Electrical conductivity of polyurethane/MWCNT nanocomposite foams

Polymeric foams with electrical conductivity represent a novel and very interesting class of materials rather sporadically studied. In this study, the feasibility to prepare electrically conductive Rigid Polyurethane (PUR) foams at various densities using multiwall carbon nanotubes (MWCNT) at varying contents was investigated. The produced PUR/MWCNT foams exhibited electrical conductivity over a wide range of densities and nanofiller contents. The effect of these two parameters on the electrical conductivity of the final foam system was studied. To explain the behavior, Statistical Percolation laws were employed. Model parameters were elaborated for both cases showing that the percolation model can adequately describe the behavior. The foaming process is analyzed in further detail to assist in the explanation and understanding of theexperimental observations. Finally, a material design map is proposed for the preparation of electrically conductive foams. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Influence of nanotube characteristics on electrical and thermal properties of MWCNT/polyamide 6,6 composites prepared by melt mixing

Differential scanning calorimetry (DSC), X-ray diffraction, dynamic mechanical analysis (DMA) and electrical conductivity measurements were performed on multiwalled carbon nanotube/polyamide 6,6 composites with four different types of well-characterized tubes manufactured using fixed-bed catalytic processes. The tubes differed in diameter, number of walls and surface chemistry. Except for one very poorly formed set of tubes, there were not large differences in behavior with respect to modulus, maximum electrical conductivity and percolation threshold; none of which differed by more than a factor of 2 for the three types of tubes. However, the shape of the percolation region was very different for the larger diameter tubes in that the percolation region occurred over a much wider concentration. Glass transition and crystallization/melting characteristics also showed very small differences between the three types of tubes. One unique observation made in this work was that the glass transition temperature (T_g) showed a qualitatively different behavior depending on what was used to measure the transition: DSC indicated an increase in T_g with added nanotubes while DMA showed a decrease in T_g. Other than the difference being related to how the T_g was measured, it is not clear what caused the qualitatively different behavior.     

Mechanical properties of polyurethane/montmorillonite nanocomposite prepared by melt mixing

Nanocomposites from polyurethane (PU) and montmorillonite (MMT) were prepared under melt‐mixing condition, by a twin screw extruder along with a compatibilizer to enhance dispersion of MMT. MMT used in this study was Cloisite 25A (modified with dimethyl hydrogenated tallow 2‐ethylhexyl ammonium) or Cloisite 30B (modified with methyl tallow bis‐2‐hydroxyethyl ammonium). Maleic anhydride grafted polypropylene (MAPP) was used as the compatibilizer. XRD and TEM analysis demonstrated that melt mixing by a twin‐screw extruder was effective in dispersing MMT through the PU matrix. The PU/Cloisite 30B composite exhibited better interlayer separation than the PU/Cloiste 25A composite. Nanoparticle dispersion was the best at 1 wt % of MMT and improved with compatibilizer content for both composites. Properties of the composites such as complex viscosity and storage modulus were higher than that of a pure PU matrix and increased with the increase in MMT content, but decreased with the increase in compatibilizer content. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Performance of MWCNT/HDPE Nanocomposites at High Strain Rates

Performance of HDPE/MWCNT composite at high strain rate up to 10⁴ s^?1 was investigated in a split Hopkinson pressure bar. The results revealed that the incorporation of MWCNTs into HDPE can enhance the impact strength of HDPE. High strain rate impact has a significant influence on morphology, density, crystallinity and melting temperature of the composite. With increase in strain rate, the densities of both HDPE and HDPE/MWCNT composite decreased. The drop of the density of HDPE/MWCNT composite was quicker than that of HDPE density. This could be the reason that much more cracks were formed in the HDPE/MWCNT composite, which could result in high energy dissipation, during SHPB test. The corporation of MWCNTs did lead to the decrease in yield stress.

     

Moderate anisotropy in the electrical conductivity of bulk MWCNT/epoxy composites

Bulk aligned multi-walled carbon nanotube films and their epoxy composites were prepared and their DC and AC conductivity studied. Nanotube films of up to 2 mm thickness were grown by catalytic chemical vapor deposition. Composites of nanotubes were made by infiltrating the films with a commercial epoxy. DC electrical resistivities in the axial direction of as-grown and purified films were found to be ∼1.2 Ωmm and ∼3.4 Ωmm, respectively. For the transverse direction the resistivity values were higher only with a factor of ∼2. In the case of composites, anisotropy is more pronounced showing more than an order of magnitude higher resistivity in the transverse direction (∼71.4 Ωmm) as compared to the axial value (∼4.2 Ωmm). AC behavior of the films investigated between 1 MHz and 3 GHz shows the presence of inductive and capacitive components at frequencies above ∼100 MHz. The moderate anisotropy for both DC and AC electrical properties are explained on the basis of the films’ structure combined with percolation theory and equivalent circuit models.     

Surfactant-free ionic liquid-based nanofluids with remarkable thermal conductivity enhancement at very low loading of graphene

We report for the first time the preparation of highly stable graphene (GE)-based nanofluids with ionic liquid as base fluids (ionic liquid-based nanofluids (Ionanofluids)) without any surfactant and the subsequent investigations on their thermal conductivity, specific heat, and viscosity. The microstructure of the GE and MWCNTs are observed by transmission electron microscope. Thermal conductivity (TC), specific heat, and viscosity of these Ionanofluids were measured for different weight fractions and at varying temperatures, demonstrating that the Ionanofluids exhibit considerably higher TC and lower viscosity than that of their base fluids without significant specific heat decrease. An enhancement in TC by about 15.5% and 18.6% has been achieved at 25 °C and 65 °C respectively for the GE-based nanofluid at mass fraction of as low as 0.06%, which is larger than that of the MWCNT-dispersed nanofluid at the same loading. When the temperature rises, the TC and specific heat of the Ionanofluid increase clearly, while the viscosity decreases sharply. Moreover, the viscosity of the prepared Ionanofluids is lower than that of the base fluid. All these advantages of this new kind of Ionanofluid make it an ideal fluid for heat transfer and thermal storage.     

低电导率酪蛋白胶的研制

以酪蛋白、尿素、可溶性淀粉、交联剂、防腐剂和消泡剂等为原料,经45~55℃溶解、75~80℃熟化、45~50℃过滤、室温陈化24 h后制得低电导率酪蛋白胶,同时对制备该酪蛋白胶的温度、反应时间和黏度等进行了对比试验。研究结果表明:该酪蛋白胶的电导率(19.0℃)为51.4 m S/cm、黏度(25℃)为3.5 Pa·s和p H(25℃)为7.3,并且是一种环保型胶粘剂。     

Enhanced dielectric constant and suppressed electrical conductivity in polymer nanocomposite films via loading MXene/TiO2/MoS2 nanosheets

Conductor/polymer nanocomposites can achieve high dielectric constant with low filler loading, but conductive fillers come into contact with each other easily, resulting in the formation of conductive paths. In this work, MXene/TiO₂/MoS₂ nanosheets were prepared by one-step hydrothermal method, and MXene/TiO₂/MoS₂/poly(vinylidene fluoride-co-hexafluoropropylene) (P(VDF-HFP)) nanocomposite films were prepared by solution casting method. At 1 kHz, with an optimized MXene/TiO₂/MoS₂ nanosheets loading of 8.0 wt%, MXene/TiO₂/MoS₂/P(VDF-HFP) nanocomposite films achieve a high dielectric constant of 944 and maintain a low dielectric loss of 0.19. TiO₂ and MoS₂ semiconductive layers on the surface of MXene nanosheets can prevent the formation of conductive paths, and therefore, nanocomposite films possess suppressed electrical conductivity. Moreover, MXene/TiO₂/MoS₂ nanosheets can build more microcapacitor structures in nanocomposite films with higher filler loading, which further improves the dielectric constant of nanocomposite films. Finite element simulation shows that TiO₂ and MoS₂ semiconductive layers can lower the electric field intensity and polarization intensity at the interface between conductive fillers and polymer matrix. Herein, MXene/TiO₂/MoS₂/P(VDF-HFP) nanocomposite films possess not only excellent dielectric properties, but also excellent mechanical properties, which can be used as flexible dielectric materials in electronic packaging technology.     

Influence of EMAA compatibilizer on the structure and properties of HDPE/hydrotalcite nanocomposites prepared by melt mixing

High‐density polyethylene (HDPE)/hydrotalcite nanocomposites were prepared and characterized with a partially neutralized sodium ionomer of poly(ethylene‐co‐methacrylic acid) (EMAA) as a compatibilizer. Moreover, nanocomposites based on this ionomer were characterized as patterns to analyze the interactions between the hydrotalcite sheets and the methacrylic groups on the ionomer. Hydrotalcite particles were organically modified with sodium dodecyl sulfate ions. Their presence in the interlayer space was confirmed by means of Fourier transform infrared spectroscopy (FTIR) and X‐ray diffraction (XRD). Morphological analysis carried out with XRD and transmission electron microscopy (TEM) revealed the partially exfoliated/intercalated structure achieved in the nanocomposites. The mechanical properties of the HDPE nanocomposites mainly depended on the nature of the polymer matrix. Higher values of the tensile strength and Young's modulus were found in the EMAA nanocomposites. Thermogravimetric analysis (TGA) showed that hydrotalcite particles improved the thermal stability and delayed the onset decomposition temperature of both HDPE and EMAA nanocomposites. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Role of interface on electrical conductivity of carbon nanotube/alumina nanocomposite

Interface of multiwalled carbon nanotube (MWCNT)/alumina (Al₂O₃) nanocomposites have been studied using TEM. At low sintering temperature (T_sin=1500 °C), a 3–5 nm thick amorphous interface region was noticed. Nanocomposite sintered at 1700 °C possessed a well-defined graphene layer coating on matrix grains as the interface between CNT and Al₂O₃. A mechanism of such layered interface formation has been proposed. No traceable chemical reaction product was observed at the interface even after sintering at 1700 °C. It was noticed that while DC electrical conductivity (σ_DC) of 1500 °C sintered 2.4 vol% MWCNT/Al₂O₃ nanocomposite was only~0.02 S/m, it raised to ~21 S/m when sintering was done at 1700 °C. Such 10³ times increase in σ_DC of present nanocomposite at a constant CNT loading was not only resulted from the exceptionally high electron mobility of CNT but the well-crystallized graphene interface on insulating type Al₂O₃ grains also significantly contributed in the overall increase of electrical performance of the nanocomposite, especially, when sintering was done at 1700 °C.     

Development of isotropic compatible HDPE/PP blends for structural applications

In an attempt to provide superior products for the structural applications, this study aimed at preparing isotropic compatible high density polyethylene (HDPE)/ polypropylene (PP) blends without the use of the expensive compatibilization technique. Morphological and structural characterizations of the homopolymers and blends were carried out. In addition, some of the structurally important mechanical and thermal properties were characterized. Such characterizations were performed to investigate whether or not the blends are compatible and therefore acceptable for the structural applications. Scanning electron microscope (SEM) micrographs of the blend samples indicate that the interfacial adhesion between HDPE and PP phases is intimate in the 5/95 HDPE‐PP, good in the 85/15 HDPE‐PP and 95/5 HDPE‐PP, fair in the 30/70 HDPE‐PP and very poor in the 50/50 HDPE‐PP. Similarly, mechanical and thermal responses of the first three blends are remarkable. The 30/70 HDPE‐PP blend displays a fairly good performance. Whereas, the properties of the 50/50 HDPE‐PP blend are very poor. This decides that the first three blends are compatible and, therefore, structurally attractive materials. The fourth is partially compatible and, as a consequence, can be rather acceptable for the structural applications. However, the fifth is incompatible and, of course, is not acceptable for such applications. On the other hand, SEM micrographs and differential scanning calorimetry results indicate that the crystalline structures of individual polymers are appreciably affected by blending. Additionally, the study reveals that the end use performance of blends is strongly dependent on the crystalline structure changes occurring in each component due to blending as well as the compatibility between the blend components. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

PP/clay nanocomposite: optimization of mixing conditions with respect to mechanical properties

Polypropylene/clay nanocomposites were studied with focus on optimization of mixing conditions. Two different types of commercial nanofillers Dellite^® were used (Dellite^® 72T and Dellite^® 67G). Effect of various concentrations of fillers on morphology and mechanical properties was investigated. Conditions of preparation were varied with respect to mixing time and speed of rotation of kneaders. Results of morphology study showed that nanocomposites contained agglomerates of nanofillers. The comparison of the filler types revealed that better dispersion and distribution was found for nanocomposites containing Dellite 72T which had also better tensile strength. Optimum mixing time was 30 min. 3D graphical analysis showed that the optimum speed of rotation was 60 rpm and with increasing clay content (2–10 wt%) the tensile strength increased.     

Evolution of the electrical resistivity at rest and during oscillatory shearing of co-continuous morphology (PP/PMMA)/MWCNT systems

In this work, a modified parallel-disks configuration on a strain-controlled ARES rheometer (TA Instrument) was used to study the evolution of the electrical resistivity at rest and during oscillatory shearing of a co-continuous immiscible polymer blend morphology based on polypropylene and /polymethyl(methacrylate) (PP/PMMA) in which various amounts (0–3 wt%) of multiwall carbon nanotubes (MWCNT) were added. The co-continuity of both PP and PMMA phases allowed the buildup of a conductive network due to the preferential localization of the conductive MWCNT at the interface between PP and PMMA. Under a stepwise increase of the oscillatory strain amplitude below a critical value (γ_c = 6.3%), a significant decrease in the electrical resistivity was observed for MWCNT concentrations above the percolation threshold (0.3 wt%) due to the conductive paths induced by both thermal (Brownian) motion and oscillatory shearing. However, for deformation amplitudes higher than γ_c, the resistivity increased due to the destruction of the MWCNT paths induced by the large deformation imposed on the PP/PMMA interface. These observations were also confirmed by the evolution of the storage modulus (G′) which remained constant for γ_c < 6.3% (linear viscoelastic regime), while the values decreased above γ_c due to the destruction of the system's morphology.     

