Combined effect of compatibilizer and carbon nanotubes on the morphology and electrical conductivity of PP/PS blend

In this work, maleic anhydride grafted styrene–ethylene–butadiene–styrene copolymer (SEBS‐g‐MA) and carbon nanotubes (CNTs) were introduced into the immiscible polypropylene/polystyrene (PP/PS) blend. Among the three polymer components, SEBS‐g‐MA has the strongest affinity to CNTs; thus, it exhibits dual effects to adjust the phase morphology of the blends and the dispersion state of CNTs in the blends. The experimental observations obtained from morphology characterizations using scanning electron microscope and transmission electron microscope confirm the selective localization of CNTs at the interface of the immiscible PP/PS blend. As a consequence, largely decreased percolation threshold is achieved when most of CNTs are selectively localized at the interface region between PP and PS. Copyright © 2014 John Wiley & Sons, Ltd.     

Effect of dispersion and selective localization of carbon nanotubes on rheology and electrical conductivity of polyamide 6 (PA6), Polypropylene (PP), and PA6/PP nanocomposites

Nanocomposites were prepared by adding 1–3 vol % multiwalled carbon nanotubes (MWCNTs) to polyamide 6 (PA6), polypropylene (PP), and their co‐continuous blends of 60/40 and 50/50 volume compositions. Because of the good interaction and interfacial adhesion to the PA6, nanotubes were disentangled and distributed evenly through nanocomposites containing PA6. In contrast, lack of active interactions between the matrix and the CNTs resulted in poor tube dispersion in PP. These observations were then verified by studying the rheology and electrical conductivity of their respective nanocomposites. Absence of percolated CNT clusters and possible wrapping of the tubes by PA6 resulted in low electrical conductivity of PA6/CNT nanocomposites. On the other hand, despite the weak dispersion of the tubes, electrical conductivities of PP/CNT nanocomposites were much higher than all other counterparts. This could be the result of good three‐dimensional distribution of the agglomerated bundles and secondary aggregation of tubes in PP. Adding CNTs to blends of PA6/PP (60/40 and 50/50) resulted in almost full localization of carbon nanotubes in PA6, leading to their higher effective concentration. At the same CNT loadings, the blend nanocomposites had three to seven orders of magnitude higher electrical conductivity than pure PA6. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 368–378     

Rheology,electrical conductivity,and the phase behavior of cocontinuous PA6/ABS blends with MWNT: Correlating the aspect ratio of MWNT with the percolation threshold

Multiwalled carbon nanotubes (purified, p‐MWNT and ～ NH₂ functionalized, f‐MWNT) were melt‐mixed with 50/50 cocontinuous blends of polyamide 6 (PA6) and acrylonitrile–butadiene–styrene in a conical twin‐screw microcompounder to obtain conductive polymer blends utilizing the conceptual approach of double‐percolation. The state of dispersion of the tubes was assessed using AC electrical conductivity measurements and melt‐rheology. The rheological and the electrical percolation threshold was observed to be ～ 1–2 wt % and ～ 3–4 wt %, respectively, for blends with p‐MWNT. In case of blends with f‐MWNT, the rheological percolation threshold was observed to be higher (2–3 wt %) than p‐MWNT but the electrical percolation threshold remained almost same. However, the absolute values were significantly lower than blends with p‐MWNT. In addition, significant refinement in the cocontinuous morphology of the blends with increasing concentration of MWNT was observed in both the cases. Further, an attempt was made to understand the underlying concepts in relation to cocontinuous morphologies that how the geometrical percolation threshold which adversely suffered because of the attrition of tubes under prolonged shear contributed further in retaining the rheological percolation threshold. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1619–1631, 2008     

Nucleation ability of multiwall carbon nanotubes in polypropylene composites

The nonisothermal crystallization of multiwall carbon nanotube (MWNT)/isotactic polypropylene (iPP) nanocomposites was investigated. The results derived from the differential scanning calorimetry curves (onset temperature, melting point, supercooling, peak temperature, half‐time of crystallization, and enthalpy of crystallization) were compared with those of neat iPP. The data were also processed according to Ozawa's theory and Dobreva's approach. These results and X‐ray diffraction data showed that the MWNTs acted as α‐nucleating agents in iPP. Accordingly, MWNT/iPP was significantly different from neat iPP: A fibrillar morphology was observed instead of the usual spherulites. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 520–527, 2003     

