nanotube (F‐MWCNT) based composite films were prepared using solution casting method. Nanoindentation and scratch measurements were carried out to study the influence of F‐MWCNT as the reinforcement on the mechanical properties of the composite at the sub‐micron scale. The composites were prepared with varying weight percentages of F‐MWCNT in the PMMA matrix. The composites containing an adequate amount (0.25 wt%) of F‐MWCNT was found to demonstrate the maximum nanomechanical properties, viz. hardness, elastic modulus, recovery index. Scratch resistance measured in terms of coefficient of friction, also showed maximum value for the PMMA composite reinforced with 0.25 wt% of F‐MWCNT. POLYM. COMPOS., 35:948–955, 2014. © 2013 Society of Plastics Engineers     

Conductive poly(vinylidene fluoride)/polyethylene/graphene blend‐nanocomposites: Relationship between rheology,morphology, and electrical conductivity

Relationship between rheology, morphology, and electrical conductivity of the poly(vinylidene fluoride)/polyethylene/graphene nano‐platelets ternary system (PVDF/PE/GnP) were investigated. All the blend nanocomposites were prepared via a two‐step melt mixing method. GnP (0.75 and 1.5 wt %) was first compounded with PVDF and then the resulted premixtuers were melt mixed with PE to achieve the desired compositions. The corresponding reference nanocomposites and filler‐less blends were also prepared. Effect of an interfacial agent (PEMA; maleic anhydride grafted polyethylene) was also studied in this work. The results of rheological analysis in conjunction with the Raman spectroscopy experiments revealed that GnP had higher affinity to PVDF than PE, which in turn led to creation of conductive networks of GnP (1.5 wt %) in PVDF matrix exhibiting the electrical conductivity of about 10^?2 (S/cm). Double percolated micro‐structure was predicted for the PE/PVDF 40/60 (wt/wt) blend containing low GnP content (0.9 wt %) and confirmed via direct electron microscopy and conductivity analysis. Using 5 wt % of the PEMA reduced the conductivity to 10^?5 (S/cm) and further increase in PEMA content to 10 wt % led to non‐conductive characteristics. The latter was attributed to the migration of GnP from the PVDF phase to PE/PEMA phase and hence disturbance of double percolated micro‐structure. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46333.     

Preparation,morphology, and properties of silane‐modified MWCNT/epoxy composites

Both epoxy resin and acid‐modified multiwall carbon nanotube (MWCNT) were treated with 3‐isocyanatopropyltriethoxysilane (IPTES). Scanning electron microscopy (SEM) and transmission electronic microscope (TEM) images of the MWCNT/epoxy composites have been investigated. Tensile strength of cured silane‐modified MWCNT (1.0 wt %)/epoxy composites increased 41% comparing to the neat epoxy. Young's modulus of cured silane‐modified MWCNT (0.8 wt %)/epoxy composites increased 52%. Flexural strength of cured silane‐modified MWCNT (1.0 wt %)/epoxy composites increased 145% comparing to neat epoxy. Flexural modulus of cured silane‐modified MWCNT (0.8 wt %)/epoxy composites increased 31%. Surface and volume electrical resistance of MWCNT/epoxy composites were decreased with IPTES‐MWCNT content by 2 orders and 6 orders of magnitude, respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Dielectric properties of multiwalled carbon nanotube/clay/polyvinylidene fluoride nanocomposites: Effect of clay incorporation

This study investigates the effect of clay addition on the broadband dielectric properties of multi‐walled carbon nanotube/polyvinylidene fluoride (MWCNT/PVDF) composites, that is, frequency range of 10¹−10⁶ Hz. Different loadings of MWCNT and clay were used for the preparation of three‐phase (MWCNT/Clay/PVDF) nanocomposites via melt‐mixing method. The crystalline structure and morphology of nanocomposites were examined by employing characterization techniques such as X‐ray diffraction, transmission electron microscopy, and differential scanning calorimetry. The dielectric spectroscopy showed that introducing clay into the MWCNT/PVDF nanocomposites at a critical MWCNT concentration improved dielectric properties tremendously. It was interestingly observed that the incorporation of a specific amount of clay, that is, 1.0 wt%, into the (MWCNT/PVDF) nanocomposite at a critical MWCNT loading, that is, 0.5 wt% MWCNT, resulted in a huge increase in the dielectric permittivity (670% at 100 Hz) and a considerable reduction in the dissipation factor (68% at 100 Hz). POLYM. COMPOS., 161–167, 2016. © 2014 Society of Plastics Engineers     

Functionalized Graphene–PVDF Foam Composites for EMI Shielding

Novel foam composites comprising functionalized graphene (f‐G) and polyvinylidene fluoride (PVDF) were prepared and electrical conductivity and electromagnetic interference (EMI) shielding efficiency of the composites with different mass fractions of f‐G have been investigated. The electrical conductivity increases with the increase in concentration of f‐G in insulating PVDF matrix. A dramatic change in the conductivity is observed from 10^?16 S · m^?1 for insulating PVDF to 10^?4 S · m^?1 for 0.5 wt.% f‐G reinforced PVDF composite, which can be attributed to high‐aspect‐ratio and highly conducting nature of f‐G nanofiller, which forms a conductive network in the polymer. An EMI shielding effectiveness of ≈20 dB is obtained in X‐band (8–12 GHz) region and 18 dB in broadband (1–8 GHz) region for 5 wt.% of f‐G in foam composite. The application of conductive graphene foam composites as lightweight EMI shielding materials for X‐band and broadband shielding has been demonstrated and the mechanism of EMI shielding in f‐G/PVDF foam composites has been discussed.

     

Electrical conductivity of poly(vinylidene fluoride)/carbon nanotube composites with a spherical substructure

Poly(vinylidene fluoride) (PVDF)/multiwalled carbon nanotube (MWCNT) conducting composites were prepared with a percolation threshold as low as 0.07 wt%. The MWCNTs in a PVDF solution can lead to the formation of spherical PVDF/MWCNT composite particles by sonication. The MWCNTs coated on the surfaces of the spherical particles form a conduction network when the spheres coalesce to form a solid composite. The existence of the spherical particles with a substructure results in the reduction in MWCNT content and improves the electrical conductivity of the composites.     

Electrical,mechanical, and piezoresistive properties of carbon nanotube–polyaniline hybrid filled polydimethylsiloxane composites

The electrical, mechanical, and piezoresistive properties of ternary composites based on elastomeric polydimethylsiloxane (PDMS), carbon nanotubes (CNTs), and polyaniline (PANI) were studied and compared with those of binary PDMS–CNT composites. The presence of PANI affected the percolating network of the CNTs. At lower PANI concentrations (2.5 and 5%), the conductive network of the CNTs was constructively modified; this led to an enhancement in the conductivity in the sample containing 2% CNTs. A higher PANI content (7.5%) hindered the flow of main charge carriers through the composite. The piezoresistive response of the binary and ternary composites was studied by cyclic experiments under compression loads. In all of the samples, the electrical resistance increased monotonically up to a 10% strain. The reproducibility of the piezoresistive behavior in the binary and ternary composites provided evidence that the fillers could reversibly recover their initial position together with the PDMS chains without a significant displacement with respect to their original positions. The reduction of the piezoresistive sensibility by PANI addition was attributed to the displacement restrictions of the CNTs within the composite under pressure because of the volume exclusion of PANI particles; this maintained the probability of CNT contact and increased the possibility of the formation of new CNT conductive channels. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44780.     

Fabrication and characterization of homogeneous composites of polypropylene and multiwalled carbon nanotubes

The polypropylene‐grafted multiwalled carbon nanotubes (PP‐MWCNTs) were produced from the reaction of PP containing the hydroxyl groups and MWCNTs having 2‐bromoisobutyryl groups. The PP‐MWCNTs had a significantly rougher surface than the original MWCNTs. PP‐MWCNTs had PP layers of thickness 10–15 nm on the outer walls of the MWCNTs. PP/PP‐MWCNT composites and PP/MWCNT composites were prepared by solution mixing in o‐xylene. Unlike PP/MWCNT composites, PP‐MWCNTs were homogeneously dispersed in the PP matrix. As a consequence, the thermal stability and conductivity of PP/PP‐MWCNT composites were dramatically improved even if only 1 wt % of PP‐MWNTs was added to the PP matrix. The good miscibility of PP and PP‐MWCNTs plays a critical role in the formation of the homogeneous composites and leads the high thermal stability and conductivity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Soft and flexible conductive PDMS/MWCNT composites

Conductive elastomers based on MWCNT in polydimethylsiloxane (PDMS) have been prepared by a range of dispersion methods such as ultrasonication, speedmixing and roll milling in combination with physical or covalent modification. The ionic liquid (IL), 1‐ethyl‐3‐methylimidazolium bis(trifluoromethanesulfonyl)imide, was used to pre‐disperse MWCNT in a MWCNT/IL‐gel that was used for preparation of MWCVNT/PDMS composites. The method was seen to be effective at low levels of MWCNT, but required combination with a roll mill to obtain a stable dispersion at 4 wt % MWCNT. With higher amounts of MWCNT a reduction in conductivity was observed, which was attributed to a change in morphology occurring between 4 and 5 wt % MWCNT. As an alternative to IL dispersing aids a novel functionalized MWCNT was prepared by free radical polymerization using α‐methacryloxypropyl‐polydimethylsiloxane, which could be used directly for preparation of MWCNT/PDMS composites. Composites prepared by use of the IL dispersion method, use of a roll mill or by use of the f‐MWCNT all had conductivities around 0.005–0.01 s/cm and retained conductivity upon extension. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44767.     

High performance polyurethane composites with isocyanate‐functionalized carbon nanotubes: Improvements in tear strength and scratch hardness

A microwave‐assisted functionalization of carbon nanotubes (CNTs) with isocyanate groups allowed a reduction of functionalization time from 24 h to 30 min with no change in the degree of functionalization or in the nanotube characteristics. Polymer nanocomposites with enhanced mechanical properties were obtained because of the tailored interface by the covalent linkage between the surface‐modified multiwalled‐carbon nanotubes (MWCNTs) and an elastomeric polyurethane (PUE) matrix. The mechanical data revealed that the composite containing 0.25 wt % of MWCNT‐NCO showed an increase of 31% in tear strength and 28% in static toughness. A good adhesion between the matrix and individually dispersed nanotubes was observed in the scanning electron microscopy and transmission electron microscopy images. Nanoindentation and nanoscratch experiments were conducted to investigate the properties on the sub‐surface. An increase by a factor of 3 in the scratch hardness was observed for the composite with 0.50 wt % of MWCNT‐NCO with respect to the neat PUE. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44394.     

Resistivity behaviour of barium titanate (BaTiO3)/polyvinylidene fluoride (PVDF) composites

The resistivity behaviour of Barium Titanate (BaTiO₃) / Polyvinylidene Fluoride (PVDF) composites studied by changing the wt. fraction of BaTiO₃. The resistivity behaviour of composites followed that of PVDF up to 50% wt. fraction of BaTiO₃ in the composite. The resistivity of the composite with 70% wt. fraction of BaTiO₃ varied one order. The results are correlated with SEM studies on the composites. At a lower wt. fraction of BaTiO₃ in composites, PVDF formed an insulating layer over BaTiO₃ grans, which is not significant at higher wt. fractions of BaTiO₃ in the system     

Influence of Multiwalled Carbon Nanotubes on Mechanical,Thermal and Electrical Behavior of Polybenzoxazine-Epoxy Nanocomposites

Multiwalled carbon nanotubes (MWCNT)-reinforced polybenzoxazine-epoxy nanocomposites were prepared via the solvent method and were investigated for their thermal, thermo-mechanical, mechanical, electrical and morphological properties. Epoxy resin (DGEBA) was modified with 5, 10 and 15 wt.% of benzoxazines using 4,4′-diaminodiphenylmethane as a curing agent at appropriate conditions. Epoxy and benzoxazines-modified epoxy systems were further reinforced with 0.25, 0.50 and 0.75 wt.% of surface-modified MWCNT. MWCNT-reinforced polybenzoxazine-epoxy nanocomposites exhibited better thermal, mechanical and dielectric properties. Dispersion of MWCNT in benzoxazine-epoxy resins and nanostructure of the composites was confirmed by transmission electron microscopy analysis.     

Failure investigation of carbon nanotube/3Y-TZP nanocomposites

3Y-TZP matrix composites containing 0.1–1 wt.% of multi-wall (MWCNT) and single-wall (SWCNT) carbon nanotubes were fabricated by spark plasma sintering technique. The sintered composites reached full density. Hardness and fracture toughness were measured using Vickers indention method. The hardness of the composite decreased with increasing weight content of the MWNT. The fracture toughness was 5.52 MPa m^0.5 when the amount of MWCNTs was 0.5 wt.%, however it decreased to 4.5 MPa m^0.5 when the content was raised to 1.0 wt.%. The composite containing 0.5 wt.% SWCNTs showed similar fracture toughness as that of matrix. The incorporation of CNTs into 3Y-TZP matrix led to no prominent improvement on the mechanical properties. The failure mechanism was analyzed finally.     

Dielectric properties of poly(vinylidene fluoride) composites based on Bucky gels of carbon nanotubes with ionic liquids

“Bucky gels” of carbon nanotubes were successfully prepared by grinding multi‐walled carbon nanotubes (MWNTs) and ionic liquids (ILs) for several hours. A series of poly(vinylidene fluoride) (PVDF) composites with Bucky gels was obtained through simple melt compounding. The Raman spectrum showed significant interaction among the ILs, MWNTs, and PVDF. The dielectric behavior of the PVDF composites based on unmodified and IL‐modified MWNTs was studied from 40 Hz to 30 MHz. The addition of ILs significantly enhanced the dielectric property of the PVDF/IL/MWNT ternary composites, which was much higher than that of the sum of PVDF/IL and PVDF/MWNT binary composites. The SEM results revealed that both MWNTs and ILs uniformly dispersed throughout the PVDF/IL/MWNT composites because of the strong interaction between them. The DSC and XRD results showed that the addition of ILs in the composites changed the crystallinity and crystal form of the PVDF. POLYM. COMPOS., 36:94–101, 2015. © 2014 Society of Plastics Engineers