Charakterisierung der Dispersionsgüte von Carbon Nanotubes in Polymer‐Nanokompositen

A practical overview of possibilities and limits to characterize the state of dispersion of carbon nanotubes (CNT) in polymer based nanocomposites is given. The most important and widely available methods are discussed with practical employment in mind. One focus is the quantitative characterization of the state of dispersion in solid samples using microscopy techniques such as optical microscopy or transmission electron microscopy. For dispersions of CNTs in aqueous media, solvents or monomers a sedimentation analysis is presented. This way dispersability and dispersion state of CNTs can be assessed. Indirect methods such as electrical conductivity measurements and rheological tests, dynamic differential scanning calorimetry and mechanical test are discussed.     

Influence of dispersion states of carbon nanotubes on physical properties of epoxy nanocomposites

Effects of different dispersion states of carbon nanotubes (CNTs) on rheological, mechanical, electrical, and thermal properties of the epoxy nanocomposites were studied. The dispersion states were altered depending upon whether a solvent was employed or not. To characterize dispersion of the CNTs, field emission scanning electron microscope (FESEM) and transmission electron microscopy (TEM) were used. It was found that the nanocomposites containing poorly dispersed CNTs exhibited higher storage modulus, loss modulus, and complex viscosity than ones with well dispersed CNTs. It means that the poorly dispersed CNTs/epoxy composites have, from a rheological point of view, a more solid-like behavior. Tensile strength and elongation at break of the nanocomposites with different dispersion of CNTs were measured. Both of the well and the poorly dispersed CNTs composites showed a percolation threshold of electrical conductivity at less than 0.5 wt.% CNTs loading and the former had higher electrical and thermal conductivities than the latter. Effects of the CNTs content on the physical properties were also examined experimentally. As loading of the CNTs increased, improved results were obtained. From the morphological observation by FESEM and TEM, it was found that when the solvent was not used in the CNTs dispersion process, aggregates of pristine CNTs remained in the nanocomposites.     

A systematic study on dispersion stability of carbon nanotube-modified epoxy resins

It is well accepted that the state of dispersion of carbon nanotubes (CNTs) considerably influences the performance of epoxy nanocomposites. Previous studies suggest that CNTs might reagglomerate during the processing of epoxy nanocomposites. Shear forces, resin viscosity, thermal excitation, curing reaction, and CNTs concentration are among the main factors suggested to influence the dispersion stability. The present work focuses on understanding the important role of each parameter on the dispersion stability and explaining the mechanisms by which the dispersion evolves during processing. In this regard, an in-situ dispersion monitoring technique was utilized to acquire dispersion micrographs from the sample of interest during a given heating profile. The results were supported by the rheological and contact angle measurements. It was found out that the increased mobility of CNTs in conjunction with the ineffective interfacial interaction between the nanotubes and resin was the main reason for the degradation of dispersion during the curing process.     

Network behavior of thermosetting polyimide/multiwalled carbon nanotube composites

In previous published research, network formation has been used to understand morphology and properties in polymer nanocomposites containing carbon nanotubes (CNTs) through measurements of rheological and electrical percolation thresholds, largely in thermoplastic matrices. In this research, these tools are explored as a means to understand network transport mechanisms and changes in CNT dispersion during curing in a thermosetting matrix. Specifically, rheological and electrical measurements were performed on the uncured nanocomposites, and electrical measurements were performed on the cured nanocomposites. The resulting data were applied to a percolation model. The results showed that the uncured resin played a limited role in mediating rheological transport and that little CNT aggregation occurred during curing. The results of this initial work suggest that such a combination of techniques is applicable to understanding dispersion changes resulting from curing and provides complementary insight to that provided by electron microscopy imaging of the same phenomenon.     

Ultrasound assisted twin screw extrusion of polymer-nanocomposites containing carbon nanotubes

The unique morphology and strong intertube attraction between carbon nanotubes (CNTs) make the dispersion of CNTs challenging and hence limit its effective use. A novel method for the continuous dispersion of multi-walled carbon nanotubes (MWNTs) in a polymer matrix for manufacturing high performance nanocomposites was developed using an ultrasonically assisted twin screw extrusion process. Reduction of the die pressure and variation of the ultrasonic power consumption as a function of amplitude were measured at various MWNT loadings. The effect of ultrasound on rheological, electrical, morphological and mechanical properties of polyetherimide (PEI) matrix and PEI-filled with 1-10 wt% MWNTs was studied. In the treated nanocomposites, the complex viscosity, storage and loss moduli were increased and damping characteristics were decreased as compared to untreated ones. Rheological and electrical percolations were found to be between 1 and 2 wt% MWNT loading. Ultrasonic treatment does not affect the electrical conductivity of nanocomposites. Mechanical properties such as Young's modulus and tensile strength were significantly increased with MWNT loading but moderately with ultrasonic treatment at high loadings and certain ultrasonic amplitudes. The morphology and state of dispersion of MWNTs were investigated by means of HRSEM. In the ultrasonically treated nanocomposites, the obtained micrographs showed excellent dispersion of MWNTs in PEI matrix.     

