Polyethylene multiwalled carbon nanotube composites

Polyethylene (PE) multiwalled carbon nanotubes (MWCNTs) with weight fractions ranging from 0.1 to 10 wt% were prepared by melt blending using a mini-twin screw extruder. The morphology and degree of dispersion of the MWCNTs in the PE matrix at different length scales was investigated using scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM) and wide-angle X-ray diffraction (WAXD). Both individual and agglomerations of MWCNTs were evident. An up-shift of 17 cm⁻¹ for the G band and the evolution of a shoulder to this peak were obtained in the Raman spectra of the nanocomposites, probably due to compressive forces exerted on the MWCNTs by PE chains and indicating intercalation of PE into the MWCNT bundles. The electrical conductivity and linear viscoelastic behaviour of these nanocomposites were investigated. A percolation threshold of about 7.5 wt% was obtained and the electrical conductivity of PE was increased significantly, by 16 orders of magnitude, from 10⁻²⁰ to 10⁻⁴ S/cm. The storage modulus (G′) versus frequency curves approached a plateau above the percolation threshold with the formation of an interconnected nanotube structure, indicative of ‘pseudo-solid-like’ behaviour. The ultimate tensile strength and elongation at break of the nanocomposites decreased with addition of MWCNTs. The diminution of mechanical properties of the nanocomposites, though concomitant with a significant increase in electrical conductivity, implies the mechanism for mechanical reinforcement for PE/MWCNT composites is filler-matrix interfacial interactions and not filler percolation. The temperature of crystallisation (T_c) and fraction of PE that was crystalline (F_c) were modified by incorporating MWCNTs. The thermal decomposition temperature of PE was enhanced by 20 K on addition of 10 wt% MWCNT.     

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     

Thermosetting polyurethane multiwalled carbon nanotube composites

Thermosetting polyurethane (PU) multi‐walled carbon nanotube (MWCNT) nanocomposites at loadings up to 1 wt % were prepared via an addition polymerization reaction. The morphology of the nanocomposites and degree of dispersion of the MWCNTs was studied using a combination of scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM) and wide angle X‐ray diffraction (WAXD), and revealed the nanotubes to be highly dispersed in the PU matrix. Addition of just 0.1 wt % MWCNTs resulted in significant enhancements in stiffness, strength and toughness. Increases in Young's modulus, % elongation at break and ultimate tensile strength of 561, 302 and 397% were measured for the nanocomposites compared to the unfilled PU. The effect of the MWCNTs on the modulus of the PU was evaluated using the Rule of Mixtures, Krenchel and Halpin‐Tsai models. Only the Halpin‐Tsai model applied to high aspect ratio nanotubes was in good agreement with the modulus values determined experimentally. Strong interfacial shear stress was found between PU chains and nanotubes, up to 439 MPa, calculated using a modified Kelly‐Tyson model. Evidence for strong interfacial interactions was obtained from the Raman spectra of both the precursor materials and nanocomposites. When the MWCNTs were added to the isophorone diisocyanate an up‐shift of 14 cm^?1 and on average 40 cm^?1 was obtained for the position of the carbon‐hydrogen (C? H) out‐of plane bending (766 cm^?1) and isocyanate symmetric stretch (1420 cm^?1) modes respectively. Moreover, an up‐shift of 24 cm^?1 was recorded for the nanotube tangential mode (G‐band) for the 1.0 wt % nanocomposite because of the compressive forces of the PU matrix acting on the MWCNTs. The dynamic mechanical (DMA) properties of the PU thermoset and the nanocomposites were measured as a function of temperature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Fabrication of N-doped carbon nanobelts from a polypyrrole tube by confined pyrolysis for supercapacitors

In this present work, N-doped carbon nanobelts (N-CNBs) were prepared by a confined-pyrolysis approach and the N-CNBs were derived from a polypyrrole (Ppy) tube coated with a compact silica layer. The silica layer provided a confined space for the Ppy pyrolysis, thereby hindering the rapid overflow of pyrolysis gas, which is the activator for the formation of carbonaceous materials. At the same time, the confined environment can activate the carbon shell to create a thin wall and strip the carbon tube into belt morphology. This process of confined pyrolysis realizes self-activation during the pyrolysis of Ppy to obtain the carbon nanobelts without adding any additional activator, which reduces pollution and preparation cost. In addition, this approach is simple to operate and avoids the disadvantages of other methods that consume time and materials. The as-prepared N-CNB shows cross-linked nanobelt morphology and a rich porous structure with a large specific surface area. As supercapacitor electrode materials, the N-CNB can present abundant active sites, and exhibits a specific capacitance of 246 F·g⁻¹, and excellent ability with 95.44% retention after 10000 cycles. This indicates that the N-CNB is an ideal candidate as a supercapacitor electrode material.     

