Cellulose acetate/multiwalled carbon nanotube nanocomposites with improved mechanical,thermal, and electrical properties

Cellulose acetate (CA)‐based nanocomposites with various contents of neat multiwalled carbon nanotube (MWCNT) or acid‐treated one (MWCNT‐COOH) are prepared via melt‐compounding method and investigated their morphology, thermal stability, mechanical, and electrical properties. SEM microphotographs reveal that MWCNT‐COOHs are dispersed uniformly in the CA matrix, compared with neat MWCNTs. FTIR spectra support that there exists a specific interaction between carboxyl groups of MWCNT‐COOHs and ester groups of CA, indicating good interfacial adhesion between MWCNT‐COOHs and CA matrix. Accordingly, thermal stability and dynamic mechanical properties of CA/MWCNT‐COOH nanocomposites were higher than those of CA/MWCNT composites. On the contrary, electrical volume resistivities of CA/MWCNT‐COOH nanocomposites are found to be somewhat higher than those of CA/MWCNT composites, which is because of the deterioration of graphene structures for MWCNT‐COOHs and the good dispersion of MWCNT‐COOHs in the CA matrix. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Multiwall‐carbon‐nanotube‐reinforced poly(ethylene terephthalate) nanocomposites by melt compounding

Poly(ethylene terephthalate) (PET) nanocomposites reinforced with multiwall carbon nanotubes (MWCNTs) were prepared through melt compounding in a twin‐screw extruder. The presence of MWCNTs, which acted as good nucleating agents, enhanced the crystallization of PET through heterogeneous nucleation. The incorporation of a small quantity of MWCNTs improved the thermal stability of the PET/MWCNT nanocomposites. The mechanical properties of the PET/MWCNT nanocomposites increased with even a small quantity of MWCNTs. There was a significant dependence of the rheological properties of the PET/MWCNT nanocomposites on the MWCNT content. The MWCNT loading increased the shear‐thinning nature of the polymer‐nanocomposite melt. The storage modulus and loss modulus of the PET/MWCNT nanocomposites increased with increasing frequency, and this increment effect was more pronounced at lower frequencies. At higher MWCNT contents, the dominant nanotube–nanotube interactions led to the formation of interconnected or networklike structures of MWCNTs in the PET/MWCNT nanocomposites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1450–1457, 2007     

Enhancement of dispersion of carbon nanotube and physical properties of poly(styrene‐co‐acrylonitrile)/multiwalled carbon nanotube nanocomposite via surface initiated ATRP

Dispersion behavior of multiwalled carbon nanotube (MWCNT), rheological and mechanical properties of various MWCNT/poly(styrene‐co‐acrylonitrile) (SAN) nanocomposites were investigated. MWCNT/SAN nanocomposites were prepared by three different methods; MWCNT/SAN melt blending, MWCNT/SAN in situ atom transfer radical polymerization (ATRP) and functionalized‐MWCNT/SAN in situ ATRP. Formation of SAN onto the surface of MWCNT and the molecular weight of grafted‐SAN were confirmed by fourier transform infrared spectra, ¹H‐NMR and ¹³C‐NMR. Crossover frequency of storage and loss modulus from rheological measurement and dynamic mechanical analysis showed that functionalized MWCNT/SAN in situ ATRP nanocomposite showed more uniform dispersion of MWCNT. Improved mechanical and electrical properties were observed for functionalized MWCNT/SAN in situ ATRP nanocomposite. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Correlation between compounding sequence and the properties of glass fiber‐Reinforced nylon‐6,6 composite

The effects of the compounding sequence and addition of maleic anhydride grafted polypropylene (PP‐g‐MAH) as a sizing agent on the properties of glass fiber (GF)/nylon‐6,6 composite were investigated. Mechanical properties of tensile, impact, and flexural strength were measured. The fractured surface was analyzed to compare the variation of interfacial characteristics by different compounding sequences and addition of a sizing agent. It was found that mechanical and rheological properties of a composite are strongly affected by the compounding sequence and the addition of a sizing agent. In general, the addition of PP‐g‐MAH results in lowering the mechanical properties compared to GF/nylon‐6,6, while proper compounding sequence results in improved mechanical properties. Lowering melt viscosity of composites is achieved by addition of sizing agent and varied depending on the compounding sequence. POLYM. ENG. SCI., 59:155–161, 2019. © 2018 Society of Plastics Engineers     

Ethylene vinyl acetate copolymer (EVA)/multiwalled carbon nanotube (MWCNT) nanocomposite foams

In this study, multiwalled carbon nanotube (MWCNT) and ethylene vinyl acetate copolymer (EVA) nanocomposite bulk foams were prepared for static dissipative applications by using melt compounding method, the most compatible with current industrial applications. Closed‐cell structure was verified with Scanning Electron Microscope. All the mechanical properties investigated improved with increasing content of MWCNT except elongation at break. At 5 phr of MWCNT, significant improvement of mechanical properties and compression set were observed. Also, the surface resistivity begins to decrease at 5 phr of MWCNT. Interestingly, the increase of surface resistivity of nanocomposite foams with 8 and 10 phr MWCNT were observed with increasing thickness of removed surface layers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Investigation of a postprocessing method to tailor the mechanical properties of carbon nanotube/polyamide fibers

The incorporation of carbon nanotubes to thermoplastic fibers can potentially improve mechanical, thermal and electrical properties. In this article, a methodology to tailor the mechanical properties of carbon nanotube/nylon fibers is presented. Multiwalled nanotubes (MWNT) were combined to polyamide 12 through melt compounding and twin‐screw extrusion. Pellets containing between 0 and 5.0 wt % MWNT were extruded and subsequently melt spun with a capillary rheometer to produce filaments. To further promote the alignment of the polymer chains and MWNTs, postdrawing parameters were systematically investigated: temperature, drawing speed and elongation. The best improvements in terms of elastic modulus and yield strength were measured at 140°C and 500% elongation, whereas drawing speed was shown to have a negligible effect. It was confirmed through electron microscopy and X‐ray diffraction that these enhancements were mainly induced by the alignment of the polymer chains along the fibers' axis. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4375–4382, 2013     

Effect of organoclay content on the mechanical properties of ethylene‐vinyl acetate copolymer/ multi‐walled carbon nanotube/organoclay foams

The main objective of this study is to obtain ethylene‐vinyl acetate copolymer (EVA)/multi‐walled carbon nanotube (MWCNT)/organoclay foams with improved mechanical properties without increase of their density, compared with EVA/MWCNT foams. MWCNT content was fixed at 5 phr in this study. To achieve the objective, EVA was melt‐mixed with MWCNTs and organoclays in a bench kneader. And the obtained EVA/MWCNT/organoclay mixtures were mixed with chemical blowing agent and cross‐linking agent in a two roll‐mill. After being mixed in a two roll‐mill, the mixtures were put in a mold and the foams were obtained by compression‐molding. The effect of organoclay content on the mechanical properties and surface resistivity of EVA/MWCNT (5 phr)/organoclay foams was investigated. The addition of 1 phr organoclays to the EVA/MWCNT (5 phr) foams resulted in the improvement of tensile strength, 100% tensile modulus, tear strength, and compression set without increase of the density. However, further increase in content of organoclay (3 phr) leaded to a deterioration of mechanical properties. Therefore, determining the optimal content of organoclay was very important in order to achieve the main objective of this study. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

Influence of aminosilane‐functionalized carbon nanotubes on the rheometric,mechanical, electrical and thermal degradation properties of epoxidized natural rubber nanocomposites

We describe the preparation, characterization and physical properties of multiwalled carbon nanotube (MWCNT)‐filled epoxidized natural rubber (ENR) composites. To ensure better dispersion in the elastomer matrix, the MWCNTs were initially subjected to aminopropyltriethoxysilane (APS) treatment to bind amine functional groups (?NH₂) on the nanotube surface. Successful grafting of APS on the MWCNT surface through Si–O–C linkages was confirmed using Fourier transform infrared spectroscopy. Grafting of APS on the MWCNT surface was further corroborated using elemental analysis. ENR nanocomposites with various filler loadings were prepared by melt compounding to generate pristine and APS‐modified MWCNT‐filled elastomeric systems. Furthermore, we determined the effects of various filler loadings on the rheometric, mechanical, electrical and thermal degradation properties of the resultant composite materials. Rheometric cure characterization revealed that the torque difference increased with pristine MWCNT loading compared to the gum system, and this effect was more pronounced when silane‐functionalized MWCNTs were loaded, indicating that this effect was due to an increase in polymer–carbon nanotube interactions in the MWCNT‐loaded materials. Loading of silane‐functionalized MWCNTs in the ENR matrix resulted in a significant improvement in the mechanical, electrical and thermal degradation properties of the composite materials, when compared to gum or pristine MWCNT‐loaded materials.© 2013 Society of Chemical Industry     

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

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

Evaluation of multiwalled carbon nanotubes as reinforcement for natural fiber‐based composites

This paper presents the effects of multi‐walled carbon nanotube (MWCNT) as reinforcing agent on some properties of natural fiber/polypropylene composites. In the sample preparation, MWCNT contents and fiber types (bagasse stalk and poplar) were used as variable parameters. The composites with different MWCNT contents were fabricated by melt compounding in a twin‐screw extruder and then by injection molding. The mass ratio of the wood flour to polymer was 40/60 (w/w). The mechanical properties of composites in terms of tensile, flexural, and Izod impact strength were evaluated. The morphology of the specimens was characterized using scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques. Based on the findings of this study, it appears that mechanical properties reached the maximum when 2.5 wt% MWCNT were used. However, addition of 3.5 wt% MWCNT could not enhance the mechanical properties considerably. TEM micrographs showed that at high level of MWCNT loading (3.5 wt%) increased population of MWCNT leads to agglomeration and stress transfer gets blocked. The mechanical properties of composites filled with poplar fibers were generally greater than bagasse stalk composites. POLYM. COMPOS., 37:3269–3274, 2016. © 2015 Society of Plastics Engineers     

The effect of multiwalled carbon nanotube dimensions on the morphology,mechanical, and electrical properties of melt mixed polypropylene‐based composites

The effect of multiwalled carbon nanotube (MWCNT) dimensions and surface modification on the morphology, mechanical reinforcement, and electrical properties of PP‐based composites, prepared by melt mixing, has been studied. The MWCNTs of small (d < 10 nm) and large (d = 40–60 nm) diameters with various intrinsic aspect ratios (L/d) have been used as filler. Transmission electron microscopy and very cold neutrons (VCN) scattering showed that both as‐received and surface modified small diameter MWCNT(1)s exhibit a strong tendency to bundle or cluster together in melt compared to both long MWCNT(3)s and short MWCNT(2)s large diameter nanotubes. The fractions of isolated nanotubes are higher and the mass‐fractal dimensions are lower for thick MWCNT‐based nanocomposites. The nanotubes of all types are heterogeneous nucleation sites for PP crystallization. The tensile and DMA testing results revealed that both long thick MWCNT(3)s with L/d ≈ 300 and thin MWCNT(1)s with highest intrinsic L/d > 1000 exhibit similar reinforcing effects, because drastically decreasing the effective aspect ratio (L/d)_eff of the thin flexibly nanotubes within polymer matrix. The nanocomposites based on the long large diameter MWCNT(3)s demonstrated the lowest percolation threshold equal to 1.5 vol % loading, highest dielectric and electromagnetic waves shielding properties. It was concluded that the choice of optimal diameter and length of MWCNTs is right approach to the improvement in the dispersion state and straightness of multiwelled carbon nanotubes in polymer melt as well as to enhancement of their efficiency as reinforcing and conductive nanosized filler. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of carbon nanotube‐supported β nucleating agent on the thermal properties,morphology, and mechanical properties of polyamide 6/isotactic polypropylene blends

A new kind of β nucleating agent, multi‐wall carbon nanotube (MWCNT)‐supported calcium pimelate was introduced into polyamide 6 (PA 6)/isotactic polypropylene (iPP; 10/90 by weight) blend and the thermal properties, morphology, and mechanical properties were investigated. The results showed that β‐iPP appeared at low content of MWCNT‐supported calcium pimelate which surmounted the α‐nucleating effect of PA 6 for iPP, and the content of β‐iPP increased with increasing content of MWCNT‐supported calcium pimelate. The impact strength, elongation at break, and flexural modulus were improved with increasing content of MWCNT‐supported calcium pimelate without significantly deteriorating the tensile strength. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Electrical and rheological percolation in poly(vinylidene fluoride)/multi‐walled carbon nanotube nanocomposites

Nanocomposites of poly(vinylidene fluoride) (PVDF) and multi‐walled carbon nanotubes (MWCNTs) were prepared through melt blending in a batch mixer (torque rheometer equipped with a mixing chamber). The morphology, rheological behavior and electrical conductivity were investigated through transmission electron microscopy, dynamic oscillatory rheometry and the two‐probe method. The nanocomposite with 0.5 wt% MWCNT content presented a uniform dispersion through the PVDF matrix, whereas that with 1 wt% started to present a percolated network. For the nanocomposites with 2 and 5 wt% MWCNTs the formation of this nanotube network was clearly evident. The electrical percolation threshold at room temperature found for this system was about 1.2 wt% MWCNTs. The rheological percolation threshold fitted from viscosity was about 1 wt%, while the threshold fitted from storage modulus was 0.9 wt%. Thus fewer nanotubes are needed to approach the rheological percolation threshold than the electrical percolation threshold. Copyright © 2010 Society of Chemical Industry     

Influence of processing condition and carbon nanotube on mechanical properties of injection molded multi‐walled carbon nanotube/poly(methyl methacrylate) nanocomposites

In this work, multi‐walled carbon nanotubes (MWCNT) and poly(methyl methacrylate) (PMMA) pellets were compounded via corotating twin‐screw extruder. The produced MWCNT/PMMA nanocomposite pellets were injection molded. The effect of MWCNT concentration, injection melt temperature and holding pressure on mechanical properties of the nanocomposites were investigated. To examine the mechanical properties of the MWCNT/PMMA nanocomposites, tensile test, charpy impact test, and Rockwell hardness are considered as the outputs. Design of experiments (DoE) is done by full factorial method. The morphology of the nanocomposites was performed using scanning electron microscopy (SEM). The results revealed when MWCNT concentration are increased from 0 to 1.5 wt %, tensile strength and elongation at break were reduced about 30 and 40%, respectively, but a slight increase in hardness was observed. In addition, highest impact strength belongs to the nanocomposite with 1 wt % MWCNT. This study also shows that processing condition significantly influence on mechanical behavior of the injection molded nanocomposite. In maximum holding pressure (100 bar), the nanocomposites show highest tensile strength, elongation, impact strength and hardness. According to findings, melt temperature has a trifle effect on elongation, but it has a remarkable influence on tensile strength. In the case of impact strength, higher melt temperature is favorable. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43738.     

Polystyrene composites containing crosslinked polystyrene‐multiwalled carbon nanotube balls

Crosslinked polystyrene‐multiwalled carbon nanotube (PS‐MWCNT) balls, which act as conductive microfillers, were prepared by the in situ suspension polymerization of styrene with MWCNTs and divinyl benzene (DVB) as a crosslinking agent. The diameters of the synthesized crosslinked PS‐MWCNT balls ranged from 10 to 100 μm and their electrical conductivity was about 7.7 × 10^?3 S/cm. The morphology of the crosslinked PS‐MWCNT balls was observed by scanning electron microscopy and transmission electron microscopy. The change in the chemical structure of the MWCNTs was confirmed by Raman spectroscopy and Fourier transform infrared spectroscopy. The mechanical and electrical properties of the PS/crosslinked PS‐MWCNT ball composites were investigated. It was found that the tensile strength, ultimate strain, Young's modulus, and impact strength of the PS matrix were enhanced by the incorporation of the crosslinked PS‐MWCNT balls. In addition, the mechanical properties of the PS/crosslinked PS‐MWCNT ball composites were better than those of the PS/pristine MWCNT composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Property investigation of polypropylene/multiwall carbon nanotube nanocomposites prepared via in situ polymerization

In this study, polypropylene/carbon nanotube nanocomposites were prepared via in situ polymerization using a bi‐supported Ziegler ? Natta catalytic system. In this system, magnesium ethoxide and multiwall carbon nanotubes (MWCNTs) are jointly used as catalyst supports. SEM images reveal the distribution and quite good dispersion of MWCNTs throughout the polypropylene (PP) matrix. The thermal properties of the samples were examined using DSC and TGA tests. The results show that the crystallization temperature of the nanocomposites significantly increases while the melting point is not markedly affected. In addition, the thermal stability is improved. The melt rheological properties of PP/MWCNT nanocomposites in the linear and nonlinear viscoelastic response regions were studied. An increment of the complex viscosity (η^*), storage modulus (G′) and loss modulus (G′′) and a decrement of the loss factor (tan δ) compared with neat PP are observed. Steady shear flow experiments show an increase in shear viscosity with increasing the MWCNT content. © 2013 Society of Chemical Industry     

Investigation of the rheological and conductive properties of multi-walled carbon nanotube/polycarbonate composites by positron annihilation techniques