Largely improved crystallization behavior and thermal stability of poly(L‐lactide) via the synergistic effects of graphene oxide and carbon nanotubes

Graphene oxide (GO) and carbon nanotubes (CNTs) and their compound were introduced into semicrystalline poly(l ‐lactide) (PLLA) to prepare the corresponding binary and/or ternary nanocomposites, respectively. The dispersion states of nanofillers in different nanocomposites were investigated using UV‐Vis spectroscopy, scanning electron microscopy (SEM) and rheological measurement. The results showed that when GO and CNTs were simultaneously present in the PLLA matrix, good dispersion states of both GO and CNTs could be achieved and the ternary nanocomposites exhibited percolated network structure. The effects of different nanofillers on the crystallization behavior of PLLA matrix were comparatively investigated under the different crystallization conditions including melt crystallization process (nonisothermal and isothermal crystallization from the melt) and cold crystallization (crystallization occurring from an amorphous state during the annealing process). The results showed that GO and CNTs exhibited apparent synergistic effects in improving crystallization ability and enhancing crystallinity of PLLA matrix. Study on the thermal stability of nanocomposites showed that the presence of nanofillers greatly improved the thermal stability of PLLA matrix. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40143.     

Effect of dispersion on rheological and mechanical properties of polypropylene/carbon nanotubes nanocomposites

Polypropylene (PP) nanocomposites filled with the pristine multi‐wall carbon nanotubes (CNTs) and the purified CNTs were prepared by melt blending. The microstructure and linear viscoelastic properties wereinvestigated using rheological and morphological measurements. The results show that the purified CNTs disperse uniformly in the PP matrix. At low frequencies, frequency dependence of modulus weakens clearly with the addition of the CNTs, indicating that the long‐range motion of the polymer chains is restrained by the presence of the CNTs. Percolation networks form when the loading levels achieve up to 3 and 1.5 wt% for the composites with the pristine CNTs (PPCNTs) and the purified CNTs (PPcCNTs), respectively. The linear relaxation modulus increases with increasing loading level. And for composites with loading levels above percolation concentration, the modulus appears to reach a plateau at long time scales due to the formation of percolation network. Tensile strength and impact strength are simultaneously improved with the addition of the CNTs. The better the dispersion of the CNTs, the greater the improvement of the tensile strength and the impact strength. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Preparation and Electron Beam Irradiation of PVC/ENR/CNTs Nanocomposites

Poly (vinyl chloride), PVC/epoxidized natural rubber blend, ENR/carbon nanotubes, CNTs nanocomposites were prepared using melt intercalation and solution blending methods. In both preparation methods PVC: ENR: CNTs ratios were fixed at 50:50:2, while the 50/50 PVC/ENR blend without the addition of CNTs was used as control. The PVC/ENR/CNTs nanocomposites were exposed to electron beam (EB) irradiation at doses ranging from 0–200 kGy. The effects of two different preparation methods on the tensile properties, gel fraction and morphology of the PVC/ENR/CNTs nanocomposites were studied. Prior to EB irradiation, the addition of 2 phr of CNTs caused a drop in the tensile strength (Ts) of the 50/50 PVC/ENR blend, implying poor distribution of CNTs in the PVC/ENR blend matrix. However upon EB irradiation, the nanocomposites prepared by the melt blending method exhibited higher values of Ts as compared to the neat PVC/ENR blend due to occurrence of radiation-induced cross-linking in the PVC/ENR blend matrix. Transmission electron microscopy (TEM) images proved that a better dispersion of CNTs in PVC/ENR blend matrix can be achieved by melt intercalation compared to solution blending and the dispersion of CNTs was improved by irradiation. Scanning electron microscopy (SEM) results showed a distinct failure surface with formation of rough structure for the irradiated nanocomposites, which explains the higher values of tensile properties compared to the non-irradiated nanocomposites.     