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.     

Preparation and properties of multiwalled carbon nanotube/polycaprolactone nanocomposites

Multiwalled carbon nanotube/polycaprolactone nanocomposites (MWNT/PCL) were prepared by in situ polymerization, whereby as‐received MWNTs (P‐MWNTs) and purified MWNTs (A‐MWNTs) were used as reinforcing materials. The A‐MWNTs were purified by nitric acid treatment, which introduced the carboxyl groups (COOH) on the MWNT. The micrographs of the fractured surfaces of the nanocomposites showed that the A‐MWNTs in A‐MWNT/PCL were better dispersed than P‐MWNTs in PCL matrix (P‐MWNT/PCL). Percolation thresholds of the P‐MWNT/PCL and A‐MWNT/PCL, which were studied by rheological properties, were found at ～2 wt % of the MWNT. The conductivity of the P‐MWNT/PCL was between 10^?1 and 10^?2 S/cm by loading of 2 wt % of MWNT although that of the A‐MWNT/PCL reached ～10^?2 S/cm by loading of 7 wt % of MWNT. The conductivity of the P‐MWNT/PCL was higher than that of the A‐MWNT/PCL at the entire range of the studied MWNT loading, which might be due to the destruction of π‐network of the MWNT by acid treatment, although the A‐MWNT/PCL was better dispersed than the P‐MWNT/PCL. The amount of the MWNT at which the conductivity of the nanocomposite started to increase was strongly correlated with the percolation threshold. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1957–1963, 2007     

Interaction of water soluble chitosan with multiwalled carbon nanotubes

A water soluble chitosan derivative (p‐chitosan) was synthesized and used to functionalize multiwalled carbon nanotubes (MWCNTs) through the noncovalent interaction. The interaction of p‐chitosan with MWCNTs was investigated by analyzing the spectra of ultraviolet‐visible, Fourier transform infrared, Raman, and X‐ray photoelectron. Circular dichroism spectroscopy was used to study the interaction as well. The results of the circular dichroism spectra indicate that, the interaction of p‐chitosan with MWCNT makes p‐chitosan less regularly structured. It was found that the interaction of p‐chitosan with MWCNTs at a lower temperature is stronger than that at a higher temperature; pH conditions affect the interaction between p‐chitosan and MWCNTs. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Preparation and properties of plasticized starch/multiwalled carbon nanotubes composites

In this work we have studied the utilization of multiwalled carbon nanotubes (MWCNTs) as filler‐reinforcement to improve the performance of plasticized starch (PS). The PS/MWCNTs nanocomposites were successfully prepared by a simple method of solution casting and evaporation. The morphology, thermal behavior, and mechanical properties of the films were investigated by means of scanning electron microscopy, wide‐angle X‐ray diffraction, differential scanning calorimetry, and tensile testing. The results indicated that the MWCNTs dispersed homogeneously in the PS matrix and formed strong hydrogen bonding with PS molecules. Compared with the pure PS, the tensile strength and Young's modulus of the nanocomposites were enhanced significantly from 2.85 to 4.73 MPa and from 20.74 to 39.18 MPa with an increase in MWCNTs content from 0 to 3.0 wt %, respectively. The value of elongation at break of the nanocomposites was higher than that of PS and reached a maximum value as the MWCNTs content was at 1.0 wt %. Besides the improvement of mechanical properties, the incorporation of MWCNTs into the PS matrix also led to a decrease of water sensitivity of the PS‐based materials. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Crystallization behavior of polyamide 11/multiwalled carbon nanotube composites

Differential scanning calorimetry (DSC) was used to investigate the isothermal and nonisothermal crystallization kinetics of polyamide11 (PA11)/multiwalled carbon nanotube (MWNTs) composites. The Avrami equation was used for describing the isothermal crystallization behavior of neat PA11 and its nanocomposites. For nonisothermal studies, the Avrami model, the Ozawa model, and the method combining the Avrami and Ozawa theories were employed. It was found that the Avrami exponent n decreased with the addition of MWNTs during the isothermal crystallization, indicating that the MWNTs accelerated the crystallization process as nucleating agent. The kinetic analysis of nonisothermal crystallization process showed that the presence of carbon nanotubes hindered the mobility of polymer chain segments and dominated the nonisothermal crystallization process. The MWNTs played two competing roles on the crystallization of PA11 nanocomposites: on the one hand, the MWNTs serve as heterogeneous nucleating agent promoting the crystallization process of PA11; on the other hand, the MWNTs hinder the mobility of the polymer chains thus retarding the crystal growth process of PA11. The activation energies of PA11/MWNTs composites for the isothermal and nonisothermal crystallization are lower than neat PA11. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Synthesis,characterizations, and physical properties of carbon nanotubes coated by conducting polypyrrole

