Optimization of the mechanical properties of calcium phosphate/multi-walled carbon nanotubes/bovine serum albumin composites using response surface methodology

Response surface methodology (RSM) coupled with the central composite design (CCD) was used to optimize the mechanical properties of calcium phosphate cement/multi-walled carbon nanotubes/bovine serum albumin (CPC/MWCNTs/BSA) composites. In this study, CPC composites were reinforced by multi-walled carbon nanotubes (MWCNTs) and bovine serum albumin (BSA) in order to induce high mechanical properties in the CPC/MWCNTs/BSA system. The effect of various process parameters on the compressive strength of CPC/MWCNTs/BSA composites was studied using design of experiments (DOE). The process parameters studied were: wt.% of MWCNTs (0.2–0.5 wt.%), wt.% of BSA (5–15 wt.%) and type of MWCNTs (e.g. as-pristine MWCNT (MWCNT-AP), hydroxyl group functionalized MWCNT (MWCNT-OH) and carboxyl group functionalized MWCNT (MWCNT-COOH)). Based on the CCD, a quadratic model was obtained to correlate the process parameters to the compressive strength of CPC/MWCNTs/BSA composites. From the analysis of variance (ANOVA), the most significant factor affected on the experimental design response was identified. The predicted compressive strength after process optimization was found to agree well with the experimental value. The results revealed that at 0.5 wt.% of MWCNT-OH and 15 wt.% of BSA, the highest compressive strength of 14 MPa was obtained.     

Synthesis and characterization of well-dispersed multi-walled carbon nanotube/low-bandgap poly(3,4-alkoxythiophene) nanocomposites

In this study, we prepared nanocomposites of multi-walled carbon nanotubes (MWCNTs) and low-energy-bandgap conjugated polymers incorporating 3,4-alkoxythiophene monomers. Poly(3,4-dihexyloxythiophene) (PDHOT) and poly(3,4-dimethoxythiophene-co-3,4-dihexyloxythiophene) [P(DMOT-co-DHOT)] have relatively low-energy-bandgaps (ca. 1.38 and 1.34 eV, respectively), determined from the onsets of absorbances in their UV–Vis spectra, because of the electron-donating effects of their alkoxy groups. MWCNTs have poor solubility in common organic solvents; after surface modification with alkyl side chains using the Tour reaction, however, the p-hexylaniline modified MWCNT derivative (MWCNT-HA) was readily dispersed in CHCl₃ and could be mixed with the low bandgap polymers. Scanning electron microscopy images revealed that MWCNT-HA was dispersed well in each polythiophene derivative; only a few MWCNT-HA bundles could be observed at a high MWCNT-HA content (≧20 wt.%). The electrical conductivities of the MWCNTs/PDHOT composites were dependent on their MWCNT content, reaching 16 S/cm at 30 wt.% MWCNT-HA. We suspect that the two hexyloxy chains of PDHOT enhanced its solubility and allowed it to wrap around the surfaces of the MWCNTs more readily.     

Filler dispersion and electrical properties of polyamide 12/MWCNT-nanocomposites produced in reactive extrusion via anionic ring-opening polymerization

The reactive extrusion of lauryl lactam to polyamide 12 (PA12) of controlled molar mass was successfully performed in a microcompounder. The maximum residual monomer content was less than 1%. The in-situ polymerization in the presence of 1–5 wt.% multiwalled carbon nanotubes (MWCNTs) was studied and the processing conditions were optimized with respect to the electrical resistivity and MWCNT dispersion. Runs which yielded in higher molar mass PA12 resulted in better dispersion of MWCNTs, whereas nanocomposites with lower molar mass PA12 had lower electrical percolation thresholds (MWCNT concentration ∼1 wt.%). A high screw speed of 200 rpm was identified to cause best dispersion and the lowest percolation threshold.     