The effect of twin screw extrusion on structural,electrical, and rheological properties in carbon nanotube poly‐ether‐ether‐ketone nanocomposites

The influence of twin screw extruder dispersion of multiwalled carbon nanotubes (CNTs) on the structural, electrical, and rheological properties in poly(ether ether ketone) is studied. Intermediate rotational speeds (200 rpm) of co‐rotating twin screws yield higher electrical conductivity and dynamic shear modulus than for lower or higher speeds when using 3 wt % multiwall CNTs. These improved properties at intermediate speeds are correlated with the dispersion state of nanotubes in the polymer matrix by using transmission electron microscopy and multispectral Raman mapping. We find that the complex shear modulus near structural percolation depends on the dispersion of the CNTs and the residence time in the extruder plays an important role in the final properties of the nanocomposite. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of Carbon Nanotubes on the Rheological and Electrical Percolation of PP/EPDM Blend

The rheological and electrical percolation of single-walled carbon nanotubes on a thermoplastic-elastomer based on polypropylene/ethylene-propylene-diene was investigated. Polypropylene-grafted maleic anhydride was used to improve the nanotube dispersion. The shear stress and viscosity decreased with increasing temperature from 200 to 220°C. The flow activation energy for the nanocomposites increased with increasing nanotube content. The morphology and degree of dispersion of the nanotubes in the thermoplastic-elastomer matrix were investigated using SEM. The obtained rheological and electrical properties of the nanocomposites indicate that they were affected by the nanotube-nanotube network structure, which was related to the morphological behavior of nanotubes uniform dispersion.     

On the dispersion of CNTs in polyamide 6 matrix via solution methods: assessment through electrical, rheological, thermal and morphological analyses

In this study, polyamide 6 (PA 6)/multi-walled carbon nanotube (MWCNT) nanocomposites were prepared by different solution methods based on phase inversion, drop-casting and simple evaporation processes. Optical microscopy and field emission scanning electron microscopy techniques were used to investigate the dispersion states of the nanotubes in PA 6 matrix. The results indicated that the dispersion state of MWCNTs in the nanocomposites prepared by the phase inversion-based method was better than those in the nanocomposites prepared by the other two methods. Electrical, rheological, differential scanning calorimetry and thermo-gravimetric analysis measurements showed that the PA 6/MWCNTs nanocomposites prepared by the phase inversion-based method had higher electrical conductivity, storage modulus, crystallization temperature and thermal stability in comparison with those prepared by the other two methods, attributed to the better dispersion state of MWCNTs. These results confirmed achievement of a good dispersion state of MWCNTs within PA 6 matrix by the phase inversion-based efficient approach.     

Quantification of carbon nanotube dispersion and its correlation with mechanical and thermal properties of epoxy nanocomposites

An experimental study is carried out to quantitatively assess the dispersion quality of carbon nanotubes (CNTs) in epoxy matrix as a function of CNT variant and weight fraction. To this end, two weight fractions (0.05% and 0.25%) of as-grown, oxidized, and functionalized CNTs are used to process CNT/epoxy nanocomposites. Scanning electron microscopy, X-ray diffraction, and Fourier transform infrared analysis of different variants of CNTs are used to establish the efficiency of purification route. While the relative change in mechanical properties is investigated through tensile and micro-hardness testing, thermal conductivity of different nanocomposites is measured to characterize the effect of CNT addition on the average thermal properties of epoxy. Later on, a quantitative analysis is carried out to establish the relationship between the observed improvements in average composite properties with the dispersion quality of CNTs in epoxy. It is shown that carboxylic (-COOH) functionalization reduces the average CNT agglomerate size and thus ensures better dispersion of CNTs in epoxy even at higher CNT weight fraction. The improved dispersion leads to enhanced interfacial interaction at the CNT/epoxy interface and hence provides higher relative improvement in nanocomposite properties compared to the samples prepared using as-grown and oxidized CNTs. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48879.     

Multiscale fiber‐reinforced composites prepared by vacuum‐assisted resin transfer molding

Carbon nanotube (CNT)/aramid fiber epoxy composites were produced using a new manufacturing method proposed in this study. The rheological and morphological experiments of the CNT/PEO nanocomposites indicates that the PEO nanocomposites have a good dispersion state of the CNTs. The flexural mechanical properties of the aramid fiber/CNT epoxy composites were measured. The CNTs dispersed in the epoxy resin between the aramid fibers were observed using field emission scanning electron miscroscope (FESEM). It was found that the flexural properties of the multiscale fiber‐reinforced composites were higher than those of aramid fiber/epoxy composites. POLYM. COMPOS., 28:458–461, 2007. © 2007 Society of Plastics Engineers.     