A new type of carbon nanotube (CNT) (diameter of <100 nm) coated by conducting polypyrrole (PPY) was synthesized by in situ polymerization on CNTs. The structure of the resulting complex nanotubes (CNT‐PPY) was characterized by elemental analysis, X‐ray photoelectron spectroscopy, Raman spectra, and X‐ray diffraction. These indicated no significant chemical interaction between PPY and the CNT. The electrical, magnetic, and thermal properties of the complex nanotubes were measured and showed the physical properties of the CNTs were modified by conducting PPY. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2605–2610, 1999     

The enhanced mechanical properties of a covalently bound chitosan‐multiwalled carbon nanotube nanocomposite

In the present work, chitosan (CS)‐grafted multiwalled carbon nanotube (MWCNT) nanocomposites were prepared via covalently bonded CS onto MWCNTs that had weight fractions of MWCNTs ranging from 0.1 to 3.0 wt % by a simple method of solution casting. The structure, morphology, and mechanical properties of the films were investigated by Fourier transform infrared spectroscopy, field emission scanning electron microscopy, optical microscopy, wide‐angle X‐ray diffraction, contact angle, and tensile testing. The results indicated that the CS chains were attached onto the MWCNTs successfully via covalent linkages. More interestingly, the MWCNTs provided a matrix that facilitated the crystallization of CS. Compared with the pure CS, the tensile strength and Young's modulus of the nanocomposites were enhanced significantly from 39.6 to 105.6 MPa and from 2.01 to 4.22 GPa with an increase in the MWCNT loading level from 0 to 3.0 wt %, respectively. The improvement in the tensile strength and modulus were ascribed to the uniform dispersion of MWCNTs covalently linked to the CS matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Nickel‐multiwalled carbon nanotubes/polyvinylidene fluoride composites with high dielectric permittivity

Composites with nickel particles coated multiwalled carbon nanotubes (Ni‐MWNTs) embedded into polyvinylidene fluoride (PVDF) were prepared by solution blending and hot‐press processing. The morphology, structure, crystallization behavior, and dielectric properties of composites were studied. The results showed that the crystallization of PVDF was affected by Ni‐MWNTs. With the increment of Ni‐MWNTs, the content of β‐phase in PVDF increased. The dielectric permittivity was as high as 290 at 10³ Hz when the weight fraction of Ni‐MWNTs was 10%. The results can be explained by the space charge polarization at the interfaces between the insulator and the conductor, and the formation of microcapacitance structure. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3746–3752, 2013     

20 V stack of aqueous supercapacitors with carbon (−), titanium bipolar plates and CNT‐polypyrrole composite (+)

A 20 V stack of 19 supercapacitors was fabricated from titanium bipolar plates (150 × 150 × 0.1 mm³) coated on each side with carbon nanotubes and polypyrrole composite (+) and pigment carbon black (?), and microporous polymeric separators containing aqueous KCl. Internal sealing of each cell in the stack was achieved by placing a silicone rubber washer between neighboring bipolar plates. The stack was tested by high voltage cyclic voltammetry, galvanostatic charging and discharging, and electrochemical impedance spectroscopy. It approached 25 kW/kg in maximum specific power and 3.64 Wh/kg in specific energy. Performance of the stack through intermittent charging‐discharging tests in a storage period of 10 months (still ongoing) remained fairly stable. For example, it exhibited almost zero decay in capacitance after 1000 continuous galvanostatic charging‐discharging cycles in the first month of storage (10 V), and less than 6% loss in the seventh month (19 V). © 2011 American Institute of Chemical Engineers AIChE J, 2012     

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     

热解Ni/Co-ZIF-8制备碳纳米管桥连多孔碳及其在超级电容器中的应用

金属-有机骨架(MOFs)衍生碳材料具有丰富的孔道结构和超高的比表面积,在超级电容器等储能领域展现出巨大潜力。以环保型ZnO纳米球为模板,通过水热法制备核壳结构ZnO@Ni/Co-ZIF-8前体。将其在四种温度(700、800、900、950℃)下热解,获得不同形貌的Ni、Co及N掺杂的MOFs衍生碳材料Ni/Co-CN,并探究了煅烧温度对其储能性能的影响。结果表明,随着煅烧温度升高,Ni/Co-CN逐渐由多孔碳变为碳纳米管桥连多孔碳结构。当热解温度为900℃时,Ni/Co-CN-900的比电容最大。在1 mol/L的KOH电解液中对其进行循环伏安测试,曲线对称性良好,表明其具有优异的电化学可逆性。通过计算该过程电荷存储的电容贡献和扩散贡献占比可知,Ni/Co-CN的储能主要来自多孔碳的双电层吸附,少量来自N掺杂导致的法拉第反应。在0.5 A/g的电流密度下,Ni/Co-CN-900的比电容高达273.5 F/g。在10.0 A/g的电流密度下进行5000次恒流充放电后,其比电容保持率高达93.8%,展现出良好的电化学性能。     