The microstructure, rheological and conductive properties of multi-walled carbon nanotube (MWCNT)/polycarbonate (PC) composites were investigated by positron annihilation lifetime spectroscopy, positron annihilation coincidence Doppler broadening (CDB), oscillatory rheometry and electrical resistivity for different MWCNT contents. A 10 orders of magnitude increase in electrical conductivity was achieved with very small quantities of MWCNTs. CDB was used to determine a percolation threshold value, which was in good agreement with the electrical conductivity and rheological measurements. The results showed that with increasing MWCNT content, the composites underwent a phase transition from insulating to conducting at room temperature, which was attributed to the formation of a MWCNT network. The effect of MMCNTs on the microstructure of MWCNT/PC composites has been studied by positron annihilation lifetime measurements. The results showed that the fractional free volume decreased because of the MWCNTs and the formation of conductive network. The effects of MWCNT filler on the atomic scale free volume and mechanical property of MWCNT/PC composites were also discussed.     

Mechanical,rheological, and electrical properties of multiwalled carbon nanotube reinforced ASA/Na‐ionomer blend

Varying amounts of multiwalled carbon nanotubes (MWCNTs) was melt‐extruded with the acrylonitrile‐styrene‐acrylate (ASA)/Na‐ionomer blend, and mechanical, rheological, and electrical properties were studied Optical micrographs show good dispersion level at low MWCNT content and network formation at higher nanotubes percentage. DC conductivity model data shows percolation threshold reached at 1% MWCNT content and after percolation, two‐dimensional network structure was formed. The “peak and valley” type surface topology of matrix may be responsible for low percolation threshold limit. The polymer/nanotubes interactions at low MWCNT content increased the mechanical strengths, which were reduced by the network structure and agglomerates of nanotubes at higher nanotubes content. The MWCNTs interacted differently with the architecturally complex polymer chains and controlled chain dynamics accordingly. The Carreau‐Yasuda model was found fit to viscosity data and the model parameters data suggest the zero shear viscosity is function of MWCNTs content but the infinite shear viscosity is independent of nanoparticles content. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42516.     

Influence of modified carbon nanotube on physical properties and crystallization behavior of poly(ethylene terephthalate) nanocomposite

Poly(ethylene terephthalate) (PET) nanocomposites reinforced with a very small quantity of modified carbon nanotube (CNT) were prepared by melt compounding using a twin‐screw extruder. The introduction of carboxylic acid groups on the surfaces of the nanotube leads to the enhanced interactions between the nanotube and the polymer matrix through hydrogen bonding formation. The thermal stability, mechanical, and rheological properties of the PET nanocomposites are strongly dependent on the interfacial interactions between the PET and the modified CNT as well as the dispersion of the modified CNT in the PET. The introduction of the nanotube can significantly influence the non‐isothermal crystallization behavior of the PET nanocomposites. This study demonstrates that a very small quantity of the modified CNT can substantially improve the thermal stability and mechanical properties of the PET nanocomposites, depending on the dispersion of the modified CNT and the interfacial interactions between the polymer matrix and the modified CNT. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Rheology,crystallization behaviors,and thermal stabilities of poly(butylene succinate)/pristine multiwalled carbon nanotube composites obtained by melt compounding

Poly(butylene succinate) (PBS)/pristine raw multiwalled carbon nanotube (MWCNT) composites were prepared in this work via simple melt compounding. Morphological observations indicated that the MWCNTs were well dispersed in the PBS matrix. Moreover, the incorporation of MWCNTs did not affect the crystal form of PBS as measured by wide‐angle X‐ray diffraction. The rheology, crystallization behaviors, and thermal stabilities of PBS/MWCNT composites were studied in detail. Compared with neat PBS, the incorporation of MWCNTs into the matrix led to higher complex viscosities (|η*|), storage modulus (G′), loss modulus (G″), shear thinning behaviors, and lower damping factor (tan δ) at low frequency range, and shifted the PBS/MWCNT composites from liquid‐like to solid‐like, which affected the crystallization behaviors and thermal stabilities of PBS. The presence of a very small quantity of MWCNTs had a significant heterogeneous‐nucleation effect on the crystallization of PBS, resulting in the enhancement of crystallization temperature, i.e., with the addition of 0.5 wt % MWCNTs, the values of T_c of PBS/MWCNT composites could attain to 90°C, about 6°C higher than that of neat PBS, whereas the values of T_c increased slightly with further increasing the MWCNTs content. The thermogravimetric analysis illustrated that the thermal stability of PBS was improved with the addition of MWCNTs compared with that of neat PBS. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011