Titania-doped multi-walled carbon nanotubes epoxy composites: Enhanced dispersion and synergistic effects in multiphase nanocomposites

Multi-walled carbon nanotube-epoxy composites are modified with titania nanoparticles in order to obtain multiphase nanocomposites with an enhanced dispersion of carbon nanotubes. The dispersion is monitored using rheological and electrical conductivity measurements. An increase in dispersion quality can be correlated to an increased storage shear modulus of the uncured suspensions and to a decreased electrical conductivity in the bulk nanocomposite. The newly formed microstructure is revealed using transmission electron and optical microscopies. Due to chemical interactions between both types of nanoparticles an attractive potential is generated leading to a significant rearrangement in the particle network structure. Besides an enhanced dispersion, the hybrid structure leads to synergistic effects in terms of the glass transition of the nanocomposites. Although a decrease of the glass transition temperature (T_g) is observed for the nanocomposites containing only one type of filler, the combination of titania and carbon nanotubes into a hybrid structure reduces the decrease of T_g, thus demonstrating the potential of such hybrid structures as fillers for multi-functional epoxy nanocomposites.     

Experimental assessment on potential for processiblity of carbon nanotubes/epoxy system used as nanocomposites

In this study, carboxylic acid functionalized carbon nanotubes (CNTs) were used to modify epoxy with intent to develop a nanocomposite matrix for hybrid multiscale composites combining benefits of nanoscale reinforcement with well‐established fibrous composites. CNTs were dispersed in epoxy by using high energy sonication, followed by the fabrication of epoxy/CNTs composites. The processibility of CNTs/epoxy systems was explored with respect to their dispersion state and viscosity. The dependences of viscosity, mechanical and thermomechanical properties of nanocomposite system on CNTs content were investigated. The dispersion quality and reagglomeration behavior of CNTs in epoxy and the capillary infiltration of continuous fiber with the epoxy/CNTs dispersion were characterized using optical microscope and capillary experiment. As compared with neat epoxy sample, the CNTs nanocomposites exhibit flexural strength of 126.5 MPa for 1 wt% CNTs content and impact strength of 28.9 kJ m^?2 for 0.1 wt% CNTs content, respectively. A CNTs loading of 0.1 wt% significantly improved the glass transition temperatures, T_g, of the nanocomposites. Scanning electron microscopy (SEM) was used to examine the fracture surface of the failed specimens. It is demonstrated that the properties of CNTs/epoxy system are dispersion‐dominated and interface sensitive. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Synthesis and processing of PMMA carbon nanotube nanocomposite foams

Poly(methyl methacrylate) (PMMA) multi-walled carbon nanotubes (MWCNTs) nanocomposites were synthesized by several methods using both pristine and surface functionalized carbon nanotubes (CNTs). Fourier transform infrared (FTIR) spectroscopy was used to characterize the presence and types of functional groups in functionalized MWCNTs, while the dispersion of MWCNTs in PMMA was characterized using scanning electron microscopy (SEM). The prepared nanocomposites were foamed using carbon dioxide (CO₂) as the foaming agent. The cell morphology was observed by SEM, and the cell size and cell density were calculated via image analysis. It was found that both the synthesis methods and CNTs surface functionalization affect the MWCNTs dispersion in the polymer matrix, which in turn profoundly influences the cell nucleation mechanism and cell morphology. The MWCNTs are efficient heterogeneous nucleation agents leading to increased cell density at low particle concentrations. A mixed mode of nucleation mechanism was observed in nanocomposite foams in which polymer rich and particle rich region co-exist due to insufficient particle dispersion. This leads to a bimodal cell size distribution. Uniform dispersion of MWCNTs can be achieved via synergistic combination of improving synthesis methodology and CNTs surface functionalization. Foams from these nanocomposites exhibit single modal cell size distribution and remarkably increased cell density and reduced cell size. An increase in cell density of ∼70 times and reduction of cell size of ∼80% was observed in nanocomposite foam with 1% MWCNTs.     

