Synthesis and characterization of multiwall carbon nanotube/waterborne polyurethane nanocomposites

The preparation of thermoplastic nanocomposites of waterborne polyurethane (WBPU) and multiwall carbon nanotubes (MWCNTs) via an in situ polymerization approach is presented. The effects of the presence and content of MWCNTs on the morphology and thermal, mechanical and electrical properties of the nanocomposites were investigated. Carbon nanotubes were modified with amide groups in order to enhance their chemical affinity towards WBPU. Thermogravimetric studies show enhanced thermal stability of the nanocomposites. Scanning and transmission electronic microscopy images prove that functionalized carbon nanotubes can be effectively dispersed in WBPU matrix. Mechanical properties reveal that Young's modulus and tensile strength tend to increase when appropriate amounts of MWCNTs are loaded due to the reinforcing effect of the functionalized carbon nanotubes. Thermal properties show an increase in the glass transition temperature and storage modulus with an increase in MWCNT content. X‐ray diffraction reveals better crystallization of the WBPU in the presence of MWCNTs. The WBPU/MWCNT nanocomposite film containing 1 wt% of MWCNTs exhibits a conductivity nearly five orders of magnitude higher than that of WBPU film. © 2017 Society of Chemical Industry     

Influence of intercalated organoclay on the phase structure and physical properties of PTT–PTMO block copolymers

Poly(trimethylene terephthalate-block-tetramethylene oxide) (PTT–PTMO) copolymer/organoclay nanocomposites were prepared by in situ polymerization. They showed an intercalated silicate structure, as determined by X-ray diffraction and transmission electron microscopy. The influence of intercalated organoclay on the two-phase structure and mechanical properties of PTT–PTMO block copolymer was examined by using DSC and tensile tests. The DSC results imply that the silicate layers (Nanofil 32) in PTT–PTMO act as nucleation agents and accelerate the crystallization of PTT hard phase during the cooling down process from the melt. The introduction of silicate layers does not have great effect on the glass transition temperature of PTMO-rich soft phase, melting temperature of PTT hard phase, and degree of crystallinity of the nanocomposites. As the organoclay loading in the nanocomposites increase, the enhanced tensile modulus and yield stress was observed. The cyclic tensile tests showed that obtained nanocomposites have values of permanent set comparable to the neat PTT–PMO copolymer.     

Synergistic effect of three‐dimensional multi‐walled carbon nanotube–graphene nanofiller in enhancing the mechanical and thermal properties of high‐performance silicone rubber

The homogeneous dispersion of nanofillers and filler–matrix interfacial interactions are important factors in the development of high‐performance polymer materials for various applications. In the present work, a simple solution‐mixing method was used to prepare multi‐walled carbon nanotube (MWCNT)–graphene (G) (3:1, 1:1, 1:3) hybrids followed by their characterization through wide‐angle X‐ray diffraction, transmission electron microscopy and thermogravimetric analyses. Subsequently, MWCNT–G (1:1) hybrid was used as reinforcing filler in the formation of silicone rubber (VMQ) nanocomposites by solution intercalation, and their morphology and properties were investigated. Our findings showed that MWCNT–G (0.75 wt%)/VMQ composite exhibited significant improvements in tensile strength (110%) and Young's modulus (137%) compared to neat VMQ. The thermal stability of MWCNT–G (1 wt%)/VMQ was maximally improved by 154 °C compared to neat VMQ. Differential scanning calorimetry demonstrated the maximum improvement of glass transition temperature (4 °C), crystallization temperature (8 °C) and melting temperature (5 °C) for MWCNT–G (1 wt%)/VMQ nanocomposite with respect to neat VMQ. Swelling measurements confirmed that the crosslink density and solvent resistance were a maximum for hybrid nanocomposites. Such improvements in the properties of MWCNT–G/VMQ nanocomposites could be attributed to a synergistic effect of the hybrid filler. © 2013 Society of Chemical Industry     