热解Ni/Co-ZIF-8制备碳纳米管桥连多孔碳及其在超级电容器中的应用

金属-有机骨架(MOFs)衍生碳材料具有丰富的孔道结构和超高的比表面积,在超级电容器等储能领域展现出巨大潜力。以环保型ZnO纳米球为模板,通过水热法制备核壳结构ZnO@Ni/Co-ZIF-8前体。将其在四种温度(700、800、900、950℃)下热解,获得不同形貌的Ni、Co及N掺杂的MOFs衍生碳材料Ni/Co-CN,并探究了煅烧温度对其储能性能的影响。结果表明,随着煅烧温度升高,Ni/Co-CN逐渐由多孔碳变为碳纳米管桥连多孔碳结构。当热解温度为900℃时,Ni/Co-CN-900的比电容最大。在1 mol/L的KOH电解液中对其进行循环伏安测试,曲线对称性良好,表明其具有优异的电化学可逆性。通过计算该过程电荷存储的电容贡献和扩散贡献占比可知,Ni/Co-CN的储能主要来自多孔碳的双电层吸附,少量来自N掺杂导致的法拉第反应。在0.5 A/g的电流密度下,Ni/Co-CN-900的比电容高达273.5 F/g。在10.0 A/g的电流密度下进行5000次恒流充放电后,其比电容保持率高达93.8%,展现出良好的电化学性能。     

Effect of annealing treatment on the structure and properties of polyurethane/multiwalled carbon nanotube nanocomposites

The thermoplastic polyurethane/multiwalled carbon nanotube (TPU/CNT) nanocomposites with high conductivity and low percolation threshold value were prepared by melting blending and annealing treatment. The effect of annealing process on the microphase structure and the properties of TPU/CNT nanocomposites was studied. It has been shown that CNT flocculation can occur in TPU/CNT nanocomposites during the annealing process. At a critical CNT content, which defined the percolation threshold, CNTs could form conductivity network. The conductive percolation threshold value of TPU/CNT nanocomposites was decreased from 10 to 4% after annealing process, and the conductivity of TPU/CNT nanocomposites with 10 vol % of CNT could reach 1.1 S/m after an annealing time of 1 h. The significant enhancement of electrical conductivity was influenced by the annealing time and the content of CNTs. The formation of CNT networks was also verified by dynamic viscoelastic characterization. The results of X‐ray diffraction and differential scanning calorimetry indicated that annealing process reinforced the microphase separation of the nanocomposites. Mechanical properties test showed that the annealing treatment was in favor of improving the mechanical properties; however, further increase in the annealing time has negative effect on the mechanical properties. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Conductive network formation and electrical properties of poly(vinylidene fluoride)/multiwalled carbon nanotube composites: Percolation and dynamic percolation

Conductive network formation and its dynamic process for multiwalled carbon nanotubes (MWNTs) and carboxyl‐tethered MWNT (MWNT‐COOH) filled poly(vinylidene fluoride)(PVDF) systems were investigated. Based on real‐time tracing the variation of electrical resistivity of systems with isothermal treatment time, the conductive network formation was evaluated. It was found that the conductive network formation was temperature and time dependent. The percolation time, characterized at a certain annealing time where the electrical resistivity started to decrease drastically, decreased with the increase of the filler concentration or the annealing temperature. However, the values of the percolation time and the activation energy of conductive network formation for the PVDF/MWNT‐COOH system were higher than those of the PVDF/MWNT system, indicating that the interaction between MWNTs and PVDF molecules played an important role in the conductive network formation of the composites. Furthermore, a modified thermodynamic percolation model was proposed to predict the percolation time of PVDF/MWNT composites. It was found that the calculated results fit the experimental data very well. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Fabrication of one-dimensional Ag/multiwalled carbon nanotube nano-composite

ABSTRACT: Composite made of multiwalled carbon nanotubes coated with silver was fabricated by an electroless deposition process. The thickness of silver layer is about 40 to 60 nm, characterized as nano-crystalline with (111) crystal orientation along the nanotube's axial direction. The characterization of silver/carbon nanotube [Ag/CNT] nanowire has shown the large current carrying capability, and the electric conductivity is similar to the pure silver nanowires that Ag/CNT would be promising as building blocks for integrated circuits.PACS: 81.05.uj, carbon nanotubes, carbon-based materials, diamond/nanocarbon composites.     

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