Effect of SWCNT dispersion on epoxy nanocomposite properties

In nanocomposites containing single wall carbon nanotubes (SWCNTs), the final properties strongly depend on the dispersion quality of these fillers. Various methods have been used to improve the dispersion of nanofillers; however, one of the most effective ways is to functionalize carbon nanotubes (CNTs) with covalent and noncovalent functional groups. In this work, the dispersion of SWCNTs in an epoxy system was studied by using surfactants, acid (COOH), and ester groups (PGE)‐modified CNTs. Rheological and scanning electron microscopy analysis showed that functionalization of CNTs helped in improving the dispersion of fillers in the epoxy matrix. Systems with surfactant modified SWCNTs (1 wt%) exhibited the highest storage modulus at low frequencies after 5‐min sonication. This behavior is associated to a stronger network of fillers as a result of a good dispersion. However, longer sonication times lowered the storage modulus, corresponding to a degradation of the tubes. The effect of the dispersion quality on mechanical properties was also studied using a three‐point bending set‐up. POLYM. COMPOS.,, 2012. © 2012 Society of Plastics Engineers     

Thermal and electrical properties of carbon nanotubes based polysulfone nanocomposites

Carbon nanotubes (CNTs)-reinforced polysulfone (PSU) nanocomposites were prepared through solution mixing of PSU and different weight percent of multi-walled carbon nanotubes (MWCNTs). Thermal properties of nanocomposites were characterized using thermo-gravimetric analysis (TGA) and differential scanning calorimetry (DSC). TGA studies revealed an increase in thermal stability of the PSU/MWCNTs nanocomposites, which is due to the hindrance of the nanodispered carbon nanotubes to the thermal transfer in nanocomposites and also due to higher thermal stability of CNTs. Morphological properties of nanocomposites were characterized by high resolution transmission electron microscopy (HRTEM) and field emission scanning electron microscope (FESEM). The influence of CNTs loading on electrical properties of PSU/MWCNTs nanocomposites was studied by the measurement of AC and DC resistivity. Dielectric study of nanocomposites was carried out at different frequencies (10 Hz–1 MHz) by using LCR meter. An increase in dielectric constant and dielectric loss was observed with increase in CNTs content, which is due to the interfacial polarization between conducting CNTs and PSU.     

Enhanced electrical properties of polycarbonate/carbon nanotube nanocomposites prepared by a supercritical carbon dioxide aided melt blending method

Polycarbonate/carbon nanotube (CNT) nanocomposites were generated using a supercritical carbon dioxide (scCO₂) aided melt blending method, yielding nanocomposites with enhanced electrical properties and improved dispersion while maintaining the aspect ratio of the as-received CNTs. Baytubes^® C 150 P CNTs were benignly deagglomerated with scCO₂ resulting in 5 fold (5X), 10X and 15X decreases in bulk density from the as-received CNTs. This was followed by melt compounding with polycarbonate to generate the CNT nanocomposites. Electrical percolation thresholds were realized at CNT loading levels as low as 0.83 wt% for composites prepared with 15X CNT using the scCO₂ aided melt blending method. By comparison, a concentration of 1.5 wt% was required without scCO₂ processing. Optical microscopy, transmission electron microscopy, and rheology were used to investigate the dispersion and mechanical network of CNTs in the nanocomposites. The dispersion of CNTs generally improved with scCO₂ processing compared to direct melt blending, but was significantly worse than that of twin screw melt compounded nanocomposites reported in the literature. A rheologically percolated network was observed near the electrical percolation of the nanocomposites. The importance of maintaining longer carbon nanotubes during nanocomposite processing rather than focusing on dispersion alone is highlighted in the current efforts.     

Assessment of intertube interactions in different functionalized multiwalled carbon nanotubes incorporated in a phenoxy resin

In this work, about 1 wt% of different functionalized carbon nanotubes (CNTs), namely CNT? COOH (CNT with carboxylic groups), CNT? NH₂ (CNT with amine groups) and CNT? OH (CNT with hydroxyl groups), as well as nonfunctionalized CNTs were incorporated into a phenoxy resin via a melt mixing process. The extent of intertubes and polymer–tubes interactions and their influence on state of CNTs dispersion were assessed through determination of electrical, rheological, and morphological characteristics. CNT? NH₂ showed the lowest intertubes interactions followed by CNT? OH and CNT? COOH. Nanocomposite made from CNT? COOH showed the poorest state of CNTs dispersion and the biggest CNTs agglomerates and it remained nonconductive. The acid‐functionalized CNTs were not able to form strong polymer–tube interactions because of their high cohesive energy and therefore in the melt rheological investigations they exhibited the lowest storage modulus and complex viscosity as well as the highest loss factor among all the studied CNTs. A good balance between intertubes and polymer–tube interactions is necessary through proper selection of CNTs functional groups for achieving a good state of CNTs dispersion and consequently obtaining enhanced electrical and viscoelastic properties. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers