Influence of injection molding on the electrical properties of polyamide 12 filled with multi-walled carbon nanotubes

Microinjection-molded and compression-molded polyamide (PA12) matrix composites filled with 0.67, 1.33, 2 and 4 wt% multi-walled carbon nanotubes (MWNTs) were prepared from twin-screw extruded pellets. The compression molded samples have an electrical percolation threshold close to 1.2 wt%. Coupled rheological and electrical measurements show that their electrical properties start decreasing as soon as shear begins and are partially restored during flow, suggesting successively breakage and reconstruction of a percolating network. On the other hand, the electrical properties of the microinjection molded composites are close to the matrix ones, showing that cooling is too fast for the MWNTs to form a network. There is some electrical anisotropy in these composites, as evidenced by a greater conductivity measured in the flow direction. However polarized Raman spectroscopy analysis does not reveal a significant orientation of the MWNTs.     

Rheology and properties of melt-processed poly(ether ether ketone)/multi-wall carbon nanotube composites

Poly(ether ether ketone) (PEEK)/multi-wall carbon nanotube (MWNT) composites containing up to 17 wt% filler were prepared using a twin screw extruder. Transmission electron microscopy (TEM) images reveal that the MWNTs were homogeneously dispersed in the PEEK matrix. Linear viscoelastic measurements show that both complex viscosity and moduli increase with increasing MWNT concentration. The storage modulus, G^′ exhibits a dramatic seven order increase in magnitude around 1 wt%, leading to a solid-like low-frequency behaviour at higher loadings; the effect can be attributed to network formation at a rheological percolation threshold. Rheotens measurements show that the melt strength also increases significantly on addition of nanotubes, however, the drawability decreases. An analytical Wagner model was used to calculate the apparent elongational viscosity over a wide range of elongational rates, and to reveal significant increases on addition of MWNTs, with a similar threshold behaviour. The electrical response is also dominated by percolation effects, increasing by nearly 10 orders of magnitude from 10⁻¹¹ to 10⁻¹ S/cm, on the addition of only 2 wt% MWNTs. In contrast, the thermal conductivity and tensile elastic modulus of the composites increased linearly with nanotube content, rising by 130% and 50%, at 17 wt% MWNTs, respectively.     

Processing and properties of MWNT/HDPE composites

Multi-walled carbon nanotube (MWNT) composites were fabricated using the screw extrusion and injection technique. The polymer-wrapped MWNTs were dispersed in fumed silicon dioxide with the help of ultrasonic stirring, and then further dispersed in a high density polyethylene (HDPE) matrix by a twin-screw extruder. It was found that there was a critical MWNT concentration around 1.0 wt% where a fine network of MWNT/SiO₂ was formed. This gives the MWNT/HDPE composites much improved mechanical properties. From the mechanical property, it was found that the surface treatment of MWNT/SiO₂ had a large effect on the performance of the composites. Thermogravimetric analysis (TGA) measurement showed that MWNT could stabilize HDPE when its weight content was greater than 2.0 wt%, whereas silicon dioxide accelerated thermo-oxidation of the composites.     

Morphology and electrical conductivity of polyethylene/polypropylene blend filled with thermally reduced graphene oxide and surfactant exfoliated graphene

High‐density polyethylene (HDPE)/polypropylene (PP) composites with graphenes were prepared by melt‐compounding method. Graphene sheets were prepared through thermally reduced graphene oxide (TRG) and surfactant exfoliated graphene (SEG), respectively. Structural characterization showed that the TRG sheets exhibited a few‐layers composition with more defects compared to the SEG sheets. Morphological observations of the composites demonstrated that the graphene was preferentially dispersed in the HDPE phase and the addition of graphene (TRG and SEG) influenced the phase structure of the HDPE/PP composites. The distribution of the TRG sheets in the HDPE phase was better than the SEG sheets, and the obtained HDPE/PP composites exhibited a low electrical percolation threshold with the highly dispersed graphene. The TRG/HDPE/PP composite showed a low electrical percolation threshold of 3 wt% (1.25 vol%). For the SEG/HDPE/PP system, the percolation threshold was 7 wt% (2.98 vol%). Differences in the behavior of the two graphene components (TRG and SEG) in the HDPE/PP composites influenced the formation of percolation networks and electrical properties. POLYM. COMPOS., 38:2098–2105, 2017. © 2015 Society of Plastics Engineers     

Influence of twin-screw extrusion conditions on the dispersion of multi-walled carbon nanotubes in a poly(lactic acid) matrix

Twin-screw extrusion using a co-rotating Berstorff ZE25 extruder was applied to disperse multi-walled carbon nanotubes (MWNT) in poly(lactic acid) (PLA). The masterbatch dilution technique was used whereas four different masterbatches were produced under variation of MWNT content, screw profile, temperature profile, and rotation speed which then were diluted to composites with 0.75 wt% MWNT under varied process conditions. The state of dispersion was investigated by light microscopy from which a dispersion index was quantified. Transmission electron microscopy was performed to observe the MWNT dispersion and network formation in the sub-micron scale.The state of MWNT dispersion within the diluted composites was predominated by the state of filler dispersion in the masterbatches. High rotation speed (500 rpm) that still ensures a certain residence time of the melt combined with a screw profile containing mainly mixing elements were found to be highly convenient to disperse and distribute the MWNT in the PLA matrix as well during masterbatch production as the dilution step. The temperature profile showed less influence, however, an increasing profile resulted in slightly better nanotube dispersions. By means of these processing conditions a percolation set was performed indicating an electrical percolation threshold below 0.5 wt% MWNT content as measured on compression molded samples.     

Effect of microfiber reinforcement on the morphology,electrical, and mechanical properties of the polyethylene/poly(ethylene terephthalate)/carbon nanotube composites

In situ microfiber reinforced conductive polymer composites consisting of high‐density polyethylene (HDPE), poly(ethylene terephthalate) (PET), and multiwalled carbon nanotube (CNT) were prepared in a twin screw extruder followed by hot stretching of PET/CNT phase in HDPE matrix. For comparison purposes, the HDPE/PET blends and HDPE/PET/CNT composites were also produced without hot stretching. Extrusion process parameters, hot‐stretching speed, and CNT amount in the composites were kept constant during the experiments. Effects of PET content and molding temperature on the morphology, electrical, and mechanical properties of the composites were investigated. Morphological observations showed that PET/CNT microfibers were successfully formed in HDPE phase. Electrical conductivities of the microfibrillar composites were in semi‐conductor range at 0.5 wt% CNT content. Microfiber reinforcement improved the tensile strength of the microfibrillar HDPE/PET/CNT composites in comparison to that of HDPE/PET blends and HDPE/PET/CNT composites prepared without hot stretching. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

Low percolation threshold in single-walled carbon nanotube/high density polyethylene composites prepared by melt processing technique

A new method was developed to disperse carbon nanotubes (CNTs) in a matrix polymer and then to prepare composites by melt processing technique. Due to high surface energy and strong adsorptive states of nano-materials, single-walled carbon nanotubes (SWNTs) were adsorbed onto the surface of polymer powders by spraying SWNT aqueous suspected solution onto fine high density polyethylene (HDPE) powders. The dried SWNTs/powders were blended in a twin-screw mixture, and the resulting composites exhibited a uniformly dispersion of SWNTs in the matrix polymer. The electrical conductivity and the rheological behavior of these composites were investigated. At low frequencies, complex viscosities become almost independent of the frequency as nanotubes loading being more than 1.5 wt%, suggesting an onset of solid-like behavior and hence a rheological percolation threshold at the loading level. However, the electrical percolation threshold is ∼4 wt% of nanotube loading. This difference in the percolation thresholds is understood in terms of the smaller nanotube-nanotube distance required for electrical conductivity as compared to that required to impede polymer mobility. The measurements of mechanical properties indicate that this processing method can obviously improve the tensile strength and the modulus of the composites.     

Effects of filler geometry on internal structure and physical properties of polycarbonate composites prepared with various carbon fillers

BACKGROUND: The effects of filler geometry are important for understanding the internal structure and physical properties of polymer composites. To investigate the effects of filler geometry on electrical conductivity as well as morphological and rheological properties, three types of polycarbonate (PC) composites were prepared by melt compounding with a twin‐screw extruder. RESULTS: The electrical conductivity of PC/carbon black (CB) and PC/graphite (carbon) nanofibre (CNF) composites did not show a percolation threshold through the entire filler loading ranges. However, PC‐blend‐carbon nanotube (CNT) composites showed a percolation electrical threshold for a filler loading of 1.0 to 3.0 wt% and their maximum electrical conductivity approached 10^?3 S m^?1. PC‐blend‐CB and PC‐blend‐CNF composites showed Newtonian behaviour like pure PC matrix, but PC‐blend‐CNT composites showed yield stress as well as increased storage modulus and strong shear thinning behaviour at low angular frequency and shear rate due to strong interactions generated between CNT–CNT particles as well as PC molecules and CNT particles on the nanometre scale. CONCLUSIONS: The electrical conductivity of the PC composites with different carbon constituents was well explained by the continuous network structure formed between filler particles. The network structure was confirmed by the good dispersion of fillers as well as by the yield stress and solid‐like behaviour observed in steady and dynamic shear flows. Copyright © 2009 Society of Chemical Industry     

Ultrahigh-shear processing for the preparation of polymer/carbon nanotube composites

Poly(vinylidene fluoride) (PVDF)/multiwalled carbon nanotube (MWCNT) composites were prepared using a novel ultrahigh-shear extruder by directly mixing MWCNT with PVDF in the molten state. A special feedback-type screw was used to obtain a high shear field and obtain a very uniform dispersion of the nanotubes in the polymer matrix under a higher screw rotation speed. Raman spectroscopy and scanning electron microscopy were used to determine the interaction and dispersion of nanotubes in the PVDF. The linear viscoelastic behavior and electrical conductivity of these composites were investigated. At low-frequencies, the storage shear modulus (G′) becomes almost independent of the frequency as nanotube loading increases, suggesting the onset of solid-like behavior in these composites. By plotting G′ vs. nanotube loading and fitting with a power-law function, we found that the rheological threshold of high-shear processed composites is about 0.96 wt% whereas that of low-shear processed composites is about 1.76 wt%. The electrical percolation threshold of high-shear processed composites is lower than that of low-shear processed composites.     

Electrical conductivity and percolation threshold of hybrid carbon/polymer composites

The electrical conductivity and percolation threshold of single and hybrid carbon filled composites are experimentally investigated. Polystyrene, carbon fiber (CF) and carbon black (CB) at three CF/CB ratios of 1.67, 3.33, 6.67 were compounded in a twin screw extruder micro‐compounder and compression molded into sheets. The through‐plane and in‐plane electrical conductivity of the composites are measured by 2 and 4 probe techniques. The percolation threshold of the single filler and hybrid composites are determined from the experimental results using a percolation model. The hybrid composites have a higher value of electrical conductivity and lower percolation threshold than the single CF filler composite except for the CF/CB ratio of 6.67. The percolation threshold for the cases of single filler and hybrid composites are modeled. The hard core / soft shell model is used and it is assumed that the percolation in a particle filled system depends on the ratio of tunneling distance to particle diameter. This ratio is determined by modeling single filler composites using the experimental data and kept constant in the modeling of the hybrid system. Finite size scaling is used to determine the percolation threshold for the infinite size hybrid system containing (nanosize) particles and micron size fibers for three CF/CB ratios. The simulation results show that the percolations of hybrid composites have the same trends observed in the experimental results. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41744.     

Nanoclay reinforced polyethylene composites: Effect of different melt compounding methods

Nanoclay (NC) reinforced high‐density polyethylene (HDPE) composites were prepared by different melt compounding methods using (1) a single screw extruder (SSE), (2) twin screw extruder (TSE), (3) a combination of SSE and extensional flow mixer (EFM), and (4) a bowl mixer masterbatch method (MB). PE‐grafted maleic anhydride (PE‐g‐MA) was used as a compatibilizer. EFM increased complex melt viscosity (η*) of the HDPE/NC composites as compared to the neat HDPE and also provided a better interaction between HDPE and NC to create slightly lower melt η* as compared to MB and PE‐g‐MA composites. The low viscosity melt behavior of the pure HDPE changes to more solid like melt behavior in the PE‐g‐MA HDPE/NC composites in the low frequency (ω) region. PE‐g‐MA + EFM method exhibited better impact strength compared to the other HDPE/NC composites. Using the PE‐g‐MA and masterbatch compounding methods had a beneficial role in improving mechanical properties. POLYM. ENG. SCI., 57:324–334, 2017. © 2016 Society of Plastics Engineers     

Development of electrical conductivity in PP/HDPE/MWCNT nanocomposite by melt mixing at very low loading of MWCNT

A method of developing an electrical conductivity in polypropylene (PP) with a very low loading of multiwalled carbon nanotube (MWCNT) by melt‐mixing method was described. PP/high‐density polyethylene (HDPE; 70/30, w/w) was melt blended simultaneously in the presence of MWCNT using two sequential heating protocol (MWCNT was first interacted with HDPE chain at 140°C followed by melt blending of PP at 200°C). Very interestingly, a cocontinuous morphology in the blend was found even for very high asymmetric composition. This has been explained in terms of barrier effect of the MWCNT dispersed selectively in the HDPE phase that restricts the phase inversion into the matrix droplet morphology. A simple method was used for proper dispersion, distribution, and formation of effective conducting network path [carbon nanotube (CNT)–CNT contact] of MWCNT through cocontinuous HDPE phase (minor phase) into PP matrix of the blend which in turn enhanced the electrical conductivity of the nanocomposite with minimum percolation threshold. The percolation threshold of PP/HDPE/MWCNT nanocomposite found at 0.352 wt% loading of MWCNT, which is significantly lower than those reported for developing electrical conductivity in PP/MWCNT nanocomposite. Phase morphology, extent of dispersion and location of the MWCNT in the blend has been investigated with a scanning and transmission electron microscopy. Thermal and mechanical properties of PP/HDPE/MWCNT nanocomposite with variation of MWCNT loading have also been studied. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

Rheological behavior of multiwalled carbon nanotube/polycarbonate composites

The rheological behavior of compression molded mixtures of polycarbonate containing between 0.5 and 15 wt% carbon nanotubes was investigated using oscillatory rheometry at 260 °C. The nanotubes have diameters between 10 and 15 nm and lengths ranging from 1 to 10 μm. The composites were obtained by diluting a masterbatch containing 15 wt% nanotubes using a twin-screw extruder. The increase in viscosity associated with the addition of nanotubes is much higher than viscosity changes reported for carbon nanofibers having larger diameters and for carbon black composites; this can be explained by the higher aspect ratio of the nanotubes. The viscosity increase is accompanied by an increase in the elastic melt properties, represented by the storage modulus G′, which is much higher than the increase in the loss modulus G″. The viscosity curves above 2 wt% nanotubes exhibit a larger decrease with frequency than samples containing lower nanotube loadings. Composites containing more than 2 wt% nanotubes exhibit non-Newtonian behavior at lower frequencies. A step increase at approximately 2 wt% nanotubes was observed in the viscosity-composition curves at low frequencies. This step change may be regarded as a rheological threshold. Ultimately, the rheological threshold coincides with the electrical conductivity percolation threshold which was found to be between 1 and 2 wt% nanotubes.     

Effects of the blending sequence in polyolefin ternary blends

Ternary blends of isotactic polypropylene (PP), ethylene–octene copolymer (mPE), and high‐density polyethylene (HDPE) were prepared by melt mixing in a twin‐screw extruder with two different sequences of mixing: the simultaneous mixing of the three components (method I) and the premixing of mPE and HDPE followed by mixing with PP (method II). Regardless of the mixing sequence, mPE encapsulated HDPE in the PP matrix, although better mechanical properties were generally obtained with method II. The domain size was mainly determined by the viscosity ratio of mPE to PP in method I and by the viscosity ratio of the binary blend (mPE/HDPE) to PP in method II. Specimens prepared by injection molding gave much finer dispersions than compression‐molded specimens. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 804–811, 2004     

Enhancing electrical properties of MWCNTs in immiscible blends of poly(methyl methacrylate) and styrene‐acrylonitrile copolymer by selective localization

Multiwalled carbon nanotubes (MWCNTs) were introduced into poly(methyl methacrylate) (PMMA) and styrene‐acrylonitrile copolymer (SAN) blends by melt mixing in an asymmetric miniature mixer (APAM). A composition of 70 wt% of PMMA and 30 wt% of SAN was mixed to create a co‐continuous morphology. Transmission electron microscopy images of ultra‐microtomed samples (70 nm in thickness) showed selective localization of MWCNTs inside the percolated SAN phase. The occurrence of the double percolation phenomenon resulted in lower electrical percolation thresholds of PMMA/SAN/MWCNT blends molded at high temperatures. Dielectric spectroscopy indicated a higher electrical permittivity for samples that were compression molded at 260°C. Due to the higher affinity of MWCNTs to SAN, there was a migration of MWCNTs into the SAN phase during the melt processing. Conductivity measurements revealed a significant decrease in electrical percolation threshold (0.4 wt%) for PMMA70/SAN30 blends compared with MWCNT‐filled SAN and MWCNT‐filled PMMA (ca. 0.8 wt%). POLYM. COMPOS., 37:1523–1530, 2016. © 2014 Society of Plastics Engineers     

Processing and mechanical properties of thermoplastic composites based on cellulose fibers and ethylene—acrylic acid copolymer

The melt processing and the tensile mechanical properties of composites consisting of 30 wt% softwood kraft pulp cellulose fibers and ethylene‐acrylic acid copolymer (EAA) with 7% acrylic acid content were studied. The compounding techniques used were extrusion mixing performed with a single screw extruder and elongation dispersive mixing performed with the injection‐molding machine. All blends were injection‐molded in a final step. Fiber length, fiber content, and mechanical properties were measured and the number and the size of the fiber aggregates were determined by microscopy analysis. It was concluded that two passes of elongation dispersive mixing had a beneficial effect on the mechanical properties, which could be related to the fewer and smaller amounts of aggregates. The different types of processing performed had a small or insignificant effect on the fiber length since the fiber lengths measured were within the same range as that of the starting material. POLYM. ENG. SCI., 52:1951–1957, 2012. © 2012 Society of Plastics Engineers     

多壁碳纳米管/聚碳酸酯复合材料的制备与性能

经硝酸氧化纯化的碳纳米管,在离子液体[Bmim]PF6存在下,溶液混合法制备了MWNTs/PC纳米复合薄膜。利用TEM、SEM对碳纳米管处理前后的形态结构、复合薄膜的微观结构进行了表征,考察了碳纳米管用量对MWNTs/PC复合材料的电学性质和力学性能的影响。结果表明,碳纳米管比较均匀地分散在PC基体中,在[Bmim]PF6作用下改善了碳纳米管与PC的相容性,提高了复合材料的力学性能。同时得出,复合材料的导电阈值出现在碳纳米管质量分数为1.0%～2.0%的范围内。     

Electrical,mechanical, and crystallization properties of ethylene‐tetrafluoroethylene copolymer/multiwalled carbon nanotube composites

Multiwalled carbon nanotubes (MWCNTs) were melt‐mixed in a conical twin‐screw extruder with a random copolymer of ethylene and tetrafluoroethylene. Surprisingly, the electrical percolation threshold of the resultant composites was quite low; ～0.9 wt %. In fact, this value is as low or lower than the value for most MWCNT/semicrystalline polymer composites made with roughly equivalent aspect ratio tubes mixed in a similar manner, for example, melt mixing. This low percolation threshold, suggestive of good dispersion, occurred even though the polymer surface energy is quite low which should make tubes more difficult to disperse. Dynamic mechanical measurements confirmed the rather low percolation threshold. The effect of nanotubes on crystallization kinetics was quite small; suggesting perhaps that a lack of nucleation which in turn reduces/eliminates an insulating crystalline polymer layer around the nanotubes might explain the low percolation threshold. Finally, the modulus increased with the addition of nanotubes and the strain at break decreased. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41052.     

Structure,mechanical, and electrical properties of high‐density polyethylene/multi‐walled carbon nanotube composites processed by compression molding and blown film extrusion

The structure and properties of melt mixed high‐density polyethylene/multi‐walled carbon nanotube (HDPE/MWCNT) composites processed by compression molding and blown film extrusion were investigated to assess the influence of processing route on properties. The addition of MWCNTs leads to a more elastic response during deformations that result in a more uniform thickness distribution in the blown films. Blown film composites exhibit better mechanical properties due to the enhanced orientation and disentanglement of MWCNTs. At a blow up ratio (BUR) of 3 the breaking strength and elongation in the machine direction of the film with 4 wt % MWCNTs are 239% and 1054% higher than those of compression molded (CM) samples. Resistivity of the composite films increases significantly with increasing BURs due to the destruction of conductive pathways. These pathways can be recovered partially using an appropriate annealing process. At 8 wt % MWCNTs, there is a sufficient density of nanotubes to maintain a robust network even at high BURs. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42665.     

Fabrication of polyethylene/graphite nanocomposite from modified expanded graphite

A novel process was employed to fabricate a polymer/expanded graphite nanocomposite by modifying the conducting filler expanded graphite (EG) with unsaturated polyester resin (UPR). The modified expanded graphite (MEG) was prepared from EG in which the graphite nanosheets, already present in EG, were wrapped and isolated by the UPR during processing. The as‐prepared MEG was reduced to powder form to improve its dispersion in the matrix. MEG powders were embedded into a high‐density polyethylene (HDPE) matrix via melt‐extrusion in a single‐screw extruder to prepare the conducting composite. The as‐prepared HDPE/EG conducting composite exhibited a low percolation threshold of ～5.7 wt% due to the high aspect ratio of graphite nanosheets. Mechanical properties such as the tensile and impact strength were also studied. Scanning electron microscopy was used to characterize the microstructure of EG, MEG powder and the resulting nanocomposites. Copyright © 2006 Society of Chemical Industry