Effects of surface modification with 3‐aminopropyltriethoxysilane on structure and mechanical property of multiwalled carbon nanotube/polycarbonate composites

Hydroxyl functionalized multiwalled carbon nanotubes (H‐MWNTs) were silanized using 3‐aminopropyltriethoxysilane (APTES) in order to improve the dispersion and interfacial interaction in composites. MWNT/polycarbonate (PC) composites filled with H‐MWNTs and silanized MWNTs (S‐MWNTs) were fabricated by melt mixing and injection molding. Fourier transform infrared spectrometry (FTIR) and energy dispersion X‐ray spectroscopy (EDS) were employed to prove the presence of APTES on the surface of S‐MWNTs. In addition, thermogravimetric analysis (TGA) was used to evaluate the relative amount of introduced APTES. The microstructure and mechanical property of both composites were investigated by scanning electron microscopy (SEM), transmission electron microscope (TEM), tensile test and dynamic mechanical analysis (DMA). The SEM and TEM images showed that S‐MWNT/PC composites had better dispersion and interfacial adhesion than H‐MWNT/PC composites. A reinforcing and toughening effect on tensile behavior of composites was obtained after silane functionalization. The storage modulus of composites increased markedly as a function of MWNTs content, especially for the composites with S‐MWNTs. In summary, the silanization can improve the dispersion of MWNTs and the interfacial adhesion between MWNTs and PC so as to enhance the mechanical properties of composites. POLYM. COMPOS., 37:1914–1923, 2016. © 2015 Society of Plastics Engineers     

Effect of processing parameters on the surface resistivity of ethylene–vinyl acetate copolymer/multiwalled carbon nanotube nanocomposites

In this study, ethylene–vinyl acetate (EVA) copolymer was melt‐mixed with multiwalled carbon nanotube (MWCNT). To realize full‐scale application of MWCNT to the polymer industries, the effect of melt‐processing parameters on the surface resistivity in the polymer/MWCNT nanocomposites should be well‐understood. The effect of mixing time, rotor speed, compression molding time, and temperature on the surface resistivity was investigated. Increasing the rotor speed and longer mixing time lead to an improvement of dispersion of MWCNT in polymer matrix, resulting in a decrease of surface resistivity. The surface resistivity of EVA/MWCNT nanocomposites is also sensitive to the press temperature and time. However, the dominant processing parameters to affect surface resistivity depend on the amount of MWCNT. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Mechanical and thermal properties of functionalized multiwalled carbon nanotubes and multiwalled carbon nanotube–polyurethane composites

Multiwalled carbon nanotube (MWNT)–polyurethane (PU) composites were obtained by an in situ polycondensation approach. The effects of the number of functional groups on the dispersion and mechanical properties were investigated. The results showed that the functionalized MWNTs had more advantages for improving the dispersion and stability in water and N,N′‐dimethylformamide. The tensile strength and elongation at break of the composites exhibited obvious increases with the addition of MWNT contents below 1 wt % and then decreases with additions above 1 wt %. The maximum values of the tensile strength and elongation at break increased by 900 and 741%, respectively, at a 1 wt % loading of MWNTs. Differential scanning calorimetry measurements indicated that the addition of MWNTs resulted in an alteration of the glass‐transition temperature of the soft‐segment phase of MWNT–PU. Additionally, new peaks near 54°C were observed with differential scanning calorimetry because of the microphase‐separation structures and alteration of the segment molecular weights of the hard segment and soft segment of PU with the addition of MWNTs. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Melt Mixing of Polycarbonate with Multi‐Walled Carbon Nanotubes in Miniature Mixers

Summary: MWNT mixtures with PC were prepared in three different miniature mixers at 265 °C and 50 rpm for 6 min by the master batch dilution method. One mixer is a 4.5 cm³ DACA microcompounder (DACA Instruments) consisting of two conical co‐rotating screws with a bypass, allowing the material to circulate for defined periods. The other two miniature mixers are custom‐built in our lab: the 2.2 cm³ APAM and the 3 cm³ MBM. The volume resistivity for the nanocomposites obtained from the APAM and the MBM showed a similar trend for different MWNT compositions. The electrical percolation concentration for the nanocomposites prepared in the APAM and the MBM is between 0.50 wt.‐% (or 0.34 vol.‐%) and 0.75 wt.‐% (or 0.52 vol.‐%) MWNT, and it is between 0.75 wt.‐% (or 0.52 vol.‐%) and 1.00 wt.‐% (or 0.69 vol.‐%) for the DACA microcompounder. Rheological characterization indicates that the microstructure of PC/MWNT composites prepared from the miniature mixers changes at a concentration of 0.38 wt.‐% for the APAM and the MBM and 0.50 wt.‐% for the DACA where an interconnected network is formed. TEM micrographs show that there are some small aggregates in the nanocomposites obtained from the APAM, fewer aggregates from the MBM, and least from the DACA. AFM analysis suggests that the length of nanotubes is reduced from 0.57 µm to 0.38–0.42 µm after they were melt mixed in the three mixers.

Effect of MWNT content on volume resistivity of PC/MWNT obtained from different microcompounders.     

Dielectric spectroscopy on melt processed polycarbonate—multiwalled carbon nanotube composites

Complex permittivity and related AC conductivity measurements in the frequency range between 10⁻⁴ and 10⁷ Hz are presented for composites of polycarbonate (PC) filled with different amounts of multiwalled carbon nanotubes (MWNT) varying in the range between 0.5 and 5 wt%. The composites were obtained by diluting a PC based masterbatch containing 15 wt% MWNT by melt mixing using a Micro Compounder. From DC conductivity measurements it was found that for samples processed at a mixing screw speed of 150 rpm for 5 min, the percolation occurs at a threshold concentration (p_c) between 1.0 and 1.5 wt% MWNT. For concentrations of MWNT near the percolation threshold, the processing conditions (screw speed and mixing time) were varied. The differences in the dispersion of the MWNT in the PC matrix could be detected in the complex permittivity and AC conductivity spectra, and have been explained by changes in p_c. The AC conductivity and permittivity spectra are discussed in terms of charge carrier diffusion on percolation clusters and resistor-capacitor composites.     

High electrical conductivity of nylon 6 composites obtained with hybrid multiwalled carbon nanotube/carbon fiber fillers

The synergetic effect of multiwalled carbon nanotubes (MWNTs) and carbon fibers (CFs) in enhancing the electrical conductivity of nylon 6 (PA6) composites was investigated. To improve the compatibility between the fillers and the PA6 resin, we grafted γ‐aminopropyltriethoxy silane (KH‐550) onto the MWNTs and CFs after carboxyl groups were generated on their surface by chemical oxidation with nitric acid. Fourier transform infrared spectroscopy and thermogravimetric analysis proved that the KH‐550 molecules were successfully grafted onto the surface of the MWNTs and CFs. Scanning electron microscopy and optical microscopy showed that the obtained modified fillers reduced the aggregation of fillers and resulted in better dispersion and interfacial compatibility. We found that the electrical percolation threshold of the MWNT/PA6 and CF/PA6 composites occurred when the volume fraction of the fillers were 4 and 5%, respectively. The MWNT/CF hybrid‐filler system exhibited a remarkable synergetic effect on the electrically conductive networks. The MWNT/7% CF hybrid‐filler system appeared to show a second percolation when the MWNT volume fraction was above 4% and a volume resistivity reduction of two orders of magnitude compared with the MWNT/PA6 system. The mechanical properties of different types of PA6 composites with variation in the filler volume content were also studied. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40923.     

