Strengthening of liquid crystalline polymer by functionalized carbon nanotubes through interfacial interaction and homogeneous dispersion

Multiwalled carbon nanotubes (MWCNTs) were functionalized with two types of chemical moieties (i.e. carboxylic, ? COOH and hydroxyl benzoic acid groups, ‐HBA) on their sidewalls in order to improve their interaction with a liquid crystalline polymer (LCP) and dispersion in LCP. We have investigated the rheological, mechanical, dynamic mechanical, and thermal properties in detail with variation of HBA‐functionalized MWCNTs in the LCP matrix. Effect of the dispersion state of the functionalized MWCNTs in the LCP matrix on the rheological behavior was also studied. The composites containing HBA‐functionalized MWCNTs showed higher complex viscosity, storage, and loss modulus than the composites with the same loading of raw MWCNTs and MWCNT‐COOH. It was suggested that the HBA‐functionalized MWCNTs exhibited a better dispersion in the polymer matrix and formed stronger CNT‐polymer interaction in the composites than the raw MWCNTs and MWCNT‐COOH, which was also confirmed by FESEM and FTIR studies. As a result, the overall mechanical performance of the HBA‐MWCNT‐LCP composites could be improved significantly. For example, the addition of 4 wt% HBA‐MWCNT to LCP resulted in the considerable improvements in the tensile strength and modulus of LCP (by 66 and 90%, respectively). Copyright © 2010 John Wiley & Sons, Ltd.     

多壁碳纳米管对聚甲醛性能的影响

将多壁碳纳米管(MWCNTs)和聚甲醛(POM)在转矩流变仪中熔融混合得到POM/MWCNT复合材料.研究了复合材料的形态,导热性能,导电性能,流变性能和结晶性能.结果表明,MWCNTs在没有经过处理的情况下能够均匀地分散在POM基体中;当向POM中添加1.0 wt%含量MWCNTs时,复合材料的导热系数上升到0.5289 W/(K m),比纯POM的导热系数0.198 W/(K m)提高1.5倍,通过有效介质方法(EMA)验证了体系导热系数提高幅度不大的原因是MWCNTs与POM之间形成了很高的界面热阻;当MWCNTs的含量为1.0 wt%时,体系产生了导电逾渗效应,逾渗值在0.5 wt%~1.0 wt%之间;MWCNTs对POM有显著的成核作用,当向POM中添加0.5 wt%含量的MWCNTs时,POM的结晶温度提高6℃左右,但当MWCNTs的添加量进一步增加时,结晶温度几乎不再变化,成核效果呈现"饱和"状态.另外,材料的复数黏度,储能模量和损耗模量随MWCNTs含量的增加而增加.     

Influence of organo-clay on electrical and mechanical properties of PP/MWCNT/OC nanocomposites

The electrical, thermal and mechanical properties of nanocomposites, based on polypropylene (PP) filled by multi-walled carbon nanotubes (MWCNTs) and organo-clay (OC), were studied with the purpose of finding out the effect of OC on the microstructure of MWCNTs dispersion and PP/MWCNT/OC composites. It was found that addition of organo-clay nanoparticles improved nanotube dispersion and enhanced electrical properties of PP/MWCNT nanocomposites. Addition of organo-clay (MWCNT/OC ratio was 1/1) reduced the percolation threshold of PP/MWCNT nanocomposites from ?_c = 0.95 vol.% to ?_c = 0.68 vol.% of carbon nanotubes, while the level of conductivity became 2–4 orders of magnitude higher. The DSC and DMA analyses have shown that the influence of organo-clay on the thermal and mechanical properties of material was not significant in composites with both fillers as compared to PP/OC. Such an effect can be caused by stronger interaction of OC with carbon nanotubes than with polymer matrix.     

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.     