Surface morphology and electrical properties of polyurethane nanofiber webs spray‐coated with carbon nanotubes

Multiwalled carbon nanotubes (MWNTs) were spray‐coated on electrospun polyurethane nanofiber webs for electrical conductive application. For the effective coating of MWNTs, hyperbranched polyurethane (HBPU) was used by blending with linear polyurethane, which was synthesized in the A₂ + B₃ approach using poly(ε‐caprolactone)diol, 4,4′‐methylene bis(phenylisocynate), and castor oil. SEM measurements showed that the MWNTs could be coated well along the surface of nanofibers when the HBPU was blended in the linear polyurethane nanofibers. Blending of HBPU in the nanofibers also affected the electrical conductivity of MWNT‐coated nanofiber webs. The low electrical resistance from 20 to 400 Ω/sq was obtained for MWNT‐coated nanofiber webs and their electrical resistance decreased with an increase of spraying frequency. As a potential application of MWNT‐coated nanofiber webs, the electrical heating effect because of applied voltage was demonstrated. Copyright © 2011 John Wiley & Sons, Ltd.     

Enhanced electrical and mechanical properties of multiwall carbon nanotube rubber composites

Multiwall carbon nanotube‐filled elastomers are prepared by solution blending using a sonication process. It is shown that the processing conditions have a strong effect on the composite properties especially on electrical properties, which are very sensitive to nanotube dispersion within the elastomeric matrix. The percolation threshold is seen to be shifted to a lower nanotube content than that previously reported. With regard to the unfilled elastomer, large increases in the elastic and tensile moduli are obtained with the nanotube loading, thus highlighting the potential of this type of particles as reinforcing fillers for elastomeric matrices. Raman spectroscopy under strain has been used to evaluate the strength of the polymer–filler interface. Weak interfacial interactions are deduced, but the debundling of the nanotubes and the orientational effects of the polymeric chains are observed when the composite is submitted to a uniaxial deformation. Copyright © 2012 John Wiley & Sons, Ltd.     

Molecular motion,morphology, and thermal properties of multiwall carbon nanotube/polysilsesquioxane composite

Diglycidyl ether of bisphenol A (DGEBA)‐bridged polyorganosiloxane precursors have been prepared successfully by reacting diglycidyl ether of bisphenol A epoxy resin with 3‐aminopropyltriethoxysilane. Acid‐modified and unmodified multiwalled carbon nanotube (MWCNT) were dispersed in the diglycidyl ether of bisphenol A‐bridged polyorganosiloxane precursors and cured to prepare the carbon nanotube/diglycidyl ether of bisphenol A‐bridged polysilsesquioxane (MWCNT/DGEBA‐PSSQ) composites. The molecular motion of MWCNT/DGEBA‐PSSQ nanocomposites was studied by high‐resolution solid‐state ¹³C NMR. Acid‐modification can improve the affinity between MWCNT and the polymer matrix. The molecular motion of the DGEBA‐PSSQ decreased with acid‐modified MWCNT content. However, when unmodified MWCNT was used, the molecular motion of the DGEBA‐PSSQ was increased. SEM and TEM microphotographs confirm that acid‐modified MWCNT exhibits better dispersion than unmodified MWCNT in DGBEA‐PSSQ. The dynamic mechanical properties of acid‐modified MWCNT/DGBEA‐PSSQ composites are more favorable than those of unmodified MWCNT. T_g of the DGEBA‐PSSQ decreased from 174.0 °C (neat DGEBA‐PSSQ) to 159.0 °C (1 wt % unmodified MWCNT) and 156.0 °C (1 wt % acid‐modified MWCNT). The storage modulus (at 30 °C) of the DGEBA‐PSSQ increased from 1.23 × 10⁹ Pa (neat DGEBA‐PSSQ) to 1.65 × 10⁹ Pa (1 wt % acid‐modified MWCNT). However, when unmodified MWCNT was used, the storage modulus of the DGEBA‐PSSQ decreased to 6.88 × 10⁸ Pa (1 wt % unmodified MWCNT). At high temperature, above 150 °C, storage modulus of nanocomposites was higher than that of neat polymer system. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 472–482, 2008     