Influence of twin-screw extrusion conditions on the dispersion of multi-walled carbon nanotubes in a poly(lactic acid) matrix

Twin-screw extrusion using a co-rotating Berstorff ZE25 extruder was applied to disperse multi-walled carbon nanotubes (MWNT) in poly(lactic acid) (PLA). The masterbatch dilution technique was used whereas four different masterbatches were produced under variation of MWNT content, screw profile, temperature profile, and rotation speed which then were diluted to composites with 0.75 wt% MWNT under varied process conditions. The state of dispersion was investigated by light microscopy from which a dispersion index was quantified. Transmission electron microscopy was performed to observe the MWNT dispersion and network formation in the sub-micron scale.The state of MWNT dispersion within the diluted composites was predominated by the state of filler dispersion in the masterbatches. High rotation speed (500 rpm) that still ensures a certain residence time of the melt combined with a screw profile containing mainly mixing elements were found to be highly convenient to disperse and distribute the MWNT in the PLA matrix as well during masterbatch production as the dilution step. The temperature profile showed less influence, however, an increasing profile resulted in slightly better nanotube dispersions. By means of these processing conditions a percolation set was performed indicating an electrical percolation threshold below 0.5 wt% MWNT content as measured on compression molded samples.     

Electrical resistivity of polycarbonate/multiwalled carbon nanotube composites under varying injection molding conditions

Multiwalled carbon nanotube (MWCNT)‐filled polycarbonate composites were prepared by a corotating intermeshing twin‐screw extruder. The surface resistivities of compression‐ and injection‐molded specimens were quite different, the difference ranging from 10³ to 10⁷ Ω/sq at varying MWCNT concentrations. The surface resistivity of the injection‐molded specimen at 2 wt % loading varied up to 10⁵ Ω/sq in the specimen thickness direction and up 10⁴ Ω/sq in the polymer flow direction with respect to the gate. The difference in surface resistivity with the positions of injection‐molded specimen was confirmed with the morphology, which showed the difference in MWCNT number density (numbers/surface area). There was no significant effect on surface resistivity with injection pressure, holding pressure, and molding temperature. The specimens prepared at the injection speed of 13 mm/s showed surface resistivities 10³–10⁴ Ω/sq depending on the positions, which was comparable with the compression‐molded specimens, which had a surface resistivity of 10³ Ω/sq. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

Enhancement of the surface and bulk mechanical properties of polystyrene through the incorporation of raw multiwalled nanotubes with the twin‐screw mixing technique

In this article, we present the effects of incorporated multiwalled nanotubes (MWNTs) on a metal surface and the bulk mechanical properties of as‐synthesized polystyrene (PS)–MWNT composites prepared with the twin‐screw mixing technique. The MWNTs used for preparing the composites were raw compounds that were not treated with any surface modifications. The morphology for the dispersion capability of the MWNTs in the PS matrix was subsequently characterized with transmission electron microscopy. Surface mechanical property studies (i.e., wear resistance and hardness) showed that the integration of MWNTs led to a distinct increase in the wear resistance and also the micro/nanohardness with up to a 5 wt % MWNT loading in the composites. Moreover, the enhancement of the wear resistance of the as‐prepared composites, in comparison with pure PS, was further identified with scanning electron microscopy observations of the surface morphology after testing. On the other hand, for bulk mechanical property studies (i.e., the tensile strength and flexural strength), the composites containing a 3 wt % concentration of MWNTs in the PS matrix exhibited the best performance with respect to the tensile strength and flexural strength. This means that this composition of MWNTs exhibited good compatibility with the PS matrix, and this can be attributed to the π–π interacting forces existing between the aromaticity of the MWNTs and PS matrix. Furthermore, at higher MWNT loadings (e.g., 5 wt %), raw MWNTs were aggregated in the polymer matrix, as observed by transmission electron microscopy. Also, this led to an obvious decrease in the tensile strength and flexural strength. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Impact of injection‐molding processing parameters on the electrical,mechanical, and thermal properties of thermoplastic/carbon nanotube nanocomposites