Thermal and electrical properties of poly(l-lactide)-graft-multiwalled carbon nanotube composites

The dispersion of the nanometer-sized carbon nanotubes in a polymer matrix leads to a marked improvement in the properties of the polymer. This approach can also be applied to biodegradable synthetic aliphatic polyesters such as poly(l-lactide) (PLLA), which has received a great deal of attention due to environmental concerns. In this study, PLLA was melt compounded with multiwalled carbon nanotubes (MWCNTs). A high degree of dispersion of the MWCNTs in the composites was obtained by grafting PLLA onto the MWCNTs (PLLA-g-MWCNTs). After oxidizing the MWCNTs by treating them with strong acids, they were reacted with l-lactide to produce the PLLA-g-MWCNTs. The morphology of the composite was observed with scanning electron microscopy. The mechanical properties of the PLLA/PLLA-g-MWCNT composite were higher than those of the PLLA/MWCNT composite. The thermal stability of the composites was studied using thermogravimetric analysis and their activation energy during thermal degradation was determined using the Kissinger and Flynn-Wall-Ozawa methods. The activation energy of PLLA/PLLA-g-MWCNT was higher than that of PLLA/MWCNT, which indicates that the composite made with the PLLA-g-MWCNTs was more thermally stable than the composite made with the MWCNTs.     

In situ polymerization of methyl methacrylate/multi-walled carbon nanotube composites using cationic stearyl methacrylate copolymers as dispersants

Novel water-soluble amphiphilic copolymers (poly[(stearyl methacrylate)-stat-([2-(methacryloyloxy)ethyl] trimethyl ammonium iodide)]) for dispersing multi-walled carbon nanotubes (MWCNTs) were used to carry out in situ methyl methacrylate (MMA) polymerization. The morphology of the poly(methyl methacrylate)/MWCNT composites and the dispersion of the MWCNTs were analyzed by transmission electron microscopy. The dispersion of multi-walled carbon nanotubes in the composites was excellent for cationic SMA (stearyl methacrylate) copolymers, even at high MWCNT loading (6.0 wt.%). The mechanical properties and electrical and thermal conductivities of the composites were also analyzed. Mechanical properties were improved by MWCNTs; the strain at break values remained stable up to 6.0 wt.% MWCNT loading. Both electrical and thermal conductivities were improved by the addition of MWCNTs.     

Synergic effect of multi-walled carbon nanotubes and gold nanoparticles towards immunosensing of ricin with carbon nanotube-gold nanoparticles-chitosan modified screen printed electrode

An amperometric immunosensor for the specific detection of Ricinus communis is reported. Screen printed electrodes (SPEs) were modified with gold nanoparticles (GNPs) loaded multiwalled carbon nanotubes (MWCNTs)-chitosan (Ch) film. The ratio of MWCNT and GNP was optimised to get best electrochemically active electrode. Sandwich immunoassay format was used for the immunosensing of ricin. The revealing antibodies tagged with the enzyme alkaline phosphatase (ALP) converts the substrate 1-naphthyl phosphate into 1-naphthol that was determined with the amperometric technique. The amperometric current obtained was correlated with the concentration of ricin. The prepared GNP-MWCNT-Ch-SPE showed high stability due to the Ch film, short response time with good reproducibility and increased shelf life of the electrodes immobilised with antibodies. The electrochemical activity of the electrode improved because of optimization of composition of CNTs and gold nanoparticles. Under the optimal conditions, the modified electrode showed a wide linear response to the concentration of ricin in the range of 2.5-25 ng mL(-1) with a limit of detection of 2.1 ng mL(-1) and with a relative standard deviation of 5.1% and storage life of 32 days.     

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     

Rheological and dynamic-mechanical behavior of carbon nanotube/vinyl ester-polyester suspensions and their nanocomposites

Rheological properties of vinyl ester-polyester resin suspensions containing various amounts (0.05, 0.1 and 0.3 wt.%) of multi walled carbon nanotubes (MWCNT) with and without amine functional groups (-NH₂) were investigated by utilization of oscillatory rheometer with parallel plate geometry. Dispersion of corresponding carbon nanotubes within the resin blend was accomplished employing high shear mixing technique (3-roll milling). Based on the dynamic viscoelastic measurements, it was observed that at 0.3 wt.% of CNT loadings, storage modulus (G′) values of suspensions containing MWCNTs and MWCNT-NH₂ exhibited frequency-independent pseudo solid like behavior especially at lower frequencies. Moreover, the loss modulus (G″) values of the resin suspensions with respect to frequency were observed to increase with an increase in contents of CNTs within the resin blend. In addition, steady shear viscosity measurements implied that at each given loading rate, the resin suspensions demonstrated shear thinning behavior regardless of amine functional groups, while the neat resin blend was almost the Newtonian fluid. Furthermore, dynamic mechanical behavior of the nanocomposites achieved by polymerizing the resin blend suspensions with MWCNTs and MWCNT-NH₂ was investigated through dynamic mechanical thermal analyzer (DMTA). It was revealed that storage modulus (E′) and the loss modulus (E″) values of the resulting nanocomposites increased with regard to carbon nanotubes incorporated into the resin blend. In addition, at each given loading rate, nanocomposites containing MWCNT-NH₂ possessed larger loss and storage modulus values as well as higher glass transition temperatures (T_g) as compared to those with MWCNTs. These findings were attributed to evidences for contribution of amine functional groups to chemical interactions at the interface between CNTs and the resin blend matrix. Transmission electron microscopy (TEM) studies performed on the cured resin samples approved that the dispersion state of carbon nanotubes with and without amine functional groups within the matrix resin blend was adequate. This implies that 3-roll milling process described herein is very appropriate technique for blending of carbon nanotubes with a liquid thermoset resin to manufacture nanocomposites with enhanced final properties.     