Aspect ratio effects of multi‐walled carbon nanotubes on electrical,mechanical, and thermal properties of polycarbonate/MWCNT composites

Two multi‐walled carbon nanotubes (MWCNTs) having relatively high aspect ratios of 313 and 474 with approximately the same diameter were melt mixed with polycarbonate (PC) in a twin‐screw conical micro compounder. The effects of aspect ratio on the electrical, mechanical, and thermal properties of the PC/MWCNT composites were investigated. Electrical conductivities and storage moduli of the filled samples are found to be independent of the starting aspect ratio for these high aspect ratio tubes; although the conductivities and storage moduli are still significantly higher than values of composites made with nanotubes having more commercially common aspect ratios of ～100. Transmission electron microscopy results suggest that melt‐mixing reduces these longer nanotubes to the same length, but still approximately two times longer than the length of commercially common aspect ratio tubes after melt‐mixing. Molecular weight measurements show that during melt‐mixing the longer nanotubes significantly degrade the molecular weight of the polymer as compared to very similar nanotubes with aspect ratio ～100. Because of the molecular weight reduction glass transition temperatures predictably show a large decrease with increasing nanotube concentration. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 73–83     

Effect of carbon nanotubes on mechanical and electrical properties of polyimide/carbon nanotubes nanocomposites

Multi-walled carbon nanotubes (MWNTs) reinforced polyimide nanocomposites were synthesized by in situ polymerization using 4,4′-oxydianilline, MWNTs, and pyromellitic dianhydride followed by casting, evaporation and thermal imidization. A homogeneous dispersion of chemically modified MWNTs was achieved in polyimide matrix as evidenced by scanning electron microscopy and atomic force microscopy. The incorporation of the modified MWNTs enhanced the mechanical properties of the polyimide due to the presence of strong interfacial interaction between the polymer matrix and the nanotubes in polymer composites. The resultant polyimide/MWNTs nanocomposites were electrically conductive with significant conductivity enhancement at 3 wt% MWNTs, which is favorable for many practical uses.     

Complementary effects of multiwalled carbon nanotubes and conductive carbon black on polyamide 6

This article introduces a newly innovative idea for preparation of superconductive ternary polymeric composites of polyamide 6 (PA6), conductive carbon black (CCB), and multiwalled carbon nanotubes (MWCNTs) with different weight ratios by a melt‐mixing technique. The complementary effects of CCB and MWCNTs at different compositions on rheological, physical, morphological, thermal, and dynamic mechanical and electrical properties of the ternary composites have been examined systematically. We have used a novel formulation to produce high‐weight fraction ternary polymer composites that show extremely higher conductivity when compared with their corresponding binary polymer composites at the same carbon loading. For example, with an addition of 10 wt % MWCNTs into the CCB/PA6 composite preloaded with 10 wt % CCB, the electrical conductivity of these ternary composites was about 5 S/m, which was 10 times that of the CCB/PA6 binary composite (0.5 S/m) and 125 times that of the MWCNT/PA6 binary composite (0.04 S/m) at 20 wt % carbon loading. The incorporation of the MWCNTs effectively enhanced the thermal stability and crystallization of the PA6 matrix in the CCB/PA6 composites through heterogeneous nucleation. The MWCNTs appeared to significantly affect the mechanical and rheological properties of the PA6 in the CCB/PA6 composites, a way notably dependent on the MWCNT contents. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1203–1212, 2010     

Model for thermal conductivity of composites with carbon nanotubes

This paper presents a model for evaluation of effective thermal conductivity for the composites with carbon nanotubes (CNT) having log-normal function of distribution of CNT, with direct effect over depolarization factor. The CNT are considered having cylindrical shape with L/d ratio very high. The model parameters are calculated in function of the data from literature. The influence of volume fraction of reinforced materials, of the aspect ratio of the particles included and of the ratio of the two thermal conductivities is presented.     