Nanocomposites based on MWCNT and styrene–butadiene–styrene block copolymers: Effect of the preparation method on dispersion and polymer–filler interactions

Composites of Kraton-D® 1102 BT (a styrene–butadiene–styrene block copolymer) and multi-walled carbon nanotubes (MWCNTs) were prepared by melt mixing. The composites were characterized by electrical conductivity measurements (Coleman’s method), mechanical properties (DMA and stress–strain tests), thermal stability (thermogravimetry) and morphology of dispersion (SEM). Finally, the resulting composites were compared with those made by the solution casting method. The results showed a strong influence of the preparation methodology on the final properties of the composites due to changes in morphology. Composites prepared by casting showed a higher electrical conductivity than extruded ones; the composites with 6 wt.% of MWCNT prepared by extrusion presented conductivity of the same order of magnitude as the composite with 1 wt.% of MWCNT prepared by casting – 10⁻³ to 10⁻⁴ S cm⁻¹. However, the extruded samples presented better mechanical properties than the casting ones.     

Percolation behaviour of multiwalled carbon nanotubes of altered length and primary agglomerate morphology in melt mixed isotactic polypropylene-based composites

The effect of ball milling on the structural characteristics and further on the dispersion and percolation behaviour of multiwalled carbon nanotubes (MWCNTs) in melt mixed composites using a maleic anhydride modified isotactic polypropylene as matrix was investigated. TEM and SEM revealed that ball milled nanotubes were considerably shorter and showed a compact primary agglomerate morphology compared to the as-synthesised MWCNTs. At macro scale ball milled MWCNTs were found to be better dispersed, whereas at sub-micron scale the states of dispersion of both nanotube materials were comparable. The differences in the composite morphologies as well as in the composites electrical and rheological percolation behaviour were assigned to the altered MWCNT structure due to ball milling treatment. The dispersibility of ball milled MWCNTs was restricted due to their more compact agglomerate morphology. Furthermore, the ability to form percolated network structures was restrained by their shorter length and, again, their compact primary agglomerates. An effective agglomerate interaction radius depending on the nanotube structural characteristics, length and agglomerate morphology, is suggested in order to explain the experimental findings.     

Influence of dry grinding in a ball mill on the length of multiwalled carbon nanotubes and their dispersion and percolation behaviour in melt mixed polycarbonate composites

Ball milling of carbon nanotubes (CNTs) in the dry state is a common way to produce tailored CNT materials for composite applications, especially to adjust nanotube lengths. For Nanocyl^TM NC7000 nanotube material before and after milling for 5 and 10 h the length distributions were quantified using TEM analysis, showing decreases of the mean length to 54% and 35%, respectively. With increasing ball milling time in addition a decrease of agglomerate size and an increase of packing density took place resulting in a worse dispersability in aqueous surfactant solutions. In melt mixed CNT/polycarbonate composites produced using masterbatch dilution step, the electrical properties, the nanotube length distribution after processing, and the nano- and macrodispersion of the nanotubes were studied. The slight increase in the electrical percolation threshold in the melt mixed composites with ball milling time of CNTs can be assigned to lower nanotube lengths as well as the worse dispersability of the ball milled nanotubes. After melt compounding, the mean CNT lengths were shortened to 31%, 50%, and 66% of the initial lengths of NC7000, NC7000-5 h, and NC7000-10 h, respectively.     

Characterization of rheological behaviors of polypropylene/carbon nanotubes composites and modeling their flow in a twin-screw mixer

This paper focuses on the numerical simulation of the polypropylene/multi-walled carbon nanotubes (PP/MWCNT) flow into a twin-screw mixer, during the mixing phase. The PP/MWCNT behavior obeys an innovating Carreau law enriched temperature built on the rheological properties carried out previously. The polypropylene was mixed with different MWCNTs contents (1, 2, 4 and 8 wt.% of MWCNT content) and the rheological tests were performed at shear rate ranges from 10⁻¹ to 2 × 10⁴ s⁻¹ at four temperatures (180, 200, 220 and 240 °C). Thus the effects of the temperature and the MWCNTs content on the rheological properties of the PP/MWCNT composites were investigated. The finite element (FEM) analysis of the PP/MWCNT flow allows to compute the velocity, the shear rate and the temperature during the mixing phase period. A good agreement between the experimental measured torque on the screw and the calculated one is shown. Therefore, one can consider that the physical flow is generally well described, awaiting a numerical simulation of the PP/MWCNT mixing phase.     

Effect of carbon nanotube (CNT) content on the mechanical properties of CNT-reinforced aluminium composites

The interest in carbon nanotubes (CNTs) as reinforcements for aluminium (Al) has been growing considerably. Efforts have been largely focused on investigating their contribution to the enhancement of the mechanical performance of the composites. The uniform dispersion of CNTs in the Al matrix has been identified as being critical to the pursuit of enhanced properties. Ball milling as a mechanical dispersion technique has proved its potential. In this work, we use ball milling to disperse up to 5 wt.% CNT in an Al matrix. The effect of CNT content on the mechanical properties of the composites was investigated. Cold compaction and hot extrusion were used to consolidate the ball-milled Al–CNT mixtures. Enhancements of up to 50% in tensile strength and 23% in stiffness compared to pure aluminium were observed. Some carbide formation was observed in the composite containing 5 wt.% CNT. In spite of the observed overall reinforcing effect, the large aspect ratio CNTs used in the present study were difficult to disperse at CNT wt.% greater than 2, and thus the expected improvements in mechanical properties with increase in CNT weight content were not fully realized.     

Tuning the localization of functionalized MWCNTs in SAN/PC blends by a reactive component

The influence of the reactive component (N-phenylmaleimide styrene maleic anhydride) on the blend morphology, the localization of functionalized multiwalled carbon nanotubes (MWCNTs), and the electrical resistivity of MWCNT filled blend systems of polycarbonate (PC) and poly(styrene-co-acrylonitrile) (SAN) was investigated. SAN, PC, amino-functionalized MWCNTs (Nanocyl™ NC3152) and the reactive component (RC) were melt mixed in a DSM Xplore microcompounder using different mixing sequences. The RC containing maleic anhydride (MA) groups is miscible with SAN and is assumed to act as linking agent to the functionalized MWCNTs.The morphology of the SAN/PC blends was studied depending on the concentration of the RC. Thereby co-continuous morphologies were found for all blends with 40 wt.% SAN and 60 wt.% PC. In all nonmodified blends the MWCNTs were localized within the PC phase. After the addition of RC the MWCNTs migrated completely into the miscible SAN–RC phase. Consequently, the electrical resistivities of the blends changed in dependence on the localization. Whereas the SAN/PC/MWCNT blends showed low electrical resistivity values, much higher values were found for SAN–RC/PC/MWCNT blends. This was assigned to a coupling or strong interaction of MA groups to the nanotubes disturbing electrical contacts and percolation between them. The occurrence of the MWCNT migration from PC towards SAN was found to be dependent on the concentrations of RC and MWCNTs. By adapting that ratio and the mixing strategy, the localization of the carbon nanotubes in the blend phases can be tuned. The investigations indicated that MWCNTs once coupled with the RC remain in the SAN–RC phase. Thus, a chemical reaction or strong interactions seem to be the driving forces for localization of the MWCNTs in the SAN–RC blend phase.     

Multi-walled carbon nanotube/nanostructured zirconia composites: Outstanding mechanical properties in a wide range of temperature

Multi-walled carbon nanotube (MWCNT)/nanostructured zirconia composites with a homogenous distribution of different MWCNT quantities (ranging within 0.5-5 wt.%) were developed. By using Spark Plasma Sintering we succeeded in preserving the MWCNTs firmly attached to zirconia grains and in obtaining fully dense materials. Moreover, MWCNTs reduce grain growth and keep a nanosize structure. A significant improvement in room temperature fracture toughness and shear modulus as well as an enhanced creep performance at high temperature is reported for the first time in this type of materials. To support these interesting mechanical properties, high-resolution electron microscopy and mechanical loss measurements have been carried out. Toughening and creep hindering mechanisms are proposed. Moreover, an enhancement of the electrical conductivity up to 10 orders of magnitude is obtained with respect to the pure ceramics.     

Percolation behaviour of polypropylene glycol filled with multiwalled carbon nanotubes and Laponite

The percolation behaviour of the hybrid composites of polypropylene glycol (PPG) filled with multiwalled carbon nanotubes (MWCNTs) and Laponite RD (Lap), or with MWCNTs and organo-modified Laponite (LapO) was studied by wide angle X-ray diffraction (XRD), microscopic image analysis, and electrical conductivity measurements. Cetyltrimethylammoniumbromide (CTAB) was used as an organo-modifier of Laponite. The Lap and LapO were found to have rather different affinity to PPG. XRD data have evidenced finite PPG integration inside Lap and complete exfoliation of LapO stacks in a PPG matrix. In PPG + MWCNT composites containing no Lap or LapO, increase of MWCNT concentration above the critical value C_p ∼ 0.4 wt% resulted in percolation. The value of the percolation threshold, C_p, was practically the same for hybrid PPG + MWCNT + Lap composites. However, it noticeably decreased (C_p ∼ 0.2 wt%) in PPG + MWCNT + LapO materials. The observed behaviour of the percolation threshold may be attributed to the effects exerted by LapO on the size of MWCNT aggregates, state of their dispersion and homogeneity of their spatial distribution.     

Effects of grafted chain length on mechanical and electrical properties of nanocomposites containing polylactide-grafted carbon nanotubes

We herein report the effects of interfacial reinforcement on mechanical and electrical properties of nanocomposites based on polylactide (PLA) and multi-walled carbon nanotube (MWCNT). For this purpose, a series of MWCNTs grafted with PLA chains of various lengths (MWCNT-g-PLAs) were prepared by ring-opening polymerization of l-lactide with carboxylic acid-functionalized MWCNT (MWCNT-COOH). MWCNT-g-PLAs were then mixed with commercial PLA to obtain PLA/MWCNT-g-PLA nanocomposites with 1.0 wt.% MWCNT content. It was revealed that morphological, mechanical, and electrical properties of PLA/MWCNT-g-PLA nanocomposites were strongly dependent on the PLA chain length of MWCNT-g-PLAs. FE-SEM images exhibited that the nanocomposites containing MWCNT-g-PLA with longer PLA chain length exhibited better dispersion of MWCNTs in the PLA matrix. Initial moduli and tensile strengths of PLA/MWCNT-g-PLA composites increased with the increment of chain length of PLA grafted on MWCNTs, which attributes to the improved interfacial adhesion between the grafted PLA chains of MWCNT-g-PLA and the PLA matrix. As a result, the experimental initial modulus (2775 ± 193 MPa) of the nanocomposite including MWCNT-g-PLA with PLA chains of average molecular weight of 530 g/mol was quite close to the theoretical value (2911 MPa) predicted for the nanocomposite with perfect interfacial adhesion. Unexpectedly, electrical resistivities of PLA/MWCNT-g-PLA nanocomposites were found to increase from ∼10⁴ to ∼10¹² Ω/sq with increasing the PLA chain length of MWCNT-g-PLA, which is due to the fact that the PLA chains grafted on MWCNTs prevent the formation of the electrical conduction path of MWCNTs in the PLA matrix.     

Development of conducting polychloroprene rubber using imidazolium based ionic liquid modified multi-walled carbon nanotubes

A simplified and an eco-friendly approach to develop polychloroprene rubber composites with high electrical conductivity is reported. The usage of room temperature ionic liquid, 1-butyl 3-methyl imidazolium bis(trifluoromethylsulphonyl)imide and a low concentration (5 phr) of commercial grade multi-walled carbon nanotubes (MWCNTs) in polychloroprene rubber exhibited an electrical conductivity of 0.1 S/cm with a stretchability >500%. The physical (cation-pi/pi-pi) interaction between the ionic liquid and the MWCNTs is evidenced by Raman spectroscopy. Transmission electron microscopy images exhibit an improved dispersion of the BMI modified tubes in matrix at various magnification scales. The dependency of dynamic properties on the concentration of ionic liquid at constant loading of nanotubes supports the fact that ionic liquid assists in the formation of filler-filler networks. The tensile modulus of 3 phr loaded modified MWCNT/CR composite is increased by 50% with regard to that of the unmodified MWCNT/CR composite. Mooney-Rivlin plot displays the existence of rubber-filler interactions.     

Structure and properties of highly oriented polyoxymethylene/multi-walled carbon nanotube composites produced by hot stretching

Highly-oriented polyoxymethylene (POM)/multi-walled carbon nanotube (MWCNT) composites were fabricated through solid hot stretching technology. With the draw ratio as high as 900%, the oriented composites exhibited much improved thermal conductivity and mechanical properties along the stretching direction compared with that of the isotropic samples before drawing. The thermal conductivity of the composite with 11.6 vol.% MWCNTs can reach as high as 1.2 W/m K after drawing. Microstructure observation demonstrated that the POM matrix had an ordered fibrillar bundle structure and MWCNTs in the composite tended to align parallel to the stretching direction. Wide-angle X-ray diffraction results showed that the crystal axis of the POM matrix was preferentially oriented perpendicular to the draw direction, while MWCNTs were preferentially oriented parallel to the draw direction. The strong interaction between the POM matrix and the MWCNTs hindered the orientation movement of molecules of POM, but induced the orientation movement of MWCNTs.     

Dielectric properties of polystyrene/onion-like carbon composites in frequency range of 0.5–500 kHz

Composites of polystyrene and onion-like carbon (OLC), produced from detonation nanodiamonds (NDs), have been fabricated by forge-rolling method. Optical microscopy and optical absorption spectroscopy were used for control of dispersion of OLC in polymer matrix after repeating rolling cycles. The impedance measurements of composites with different filler loading indicated the percolation threshold at ∼20–25 wt.% OLC concentration. The permittivity of the polystyrene/OLC composites varies from 2 to 10 with changing the OLC loading from 5 to 35 wt.%. Fitting the experimental data with model based on the Maxwell–Garnett approximation lead to conclusion that the shear deformation applied under the composite preparing disintegrates OLC agglomerates to the size ∼40–50 nm equal to the medium size of OLC in dimethylformamide slurry.     

Rubber composites based on graphene nanoplatelets,expanded graphite,carbon nanotubes and their combination: A comparative study

Solution styrene butadiene rubber (S-SBR) composites reinforced with graphene nanoplatelets (GnPs), expanded graphite (EG), and multiwalled carbon nanotubes (MWCNTs) were prepared and the electrical and various mechanical properties were compared to understand the specific dispersion and reinforcement behaviours of these nanostructured fillers. The electrical resistivity of the rubber composite gradually decreased with the increase of filler amount in the composite. The electrical percolation behaviour was found to be started at 15 phr (parts per hundred rubber) for GnP and 20 phr for EG filled systems, whereas a sharp drop was found at 5 phr for MWCNT based composites. At a particular filler loading, dynamic mechanical analysis and tensile test showed a significant improvement of the mechanical properties of the composites comprised of MWCNT followed by GnP and then EG. The high aspect ratio of MWCNT enabled to form a network at low filler loading and, consequently, a good reinforcement effect was observed. To investigate the effect of hybrid fillers, MWCNT (up to 5 phr) were added in a selected composition of EG based compounds. The formation of a mixed filler network showed a synergistic effect on the improvement of electrical as well as various mechanical properties.     

Effect of block-copolymer dispersants on properties of carbon nanotube/epoxy systems

The effects of the addition of eight different block copolymers on the dispersion stability of multi-walled carbon nanotubes (MWCNTs) are reported. Suspensions of CNTs in different components of an epoxy system have been prepared using a tip sonicator and different amounts of block copolymers. The resistance to sedimentation of MWCNTs in various media was systematically investigated by using a centrifugation technique. Block copolymers that result in dispersions of MWCNTs in epoxy and hardener stable for more than 1 week have been obtained. Dispersions using a single or a combination of two different dispersing agents have been used for the fabrication of MWCNT nanocomposites. The effect of different preparation routes and use of block copolymers on the tensile properties and surface resistivity of the composites have been evaluated. The results obtained have been related with the dispersion stability of the MWCNTs in the epoxy components.     

Electric field effects on CNTs/vinyl ester suspensions and the resulting electrical and thermal composite properties

In this study, electrical conductivity of a vinyl ester based composite containing low content (0.05, 0.1 and 0.3 wt.%) of double and multi-walled carbon nanotubes with and without amine functional groups (DWCNTs, MWCNTs, DWCNT-NH₂ and MWCNT-NH₂) was investigated. The composite with pristine MWCNTs was found to exhibit the highest electrical conductivity. Experiments aimed to induce an aligned conductive network with application of an alternating current (AC) electric field during cure were carried out on the resin suspensions with MWCNTs. Formation of electric anisotropy within the composite was verified. Light microscopy (LM), scanning electron (SEM) and transmission electron microscopy (TEM) were conducted to visualize dispersion state and the extent of alignment of MWCNTs within the polymer cured with and without application of the electric field. To gain a better understanding of electric field induced effects, glass transition temperature (T_g) of the composites was measured via Differential Scanning Calorimetry (DSC). It was determined that at 0.05 wt.% loading rate of MWCNTs, the composites, cured with application of the AC electric field, possessed a higher T_g than the composites cured without application of the AC electric field.     

Fabrication and characterization of Al-matrix composites reinforced with amino-functionalized carbon nanotubes

We report the fabrication of Al-matrix composites reinforced with amino-functionalized carbon nanotubes (fCNTs) using powder metallurgy process. Functionalization of the nanotubes was carried out by ball milling multiwalled carbon nanotubes (MWCNTs) in the presence of ammonium bicarbonate. It has been found that the mechanical properties of Al-fCNT composites were much superior to the composites fabricated using non-functionalized or acid functionalized carbon nanotubes. The enhancement in mechanical properties in these composites are attributed mainly to the better and homogeneous dispersion of fCNT in Al matrix as compared to non-functionalized or acid functionalized carbon nanotubes and the formation of a strong interfacial bonding between fCNT and Al matrix leading to an efficient load transfer from Al matrix to fCNT following high-resolution transmission electron microscopy.     

Preparation,characterization and properties of polycaprolactone diol-functionalized multi-walled carbon nanotube/thermoplastic polyurethane composite

Multi-walled carbon nanotubes (MWCNTs) were chemically functionalized to prepare thermoplastic polyurethane (PU) composites with enhanced properties. In order to achieve a high compatibility of functionalized MWCNTs with the PU matrix, polycaprolactone diol (PCL), as one of PU’s monomers, was selectively grafted on the surface of MWCNTs (MWCNT–PCL), while carboxylic acid groups functionalized MWCNTs (MWCNT–COOH) and raw MWCNTs served as control. Both MWCNT–COOH and MWCNT–PCL improved the dispersion of MWCNTs in the PU matrix and interfacial bonding between them at 1 wt% loading fraction. The MWCNT–PCL/PU composite showed the greatest extent of improvement, where the tensile strength and modulus were 51.2% and 33.5% higher than those of pure PU respectively, without sacrificing the elongation at break. The considerable improvement in both mechanical properties and thermal stability of MWCNT–PCL/PU composite should result from the homogeneous dispersion of MWCNT–PCL in the PU matrix and strong interfacial bonding between them.