Effects of electrically inert fillers on the properties of poly(<Emphasis Type="Italic">m</Emphasis>-xylene adipamide)/multiwalled carbon nanotube composites

The effects of three types of electrically-inert fillers, calcium carbonate (CaCO₃), talc and glass fiber (GF), on electrical resistivity, crystallization behavior and dynamic mechanical properties of poly(m-xylene adipamide) (MXD6)/multiwalled carbon nanotube (MWCNT) composites are investigated. The electrical resistivity of MXD6/MWCNT composites is significantly reduced with the addition of inert fillers due to the volume-exclusion effect that leads to increased effective concentration of MWCNTs in MXD6 matrix and also due to improved MWCNT dispersion. The crystallization temperature of MXD6 increases with the addition of MWCNTs, indicating that MWCNTs can act as nucleating agent and induce crystallization of MXD6. The incorporation of inert fillers has no further effect on crystallization behavior of MXD6, but significantly improves the storage modulus of MXD6/MWCNT composite, demonstrating that CaCO₃, talc and GF filled MXD6/MWCNT composites are very promising materials with not only improved electrical property but also excellent mechanical properties.     

Effects of Electrically Inert Fillers on the Properties of Poly(m-xylene adipamide)/Multiwalled Carbon Nanotube Composites

The effects of three types of electrically-inert fillers, calcium carbonate(CaCO_3), talc and glass fiber(GF), on electrical resistivity, crystallization behavior and dynamic mechanical properties of poly(m-xylene adipamide)(MXD6)/multiwalled carbon nanotube(MWCNT) composites are investigated. The electrical resistivity of MXD6/MWCNT composites is significantly reduced with the addition of inert fillers due to the volume-exclusion effect that leads to increased effective concentration of MWCNTs in MXD6 matrix and also due to improved MWCNT dispersion. The crystallization temperature of MXD6 increases with the addition of MWCNTs, indicating that MWCNTs can act as nucleating agent and induce crystallization of MXD6. The incorporation of inert fillers has no further effect on crystallization behavior of MXD6, but significantly improves the storage modulus of MXD6/MWCNT composite, demonstrating that CaCO_3, talc and GF filled MXD6/MWCNT composites are very promising materials with not only improved electrical property but also excellent mechanical properties.     

Electrocatalytic properties of platinum nanoparticles supported on fluorine tin dioxide/multi-walled carbon nanotube composites for methanol electrooxidation in acidic medium

Fluorine tin oxide (FTO) and multi-walled carbon nanotube (MWCNT) composites synthesized by a sol-gel process followed by a hydrothermal treatment process have been explored as a support for Pt nanoparticles (Pt-FTO/MWCNTs). X-ray diffraction analysis and high resolution transmission electron microscopy show that the Pt and FTO nanoparticles with crystallite size of around 4-8 nm are highly dispersed on the surface of MWCNTs. Pt-FTO/MWCNT catalyst is evaluated in terms of the electrochemical catalytic activity for methanol electrooxidation using cyclic voltammetry, steady state polarization experiments, and electrochemical impedance spectroscopy technique in acidic medium. The Pt-FTO/MWCNT catalyst exhibits a higher intrinsic catalytic activity for methanol electrooxidation with high stability during potential cycling than Pt nanoparticles supported on tin dioxide/multi-walled carbon nanotube composites. The results suggest that FTO/MWCNT composites could be considered as an alternative support for Pt-based electrocatalysts in direct alcohol fuel cells.     

Experimental and modeling analysis of mechanical-electrical behaviors of polypropylene composites filled with graphite and MWCNT fillers

The incorporation of carbon fillers can improve the thermal and electrical conductivities of polymer composites but will also have a significant effect on the flexural and tensile behavior. In this paper, two types of carbon fillers were added to polypropylene - carbon nanotubes and synthetic graphite. The influences of these filler materials on the tensile, flexural and fracture toughness characteristics were measured and the electrical conductivity of composites was also investigated. It was observed that the fillers lead to a remarkable increase in the flexural and tensile modulus of polypropylene composites. The maximum flexural and tensile strengths slightly increased with the addition of graphite, however, they were significantly increased in the case of carbon nanotubes because MWCNTs possess exceptional stiffness and strength and their length to diameter ratio is extremely high when compared with graphite. Electrical conductivity of polypropylene composites was evaluated. Noteworthy, composites based on synthetic graphite show a percolation process at one order of magnitude concentration higher than MWCNT filled polypropylene. Fracture toughness results open a wide range of applications for PP-MWCNT composites. Several prediction models were inspected in this research and it was concluded that inverse rule of mixtures model showed the most accurate predictions of the tensile modulus for composites made of polypropylene.     

A comparative study on the effect of carbon fillers on electrical and thermal conductivity of a cyanate ester resin

Carbon fillers including multi-walled carbon nanotubes (MWCNTs), carbon black (CB) and graphite were introduced in a cyanate ester (CE) resin, respectively. The effects of the fillers on the electrical and thermal conductivity of the resin were measured and analyzed based on the microscopic observations. MWCNTs, CB and graphite exhibited percolation threshold at 0.1 wt%, 0.5 wt% and 10 wt%, respectively. The maximal electrical conductivity of the composites was 1.08 S/cm, 9.94 × 10⁻³ S/cm and 1.70 × 10⁻⁵ S/cm. MWCNTs showed the best enhancement on the electrical conductivity. The thermal behavior of the composites was analyzed by calorimetry method. Incorporation of MWCNTs, CB and graphite increased the thermal conductivity of CE resin by 90%, 15% and 92%, respectively. Theoretical models were introduced to correlate the thermal conductivity of the CE/MWCNTs composite. The interfacial thermal resistance between CE resin and MWCNTs was 8 × 10⁻⁸ m²K/W and the straightness ratio was 0.2. The MWCNTs were seriously entangled and agglomerated. Simulation results revealed that thermal conductivity of the CE/MWCNTs composites can be substantially elevated by increasing the straightness ratio and/or filler content of MWCNTs.     

The effect of MWCNT on dynamic mechanical properties and crystallinity of in situ polymerized polyamide 12 nanocomposite

This work aims at investigating the dynamic mechanical properties of in situ anionic ring opening polymerized polyamide 12 in the presence of multi‐walled carbon nanotubes (MWCNT). According to the dynamic mechanical thermal analysis results, the addition of only 0.1 wt.% of MWCNTs led to 30% enhancement in modulus at room temperature which exhibited improved mechanical behavior of the nanocomposites. Test results showed that by the presence of 1.2% wt MWCNTs, the modulus is almost doubled, and it did not show any tangible changes by the addition of more nanotubes. Also, the effect of different frequencies on the viscoelastic behavior was investigated in order to determine the thermal transitions occurred in the synthesized nanocomposites. After that, the crystallinity of the samples has been studied using differential scanning calorimetry and X‐ray diffraction data in order to investigate the effect of MWCNT content on the crystals' dimension.     