Characterization and electrical transport properties of polyaniline and multiwall carbon nanotube composites

Polyaniline/multiwalled carbon nanotube (PANI/MWNT) composites were prepared by in situ polymerization. Scanning electron microscope, X‐ray diffraction, Fourier transform infrared, Uv‐Visible spectroscopy, Fluorescence spectrophotometry were done to characterize the PANI/MWNT composites. Thermal stability was measured by thermogravimetry analysis. The thermal stability of PANI/MWNT composites becomes higher than PANI. Electrical transport properties of different PANI/MWNT composites were investigated in the temperature range 77 ≤ T ≤ 300 K with and without magnetic field up to 1 T. The dc resistivity of PANI/MWNT composites shows different behavior compared to the sample without MWNT. The room temperature dc magnetoconductivity of the samples is negative; however, its sign changes to positive by lowering the temperature, which has been explained by hopping type charge transport. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1767–1775, 2010     

On the effects of morphology and molecular composition on the electrical strength of polyethylene blends

The effects of morphology and molecular composition on the electrical strength of blends of linear and branched polyethylenes were investigated. A range of blend systems were considered, in which both the molecular mass of the linear polymer and the comonomer in the branched component were varied. All the blends contained 10% linear polyethylene and 90% branched polymer and, in each system, three crystallization procedures were employed to modify the morphology. Isothermal crystallization at 124 °C generally resulted in compact linear inclusions within a branched matrix; isothermal crystallization at 115 °C produced a space‐filling network of open, spherulitic structures; and quenching gave a banded spherulitic morphology. In these systems, the electrical strength, as measured by ramp testing, was dependent on the morphology of the material but was not influenced per se by significant changes in the molecular composition of the blend. The effect of crosslinking was also examined; the inclusion of a network did not, in itself, affect the breakdown strength or the morphology. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2309–2322, 2000     

Modification of multiwall carbon nanotubes via soap‐free emulsion polymerization of acrylonitrile

A novel method for the synthesis of polyacrylonitrile (PAN)‐coated multiwall carbon nanotubes (MWCNTs) via a simple soap‐free emulsion polymerization is presented for the first time. The polymerization was initiated with conventional anionic ammonium persulfate (APS) at 65 °C. The modification of PAN on MWCNT surfaces was confirmed by Fourier‐transform infrared (FT‐IR) spectroscopy, X‐ray photoelectron spectra (XPS), transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), and Raman spectroscopy. It is found that all the surfaces of the MWCNTs were coated by PAN chains, and the PAN coating thickness could be controlled by simply adjusting the polymerization time. The obtained PAN‐coated MWCNTs could be well dispersed in water. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2057–2062, 2010     

Multi‐walled carbon nanotubes encapsulated with polyurethane and its nanocomposites

Poly(acryloyl chloride) (PACl) was employed to enhance the surface of multi‐walled carbon nanotubes (MWCNTs). MWCNTs were first acid treated to generate hydroxyl groups on the surface, which was reacted with PACl to obtain an encapsulation. The numerous acryloyl chloride groups on the out layer were esterified with a proper amount of ethylene glycol (EG). Subsequently, 4,4′‐methylenebis (phenylisocyanate) (MDI) and 1,4‐butanediol (BDO) were introduced into the system, and a polyurethane (PU) layer was formed in situ. The formation of PU layers on MWCNTs was confirmed by Fourier transform infrared spectrometer (FTIR) and X‐ray photoelectron spectroscope (XPS). The morphology of encapsulated MWCNTs was observed by transmission electron microscope (TEM) and scanning electron microscope (SEM). Thermo gravimetric analysis (TGA) showed the grafted polymer fraction was up to 90%. On introducing the modified MWCNTs into a PU matrix, an increase in tensile strength by 60.6% and improvement in modulus by 6.3% over neat PU was observed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4857–4865, 2008     

Significant enhancement of electrical and thermal conductivities of polyethylene carbon nanotube composites by the addition of a low amount of silver nanoparticles

Electrically and thermally conductive high‐density polyethylene composites filled with hybrid fillers, multiwall carbon nanotubes (MWCNTs) and silver nanoparticles (Ag‐NPs), have been prepared in the melt state. The investigation of their electrical and thermal conductivities while comparing with high‐density polyethylene/MWCNT binary composites shows that the addition of only 3 vol% of Ag‐NPs does not reduce the electrical percolation threshold (P_c) that remains as low as 0.40 vol% of MWCNTs but leads to an increase in the maximum dc electrical conductivity of PE/MWCNT composites by two orders of magnitudes. Moreover, the association of both Ag‐NPs and carbon nanotube particles improved our composite's thermal conductivity. Copyright © 2014 John Wiley & Sons, Ltd.     

类金刚石碳薄膜对碳膜导电性能的影响

以聚酰亚胺薄膜为原料,经炭化形成碳膜;进而在碳膜表面制备了类金刚石碳(DLC)薄膜,研究了制备条件对碳膜导电性能的影响.采用扫描电镜分析了薄膜的表面形貌和微观结构;采用X射线衍射仪分析了薄膜的晶体结构.结果表明,DLC薄膜的电阻率随着沉积时间的延长先减小后增加;当沉积时间达到3 h时,相应DLC薄膜的电阻率达到最小值5.66×10-5Ω.m.     

Synthesis and characterization of conducting polythiophene/carbon nanotubes composites

Conducting polythiophene (PTh)/single‐wall carbon nanotubes (SWNTs) composites were synthesized by the in situ chemical oxidative polymerization method. The resulting cablelike morphology of the composite (SWNT–PTh) structures was characterized with elemental analysis, X‐ray photoelectron spectroscopy, Raman spectroscopy, Fourier transform infrared, ultraviolet–visible spectroscopy, field emission scanning electron microscopy, thermogravimetric analysis, X‐ray diffraction, and transmission electron microscopy. The standard four‐point‐probe method was used to measure the conductivity of the samples. Field emission scanning electron microscopy and transmission electron microscopy analysis revealed that the SWNT–PTh composites were core (SWNTs) and shell (PTh) hybrid structures. Spectroscopic analysis data for the composites were almost identical to those for PTh, supporting the idea that SWNTs served as templates in the formation of a coaxial nanostructure for the composites. The physical properties of the composites were measured and also showed that the SWNTs were modified by conducting PTh with an enhancement of various properties. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5283–5290, 2006     

Selective localization of organoclay and effects on the morphology and mechanical properties of LDPE/PA11 blends with distributed and co‐continuous morphology

A study was made on the effect of small amounts of organically modified clay on the morphology and mechanical properties of blends of low‐density polyethylene and polyamide 11 at different compositions. The influence of the filler on the blend morphology was investigated using wide angle X‐ray diffractometry, scanning and transmission electron microscopy and selective extraction experiments. The filler was found to locate predominantly in the more hydrophilic polyamide phase. Although such uneven distribution does not have a significant effect on the onset of phase co‐continuity of the polymer components, it brings about a drastic refinement of the microstructure for the blends both with droplets/matrix and co‐continuous morphologies. In addition to the expected reinforcing action of the filler, the resulting fine microstructure plays an important role in enhancing the mechanical properties of the blends. This is essentially because of a good quality of stress transfer across the interface between the constituents, which also seems to benefit for a good interfacial adhesion promoted by the filler. Our results provide the experimental evidence for the capabilities of nanoparticles added to multiphase polymer systems to act selectively as a reinforcing agent for specific domains of the material and as a medium able to assist the refinement of the polymer phases during mixing. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 600–609, 2010     

Effects of carbon nanotubes on polymer physics

A single carbon nanotube has many similarities with an individual polymer chain including the fact that the end‐to‐end length of both are often about the same and the diameter of the chain is about the same (for single‐walled nanotubes) or only ～10 to 20 times larger (for multiwalled nanotubes). The combination of the solid surface and the similarity of the two materials means that polymer physics are altered in manners not seen with any other type of commonly used filler. The purpose of this review is to update a chapter that appears in a recent tome by Grady (2011) and describe how polymer physics is altered in composites that contain carbon nanotubes. Subjects that will be discussed include chain configuration, glass transition, polymer diffusion, unit cells and crystalline superstructure (lamellae, spherulites and shish‐kebabs), and crystallization kinetics. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012