Thermoplastic nanocomposites, based on high‐density polyethylene, polyamide 6, polyamide 66, poly(butylene terephthalate), or polycarbonate and containing multiwalled carbon nanotubes (CNTs), were compounded with either neat CNTs or commercial CNT master batches and injection‐molded for the evaluation of their electrical, mechanical, and thermal properties. The nanocomposites reached a percolation threshold within CNT concentrations of 2–5 wt %; however, the mechanical properties of the host polymers were affected. For some nanocomposites, better properties were achieved with neat CNTs, whereas for others, master batches were better. Then, polycarbonate and poly(butylene terephthalate), both with a CNT concentration of 3 wt %, were injection‐molded with a screening design of experiments (DOE) to evaluate the effects of the processing parameters on the properties of the nanocomposites. Although only a 10‐run screening DOE was performed, such effects were clearly observed. The volume resistivity was significantly dependent on the working temperature and varied up to 4 orders of magnitude. Other properties were also dependent on the processing parameters, albeit in a less pronounced fashion. Transmission electron microscopy indicated that conductive samples formed a percolation network, whereas nonconductive samples did not. In conclusion, injection‐molding parameters have a significant impact on the properties of polymer/CNT nanocomposites, and these parameters should be optimized to yield the best results. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Investigation of multi‐walled carbon nanotube‐reinforced high‐density polyethylene/carbon black nanocomposites using electrical,DSC and positron lifetime spectroscopy techniques

BACKGROUND: The positive temperature coefficient (PTC) effect on material properties has attracted much attention in recent years due to the prospects of many applications like temperature sensors, thermistors, self‐regulating heaters, etc. It has been suggested that incorporation of multi‐walled carbon nanotubes (MWNTs) into carbon black (CB)‐filled polymers could improve the electrical properties of composites due to high conductivity and network structure and significantly reduce the required CB loading. RESULTS: We observed no change in melting temperature and crystalline transition temperature on addition of MWNTs. However, the heat of fusion decreases as the amount of conducting carboxylated MWNT (c‐MWNT) filler increases and the resistivity of the composite decreases. The free volume shows an increase up to 1.5 wt% of c‐MWNT content and then decreases. CONCLUSION: Well‐developed crystals could not be formed due to restricted chain mobility as filler content increases. This results in minimum intermolecular interactions, and thus a decreased heat of fusion. A composite with c‐MWNT content of 0.5 wt% showed the highest PTC and higher resistivity at 150 °C possibly due to the formation of flocculated structures at elevated temperature. For filler content greater than 1.5 wt%, the decrease in free volume may be due to restricted chain mobility. Copyright © 2009 Society of Chemical Industry     

Nanotube surface functionalization effects in blended multiwalled carbon nanotube/PVDF composites

A mixed fill system of multiwalled carbon nanotubes (MWCNT) and hydroxylated MWCNT (HO‐MWCNT) in a poly(vinylidene fluoride) (PVDF) matrix was investigated to improve nanotube dispersion and enhance electrical percolation for the bulk nanocomposites. Nonfunctionalized MWCNT were blended at various concentrations into dimethylformamide solutions containing PVDF with 0, 5, or 10 wt % HO‐MWCNT. Composite samples prepared from these solutions were examined by four‐point probe resistivity measurements. The percolation threshold decreased from 0.49 wt % MWCNT in binary MWCNT/PVDF composites to 0.25 wt % for ternary composites containing MWCNT/HO‐MWCNT/PVDF, with either 5 or 10 wt % HO‐MWCNT. In the case of the ternary composite with 10 wt % HO‐MWCNT, the lowest fill percent of MWCNT (0.25 wt %) measured a conductivity that was three orders of magnitude higher than the binary MWCNT/PVDF composite containing twice the concentration of MWCNT (0.5 wt %). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Graphene nanoplate and multiwall carbon nanotube–embedded polycarbonate hybrid composites: High electromagnetic interference shielding with low percolation threshold