三元复合材料PANI／Ag／MWNT的电化学行为和比电容

通过原位聚合的方式在银纳米粒子/多壁碳纳米管（Ag/MWCNT）复合材料的表面成功聚合苯胺单体制备了聚苯胺/银纳米粒子/多壁碳纳米管（PANI/Ag/MWCNT）三元复合材料苯．通过对三元复合材料的结构以及表面形貌进行分析,表明聚苯胺层完全包覆了Ag/MWCNT复合材料,形成了核壳式结构．同时银纳米粒子则以单质晶体的形态存在于多壁碳纳米管与聚苯胺层之间．三元复合材料电极在1 mol/L的KOH溶液中具有极低的阻抗,而与聚苯胺电极相比,这些复合材料电极则表现出更低的电阻、更高的电化学活性和更好的循环稳定性．尤其是当苯胺和Ag：MWCNTs质量比为5：5时,该复合材料电极在0.25 A/g的电流密度下表现出最大的比电容值为160 F/g．     

Synthesis and field emission properties of carbon nanotube films modified with amorphous carbon nanoparticles by a simple electrodeposition method

Amorphous carbon nanoparticles （a-CNPs） on a multi-walled carbon nanotube （MWCNT） film, deposited on a silicon substrate, were synthesized using an electrodeposition combination from a methanol suspension of polydiallyldimethylammonium chloride-modified MWCNTs. A low-voltage electropho- retic deposition of the MWCNTs and a high-voltage electrochemical deposition of the a-CNPs were carried out to yield homogenously attached a-CNPs on the surfaces of the MWCNTs, and form a composite film with good adhesion to the substrate. This scalable technology can produce a large area of a-CNP/MWCNT film. And the field emission investigations show that the a-CNP/MWCNT film has turn- on electric field of 3.17 V μm- 1 （at 10 μA cm-2） and threshold field of 4.62 V μm-1 （at 1 mA cm-2）, which are lower than those of the MWCNT film. The a-CNP/MWCNT film can be deposited simply with large areas and may be a promising cathode material applied in field emission displays.     

Melt‐crystallization mechanism of poly(ethylene terephthalate)/multi‐walled carbon nanotubes prepared by in situ polymerization

A series of poly(ethylene terephthalate)/multi‐walled carbon nanotubes (PET/MWCNTs) nanocomposites were prepared by in situ polymerization using different amounts of multi‐walled carbon nanotubes (MWCNTs). The polymerization of poly(ethylene terephthalate) (PET) was carried out by the two‐stage melt polycondensation method. The intrinsic viscosity (IV) of the composites is ranged between 0.31 and 0.63 dL/g depending on the concentration of the MWCNTs. A decrease of IV was found by increasing MWCNTs content. This is due to the reactions taking place between the two components leading to branched and crosslinked macromolecules. These reactions are, mainly, responsible for thermal behavior of nanocomposites. The melting point of the nanocomposites was shifted to slightly higher temperatures by the addition till 0.55 wt % of MWCNTs while for higher concentration was reduced. The degree of crystallinity in all nanocomposites was, also, reduced by increasing MWCNTs amount. However, from crystallization temperature, it was found that MWCNTs till 1 wt % can enhance the crystallization rate of PET, whereas at higher content (2 wt %), the trend is the opposite due to the formation of crosslinked macromolecules. From the extended crystallization analysis, it was proved that MWCNTs act as nucleating agents for PET crystallization. Additionally, the crystallization mechanism due to the existence of MWCNT becomes more complicated because two mechanisms with different activation energies are taking place in the different degrees of crystallization, depending on the percentage of MWCNT. The effect of molecular weight also plays an important role. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1452–1466, 2009     

Thin films composed of multiwalled carbon nanotubes, gold nanoparticles and myoglobin for humidity detection at room temperature.

Optically transparent and electrically conductive nanocomposite thin films consisting of multiwalled carbon nanotubes (MWCNTs), gold nanoparticles (GNPs) and myoglobin molecules that glue GNPs and MWCNTs together are fabricated for the first time on glass substrates from aqueous solution. The nanocomposite thin film is capable of varying its resistance, impedance or optical transmittance at room temperature in response to changes in ambient humidity. The conductometric sensitivity to relative humidity (RH) of the nanocomposite thin film is compared with those of the pure and Mb-functionalized MWCNT layers. The pure MWCNT layer shows a small increase in its resistance with increasing RH due to the effect of p-type semiconducting nanotubes present in the film. In contrast, a four times higher sensitivity to RH is observed for both the nanocomposite and Mb-functionalized MWCNT thin films. The sensitivity enhancement is attributable to swelling of the thin films induced by water absorption in the presence of Mb molecules, which increases the inter-nanotube spacing and thereby causes a further increase of the film resistance. A humidity change as low as DeltaRH=0.3 % has been readily detected by conductometry using the nanocomposite thin film.