Nanocomposites of poly(vinylidene fluoride) with multiwalled carbon nanotubes

The preparation and characterization of nanocomposites of poly(vinylidene fluoride), PVDF, with acid treated multiwalled carbon nanotubes (MWCNT) with a wide composition range, from 0.1 to 5.0% MWCNT by weight, is reported. Effect of uniaxial orientation by zone drawing on these nanocomposites is discussed and compared with unoriented compression molded films. Static room temperature two‐dimensional wide angle X‐ray scattering and Fourier transform infrared spectroscopy were used for phase identification. Differential scanning calorimetry, polarizing optical microscopy, dynamic mechanical analysis (DMA), and thermogravimetic analysis (TGA) were used to study the thermal and mechanical properties. Incorporation of MWCNT into PVDF has no obvious effect in forming beta phase crystal in the PVDF/MWCNT bulk films, while zone drawing cause a significant alpha to beta transition in PVDF/MWCNT. Results indicate that MWCNTs act as nucleation agent during crystallization and slightly increase the degree of crystallinity of PVDF/MWCNT bulk films. TGA indicates the thermal stability is improved when MWCNT concentration increases for unoriented PVDF/MWCNT film. The modulus also increases significantly when MWCNT concentration increases. The glass transition temperature measured by the peak position of tanδ from DMA does not change with MWCNT concentration, but a slightly higher glass transition can be obtained by zone drawing. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Ethylene vinyl acetate/ethylene propylene diene terpolymer‐blend‐layered double hydroxide nanocomposites

Ethylene vinyl acetate (EVA‐45)/ethylene propylene diene terpolymer (EPDM) blend‐layered double hydroxide (LDH) nanocomposites have been prepared by solution blending of 1:1 weight ratio of EVA and EPDM with varying amounts of organo LDH (DS‐LDH). X‐ray diffraction and transmission electron microscopy analysis suggest the formation of partially exfoliated EVA/EPDM/DS‐LDH nanocomposites. Measurement of mechanical properties of the nanocomposites (3 wt% DS‐LDH content) show that the improvement in tensile strength and elongation at break are 35 and 12% higher than neat EVA/EPDM blends. Dynamic mechanical thermal analysis also shows that the storage modulus of the nanocomposites at glass transition temperature is higher compared to the pure blend. Such improvements in mechanical properties have been correlated in terms of fracture behavior of the nanocomposites using scanning electron microscopy analysis. Thermal stability of the prepared nanocomposites is substantially higher compared to neat EVA/EPDM blend, confirming the formation of high‐performance polymer nanocomposites. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Study on glass transition temperature and mechanical properties of cadmium sulfide/polystyrene nanocomposites

The cadmium sulfide/polystyrene (CdS/PS) nanocomposites with concentration (0, 2, 4, 6, and 8) wt% of CdS nanoparticles were prepared by solution casting method and characterized through fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM) measurements. The particle size of nanoparticles is found to be around 15 nm. Glass transition and mechanical behavior of CdS/PS nanocomposites were investigated using dynamic mechanical analyzer (DMA). The mechanical properties such as Young's modulus and tensile strength were determined at room, as well as at elevated temperatures through their stress–strain curves. The result shows that glass transition temperature (T_g) is shifted toward the higher temperature after the addition of CdS nanoparticles. The mechanical properties increased at low wt% loading of CdS nanoparticles and decreased for higher wt% loading of CdS nanoparticles. It was also found that mechanical properties decline with increase in the temperature. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

High‐performance electromagnetic interference shielding material based on an effective mixing protocol

A facile and economic method is developed for the fabrication of new lightweight materials with high electromagnetic interference (EMI) shielding performance, good mechanical properties and low electrical percolation threshold through melt mixing. Electrical properties, DC conductivity, EMI shielding performance and mechanical properties of poly(trimethylene terephthalate) (PTT)/multiwalled carbon nanotube (MWCNT) nanocomposites with varying filler loading of MWCNTs were investigated. High‐resolution transmission electron microscopy was used to determine the distribution of MWCNTs in the PTT matrix. The newly developed nanocomposites show excellent dielectric and EMI shielding properties. Theoretical electrical percolation threshold was achieved at 0.21 wt% loading of MWCNTs, due to the high aspect ratio and the three‐dimensional network formation of MWCNTs. Experimental DC conductivity values were compared with those of theoretical models such as the Voet, Bueche and Scarisbrick models, which showed good agreement. The PTT/3% MWCNT composite showed an EMI shielding value of ～38 dB (99.99% attenuation) with a sample thickness of 2 mm. Power balance was used to determine the actual contribution of reflection, absorption and transmission loss to the total EMI shielding value. The nanocomposites showed good tensile and impact properties and the composite with 2% MWCNTs exhibited an improvement in tensile strength of as much as 96%. © 2018 Society of Chemical Industry     

Polyaniline nanorod adsorbed on reduced graphene oxide nanosheet for enhanced dielectric,viscoelastic and thermal properties of epoxy nanocomposites

In this work, polyaniline nanorod adsorbed on reduced graphene oxide (P@G) hybrid filler was prepared via in situ polymerization of aniline monomer in the presence of reduced graphene oxide as template. Fourier transform infrared, X-ray diffraction, field emission scanning electron microscopy, and high-resolution transmission electron microscopy images revealed the formation of P@G hybrid. The P@G hybrid was dispersed in dichlorobenzene and then introduced into epoxy resin at different loadings. The epoxy nanocomposites containing 9 wt% P@G hybrids (E/P@G9) exhibited a maximum DC conductivity of 1.34 × 10⁻⁵ S/cm that is eight orders higher compared to pure epoxy. At 10³ Hz, a dielectric constant (ε′) of 163 was attained for E/P@G9, nearly 34 times higher than pure epoxy. A percolation threshold of 4 vol% was observed for ε′. Dynamic mechanical studies showed that significant enhancement in storage modulus values were exhibited for 3 and 5 wt% of hybrids. The glass transition temperature showed a maximum shift of 10°C to higher temperatures at 3 wt% loading of P@G hybrids (E/P@G3). The tensile strength, Young's modulus, and impact strength of the E/P@G3 nanocomposites enhanced by 19.7, 72, and 12%, respectively. The thermal stability of the epoxy nanocomposites also enhanced with the addition of P@G hybrid.     

Effect of multiwall carbon nanotubes on thermomechanical and electrical properties of poly(trimethylene terephthalate)

Multiwalled carbon nanotubes (MWCNTs) were synthesized using chemical vapor deposition and poly(trimethylene terephthalate) (PTT)/MWCNT composites with varying amounts of MWCNTs were prepared by melt compounding using DSM micro‐compounder. Morphological characterization by SEM and TEM showed uniform dispersion of MWCNTs in PTT matrix upto 2% (w/w) MWCNT loading. Incorporation of MWCNTs showed no effect on percent crystallinity but affected the crystallite dimensions and increased the crystallization temperature. Dynamic mechanical characterization of composites showed an increase in storage modulus of PTT upon incorporation of MWCNTs above glass transition temperature. The electrical conductivity of PTT/MWCNT composites increased upon incorporation of MWCNTs and percolation threshold concentration was obtained at a loading of MWCNTs in the range of 1–1.5% (w/w). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Aramid–multiwalled carbon nanotube nanocomposites: effect of compatibilization through oligomer wrapping of the nanotubes