This study has reported the preparation of polycarbonate (PC)/graphene nanoplate (GNP)/multiwall carbon nanotube (MWCNT) hybrid composite by simple melt mixing method of PC with GNP and MWCNT at 330°C above the processing temperature of the PC (processing temperature is 280°C) followed by compression molding. Through optimizing the ratio of (GNP/MWCNT) in the composites, high electromagnetic interference shielding effectiveness (EMI SE) value (∼21.6 dB) was achieved at low (4 wt%) loading of (GNP/MWCNT) and electrical conductivity of ≈6.84 × 10⁻⁵ S.cm⁻¹ was achieved at 0.3 wt% (GNP/MWCNT) loading with low percolation threshold (≈0.072 wt%). The high temperature melt mixing of PC with nanofillers lowers the melt viscosity of the PC that has helped for better dispersion of the GNPs and MWCNTs in the PC matrix and plays a key factor for achieving high EMI shielding value and high electrical conductivity with low percolation threshold than ever reported in PC/MWCNT or PC/graphene composites. With this method, the formation of continuous conducting interconnected GNP‐CNT‐GNP or CNT‐GNP‐CNT network structure in the matrix polymer and strong π–π interaction between the electron rich phenyl rings and oxygen atom of PC chain, GNP, and MWCNT could be possible throughout the composites. POLYM. COMPOS., 37:2058–2069, 2016. © 2015 Society of Plastics Engineers     

Effects of injection molding conditions on the electrical properties of polycarbonate/carbon nanotube nanocomposites

Polycarbonate/Carbon nanotube (PC/CNT) nanocomposites containing various CNT contents (0–5 wt%) were prepared by injection molding. The effects of CNT contents, injection speed (V) and injection temperature (T) on the electrical resistivity of the PC/CNT nanocomposites were investigated. It was found that the tensile strength of nanocomposites was enhanced slightly with increased CNT contents, and the tensile modulus was 29% greater after the 5 wt% CNT addition, but the brittle tendency became stronger. Aside from tensile properties, the electrical resistivity of the nanocomposites dropped 12 orders of magnitude after the 5 wt% CNT addition. Also, there was a tendency that the electrical resistivity was lower in the case of higher injection temperature and lower injection speed. Scanning electron microscope (SEM) images and the distribution of surface layer electrical resistivity, clearly showed a notable influence by surface layer microstructures on the electrical resistivity, and the injection conditions affected both the value of the maximum electrical resistivity and the position where it occurred. This study offers an alternative green and simple molding process to prepare conductive PC nanocomposites and to achieve the industrialization of PC/CNT nanocomposite products which can be used in electromagnetic shielding and anti‐static fields. POLYM. COMPOS., 37:3245–3255, 2016. © 2015 Society of Plastics Engineers     

A novel low‐melting‐point alloy‐loaded polymer composite. I. Effect of processing temperature on the electrical properties and morphology

Sn–Pb alloy‐loaded polystyrene (PS) composites were processed by powder mixing and hot pressing. For the composites hot‐pressed at the temperatures below the melting point of the alloy, the resistivity dropped sharply if the alloy volume fraction reached 20 vol %. When the composites were processed at temperatures above the melting point, such phenomenon disappeared. According to the SEM and energy dispersive analysis X‐ray (EDAX) analyses, the size and dispersion of Sn–Pb alloy particles in composites changed when the hot‐pressing temperature reached the melting point of the alloy, which resulted in the different forms of resistivity–filler volume fraction curves. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1044–1050, 2000     

Electrical properties of poly(phenylene sulfide)/multiwalled carbon nanotube composites prepared by simple mixing and compression

Poly(phenylene sulfide) (PPS)/multiwalled carbon nanotubes (MWNTs) conductive composites were prepared through the simple mixing of PPS granules with MWNT powder and subsequent compression. The electrical properties as a function of MWNT loading clearly showed a low percolation threshold of about 0.22 vol % and a high critical exponent value of 3.55 for composites prepared by this method. A comparison study with composites prepared via melt mixing was also carried out, where a random dispersion of MWNTs was achieved. There existed a striplike morphology of MWNTs in the PPS matrix and MWNTs were selectively located in strips caused by compression. The effects of temperature and pressure on the conductivity of the PPS/MWNT composites as prepared via simple mixing and compression are discussed. In addition, the conductivity also showed a dependence on the flow direction of the compression, with higher conductivity in the direction parallel to the flow direction than in the direction perpendicular to the flow direction. So the relationship of the processing and morphological properties was investigated in detail. The possible conductive mechanisms of conventional melt blending and preparation via sample mixing and compression are also discussed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of carbon black on electrical property of graphite nanoplatelets/epoxy resin composites

Epoxy/graphite nanoplatelets (GNPs)/carbon black (CB) composites were prepared by liquid mixing method. The morphologies and microstructures of the composites were examined by scanning electron microscope and X‐ray diffraction. The results indicated that CB can improve effectively the dispersion of GNPs and form excellent conductive network in the matrix. When the weight ratio of GNPs to CB was 9:1 (total filler content was 1 wt%), the conductivity of the composite was three orders of magnitude higher than that of composites with GNPs alone (1 wt%). The percolation threshold of GNPs_0.9CB_0.1/epoxy resin composites was 0.5 wt. %, which was lower than that of composites with GNPs alone (1 wt%). The mechanism for the effect of CB on electrical property of GNPs/epoxy resin composites was also investigated. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers.     

Polyurethane/clay nanocomposites with improved helium gas barrier and mechanical properties: Direct versus master‐batch melt mixing route

Thermoplastic polyurethane (TPU)/clay nanocomposite films were produced by incorporation of organo‐modified montmorillonite clay (Cloisite 30B) in TPU matrix by two different melt‐mixing routes (direct and master‐batch‐based mixing), followed by compression molding. In master‐batch mixing where the master‐batch was prepared by mixing of clay and TPU in a solvent, better dispersion of clay‐layers was observed in comparison to the nanocomposites produced by direct mixing. As a consequence, superior mechanical and gas barrier properties were obtained by master‐batch mixing route. The master‐batch processing resulted in 284 and 236% increase in tearing strength and tearing energy, respectively, with 5 wt % clay‐loading. Interestingly, in case of master‐batch mixing, the tensile strength, stiffness as well as breaking extension increased simultaneously up to 3 wt % clay‐loading. The helium gas permeability reduced by about 39 and 31% for the TPU/clay nanocomposites produced by mater‐batch and direct mixing routes, respectively, at 3 wt % loading of clay. Finally, the gas permeability results have been compared using three different gas permeability models and a good correlation was observed at lower volume fraction of clay. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46422.     

Effect of styrene–acrylonitrile on the electrical resistivity of polycarbonate/multiwalled carbon nanotube composites

Multiwalled carbon nanotube (MWCNT)‐filled polycarbonate (PC)/styrene–acrylonitrile (SAN) blends with a wide range of blend compositions were prepared by melt mixing in a rotational rheometer, and the effect of SAN on the electrical properties of the PC/MWCNT composites was studied. The structure/electrical property relationship was investigated and explained by a combination of MWCNT localization and blend morphology. Transmission electron micrographs showed selective localization of MWCNTs in the PC phase, regardless of the blend morphology. When the SAN concentration was 10–40 wt %, which corresponded to sea‐island (10–30 wt %) and cocontinuous (40 wt %) blend morphologies (PC was continuous in both structures), the electrical resistivity decreased with increases in the SAN content. The concept of an effective volume concentration of MWCNTs was used to explain this effect. When the SAN concentration was 70 wt % or higher, the electrical resistivity was very high because MWCNTs were confined in the isolated PC particles. In addition, SAN was replaced by other polymers [polystyrene, methyl methacrylate/styrene, and poly(methyl methacrylate)]; these yielded similar blend morphologies and MWCNT localization and showed the generality of the concept of effective concentration in explaining a decrease in the electrical resistivity upon the addition of a second polymer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.