Aramid–multiwalled carbon nanotube (MWCNT) nanocomposites with different CNT loadings were prepared by the solution‐blending technique. Aramid oligomeric chains having reactive amine end‐groups were covalently grafted and wrapped over the surface of acid‐functionalized MWCNTs. The presence of functional groups and surface modification of MWCNTs were studied using Raman, Fourier transform infrared and X‐ray photoelectron spectroscopic and transmission/scanning electron microscopic techniques. Addition of these MWCNTs resulted in a homogeneous dispersion throughout the aramid matrix. Dynamic mechanical thermal analysis showed an increase in the storage modulus and the glass transition temperature involved with α‐relaxations on CNT loading. The coefficient of thermal expansion (CTE) of aramid was reduced on loading with such CNTs. Strong interfacial interactions of the matrix with the surface‐modified CNTs reduced the stress‐transfer problem in the composite material and resulted in higher modulus of 4.26 GPa and a glass transition temperature of 338.5 °C, whereas the CTE was reduced to 101.8 ppm °C^?1 on addition of only 2.5 wt% CNTs in the aramid matrix. © 2016 Society of Chemical Industry     

Amino functionalization of multiwalled carbon nanotubes by gamma ray irradiation and its epoxy composites

In this paper, γ‐ray radiation technique was utilized to simply functionalize multi‐walled carbon nanotube (MWCNT) with amino groups. The successful amino functionalization of MWCNTs (MWCNTs‐Am) was proven and the physicochemical properties of MWCNTs before and after radiation grafting modifications were characterized using FT‐IR, X‐ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). The results indicated that the γ‐ray radiation had the visible effects on the surface properties of MWCNTs. The effects of various functionalized MWCNTs on morphological, thermal, and mechanical properties of an epoxy‐based nanocomposite system were investigated. Utilizing in situ polymerization, 1 wt% loading of MWCNT was used to prepare epoxy‐based nanocomposites. Compared to the neat epoxy system, nanocomposites prepared with MWCNT‐Am showed 13.0% increase in tensile strength, 20.0% increase in tensile modulus, and 24.1% increase in thermal decomposition temperature. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

Mechanical properties and structures of dicyanate–clay nanocomposites

Dicyanate–clay nanocomposites comprising a dicyanate resin and a type of organically modified clay were prepared and characterized, and their thermomechanical properties were investigated. The organically modified clay had silicate layers of nanometer size intercalated with an organic modifier, which improved the compatibility between the clay and organic materials, such as dicyanate resins. Dynamic mechanical analysis was performed to investigate the thermomechanical properties of the dicyanate–clay nanocomposites containing various amounts of the clay. The storage modulus of the nanocomposites below their glass‐transition temperatures slightly increased with increasing clay content. The glass‐transition temperature of the dicyanate–clay nanocomposites increased with increasing clay content. The nanostructures of the dicyanate–clay nanocomposites were characterized by transmission electron microscopy and X‐ray diffraction analysis. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2629–2633, 2003     

Functionalization of carbon nanotubes with (3‐glycidyloxypropyl)‐trimethoxysilane: Effect of wrapping on epoxy matrix nanocomposites

In this work, multiwalled carbon nanotubes (MWCNT), after previous oxidation, are functionalized with excess (3‐glycidyloxypropyl)trimethoxysilane (GLYMO) and used as reinforcement in epoxy matrix nanocomposites. Infrared, Raman, and energy‐dispersive X‐ray spectroscopies confirm the silanization of the MWCNT, while transmission electron microscopy images show that oxidized nanotubes presented less entanglement than pristine and silanized MWCNT. Thickening of the nanotubes is also observed after silanization, suggesting that the MWCNT are wrapped by siloxane chains. Field‐emission scanning electron microscopy reveals that oxidized nanotubes are better dispersed in the matrix, providing nanocomposites with better mechanical properties than those reinforced with pristine and silanized MWCNT. On the other hand, the glass transition temperature of the nanocomposite with 0.05 wt % MWCNT‐GLYMO increased by 14 °C compared to the neat epoxy resin, suggesting a strong matrix–nanotube adhesion. The functionalization of nanotubes using an excess amount of silane can thus favor the formation of an organosiloxane coating on the MWCNT, preventing its dispersion and contributing to poor mechanical properties of epoxy nanocomposites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44245.     

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.     

Mechanical and Thermal Properties Modeling,Sorption Characteristics of Multiscale (Multiwalled Carbon Nanotubes/Glass Fiber) Filler Reinforced Polypropylene Composites

The present work was aimed to investigate the individual and hybrid reinforcement effect of multiscale fillers [glass fibers (GF)/multiwalled carbon nanotubes (MWCNTs)] in polypropylene (PP) matrix. The MWCNT content in the hybrid composites was varied from 0.5 to 5 wt%, and glass fiber fraction was fixed as 20 wt%. The morphology of nano and hybrid composite revealed reasonable dispersion of MWCNTs and glass fibers in the matrix. At a MWCNT content of 3 wt%, the optimum tensile properties for the hybrid composites were achieved and beyond which it declined due to agglomeration effects as revealed by transmission electron microscopy. A comparative study of the experimental and predicted values of moduli of nano, micro, and hybrid composites using various micromechanical models was conducted. The simultaneous incorporation of MWCNTs and glass fibers in PP restricted the mobility of polymer chains as indicated by the increase in storage modulus and rise in glass transition temperature obtained by dynamic mechanical analysis. The differential scanning calorimetry studies indicated that the inclusion of 2 wt% of MWCNTs increased the crystallinity of PP from 58.2 to 69.1% in hybrid composites. The Avrami and Mo models were used to explore nonisothermal crystallization kinetics, and Mo model was in close agreement with the experimental results. The sorption behavior of the composites revealed that the formation of immobilized regions developed by the simultaneous inclusion of micro and nano fillers delayed the transport of the solvent. J. VINYL ADDIT. TECHNOL., 25:E94–E107, 2019. © 2019 Society of Plastics Engineers     

Preparation and properties of in‐situ polymerized polyurethane/stearate intercalated layer double hydroxide nanocomposites

The present work deals with the effect of stearate intercalated layered double hydroxide (St‐LDH) loadings on the morphological, mechanical, thermal, adhesive and flame retardant properties of polyurethane (PU)/St‐LDH nanocomposites prepared by the in situ polymerization method. X‐ray diffraction and transmission electron microscopy studies confirmed that exfoliation takes place at 3 wt% loading followed by intercalation at higher filler loadings in the PU matrix. The exfoliated structure has been further verified by atomic force microscopy. The measurements of stress‐strain, thermogravimetric analysis, dynamic mechanical analysis, lap shear strength and peel strength analysis showed that the nanocomposites containing 3 wt% St‐LDH exhibit excellent improvement in tensile strength (ca 175%) and log storage modulus (ca 14%), while PU/St‐LDH (5 wt%) possesses optimum improvement in glass transition temperature (ca 6 °C), lap shear strength (200%) and peel strength (130%) over neat PU. In addition, the gradual improvements in limiting oxygen index value with St‐LDH loading indicated the higher effectiveness in providing better barrier properties as well as better flame retardant behavior. Copyright © 2012 Society of Chemical Industry     

Effect of bone ash fillers on mechanical and thermal properties of biobased epoxy nanocomposites

In this study, the fabrication and characterization of bone ash filled biobased epoxy resin (Super SAP 100/1000, contains 37% biobased carbon content) nanocomposites are presented. Biosource bone ash was modified by size reduction and surface modification processes using a combination of ball milling and sonochemical techniques and characterized using X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The modified bone ash particles were incorporated into biobased epoxy with noncontact mixing process. The as-fabricated nanocomposites were characterized using various thermal and mechanical analyses. The nanocomposites showed significant improvement in flexural strength (41.25%) and modulus (34.56%) for 2 wt% filler loading. Dynamic mechanical analysis (DMA) results showed improvement in both storage modulus and loss modulus. Additionally, DMA results showed a slight reduction in glass transition temperature which also complies with differential scanning calorimetry results. Thermomechanical analysis results showed a reduction in the coefficient of thermal expansion. Thermogravimetric analysis results showed improved thermal stability at both onset of degradation and the major degradation. These enhanced thermal and mechanical performances of the epoxy nanocomposites allows them to be suitable for lightweight aerospace, automotive, and biomedical applications.     

Influence of applying microwave radiation on the LDPE/MWCNTs nanocomposite

Low density polyethylene (LDPE) and multiwall carbon nanotube (MWCNT) nanocomposites of varying MWCNT contents were prepared by melt blending and compression molding. The sample sheets were exposed to microwave irradiation and the effect on chemical, mechanical, and thermal properties as well as the sheets' morphology were determined and compared with that of nonirradiated samples with similar compositions. The percentage crystallinity of the LDPE/MWCNT nanocomposites declined after irradiation due to the degradation of polymeric chains. However, the melting temperature was hardly changed. The chemical degradation due to irradiation was also verified from the increase in the carbonyl index as determined from the Fourier transformed‐infrared spectroscopy study and the decline in the storage modulus of the dynamic mechanical analysis study. The microcalorimetry study revealed that the MWCNT nanofillers were effectively acting as a heat absorption shield by reducing the heat release rate of polymer during combustion. The Raman spectra and scanning electron microscopy photographs demonstrated improved interaction of MWCNT with the LDPE matrix after microwave irradiation. POLYM. COMPOS., 35:2036–2042, 2014. © 2014 Society of Plastics Engineers     

Dynamic mechanical characterization of PC/MWCNT composites under variable temperature conditions

A dynamic mechanical analysis has been performed on composite materials of polycarbonates (PC) and multi-walled carbon nanotubes (MWCNT) for evaluation of their mechanical hardness and storage modulus under the combined effects of variable loading frequencies and temperature conditions. The PC-based engineering machine components that are subjected to variable external loads and temperature conditions are not durable owing to the viscoelastic properties of PC. Composites of PC with MWCNT (2, 5 and 10 wt%) were fabricated and their mechanical characterization tests revealed that with increase in MWCNT composition both storage modulus and hardness enhanced significantly in comparison to pure PC. For 10 wt% PC/MWCNT composite, the average storage modulus increased in the range of 40–92%, while the average hardness was enhanced in a range of 88–121% for the combined effect of temperature range of 30–90 °C and loading frequency range of 30–230 Hz. With increase in temperature, the maxima of storage moduli and hardness for these composites shifted toward higher loading frequencies, indicating that these composites can be used for wider loading frequency range. Therefore, the experimental results of this paper have shown that the mechanical properties of PC-based composite materials with minor MWCNT compositions are enhanced significantly and hence can be used for automotive and aerospace engine parts where loading frequencies are high and temperature conditions are variable.     

Mechanical and dynamic mechanical properties of nylon 66/montmorillonite nanocomposites fabricated by melt compounding

Nylon 66 nanocomposites were prepared by melt compounding of nylon 66 with organically modified montmorillonite (MMT). The organic MMT was pre‐modified with about 14 wt% of ammonium surfactant, much lower than the 35–46 wt% in most commercial organic MMT powders. Transmission electron microscope observation indicated that the MMT layers were well exfoliated in nylon 66 matrix. Dynamic mechanical analysis confirmed the constraint effect of exfoliated MMT layers on nylon 66 chains, which benefited the increased storage modulus, increased glass transition temperature and reduced magnitude of alpha relaxation peak. The effects of organic MMT loading levels on reinforcement and fracture behaviour of the nanocomposites were evaluated using tensile and three‐point bending tests. The addition of the organic MMT clearly increased Young's modulus and tensile strength but decreased ductility and fracture toughness of nylon 66. Copyright © 2004 Society of Chemical Industry