Preparation and characterization of polypyrrole/clinoptilolite nanocomposite with enhanced electrical conductivity by surface polymerization method

In this work, polypyrrole/clinoptilolite nanocomposite was synthesized by in situ surface polymerization of pyrrole using Fe³⁺ as oxidant, incorporated on the inner and outer surface of clinoptilolite nanoparticles. Formation of nanocomposite and deposition of polypyrrole on the clinoptilolite surface was confirmed and characterized using Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD) patterns, scanning electron microscopy (SEM), and cyclic voltammetry techniques. Elemental analysis showed the loading/incorporation of 9.18 wt% polypyrrole in the clinoptilolite structure. However the electrical conductivity of polypyrrole/clinoptilolite nanocomposite pellets was higher than that of similar pure polypyrrole pellets, synthesized through the chemical oxidation polymerization method using Fe³⁺ as oxidant without the presence of clinoptilolite nanoparticles. Improved structural order or crystalinity of polypyrrole chains in nanocomposite structure which was confirmed by XRD and SEM results, may be the responsible of higher electrical conductivity of nanocomposite compared to pure polypyrrole although the low content (9.18 wt%) of polypyrrole in nanocomposite. Cyclic voltammetry studies showed that polypyrrole/clinoptilolite nanocomposite is electroactive similar to pure polypyrrole. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

A facile route to develop electrical conductivity with minimum possible multi‐wall carbon nanotube (MWCNT) loading in poly(methyl methacrylate)/MWCNT nanocomposites

Today, we stand at the threshold of exploring carbon nanotube (CNT) based conducting polymer nanocomposites as a new paradigm for the next generation multifunctional materials. However, irrespective of the reported methods of composite preparation, the use of CNTs in most polymer matrices to date has been limited by challenges in processing and insufficient dispersability of CNTs without chemical functionalization. Thus, development of an industrially feasible process for preparation of polymer/CNT conducting nanocomposites at very low CNT loading is essential prior to the commercialization of polymer/CNT nanocomposites. Here, we demonstrate a process technology that involves in situ bulk polymerization of methyl methacrylate monomer in the presence of multi‐wall carbon nanotubes (MWCNTs) and commercial poly(methyl methacrylate) (PMMA) beads, for the preparation of PMMA/MWCNT conducting nanocomposites with significantly lower (0.12 wt% MWCNT) percolation threshold than ever reported with unmodified commercial CNTs of similar qualities. Thus, a conductivity of 4.71 × 10^?5 and 2.04 × 10^?3 S cm^?1 was achieved in the PMMA/MWCNT nanocomposites through a homogeneous dispersion of 0.2 and 0.4 wt% CNT, respectively, selectively in the in situ polymerized PMMA region by using 70 wt% PMMA beads during the polymerization. At a constant CNT loading, the conductivity of the composites was increased with increasing weight percentage of PMMA beads, indicating the formation of a more continuous network structure of the CNTs in the PMMA matrix. Scanning and transmission electron microscopy studies revealed the dispersion of MWCNTs selectively in the in situ polymerized PMMA phase of the nanocomposites. Copyright © 2012 Society of Chemical Industry     

Modification of PP/HDPE blends by PP-PE sequential polymerization product

The morphology and mechanical properties of polypropylene/high-density polyethylene (PP/HDPE) blends in a wide range of compositions modified by a sequential Ziegler-Natta polymerization product (PP-PE) have been investigated. PP-PE contains multiple components such as PP, ethylene-propylene copolymer (EPC), and high molecular weight polyethylene (HMWPE). The effects of PP-PE on the mechanical properties and morphology of the PP/HDPE blends are the aggregative results of all its individual components. Addition of PP-PE to the blends not only improved the tensile strength of the blends, but the elongation at break increased linearly while the moduli were nearly unchanged. Morphological studies show that the adhesion between the two phases in all the blends of different compositions is enhanced and the dispersed domain sizes of the blends are reduced monotonously with the increment of the content of PP-PE. PP-PE has been demonstrated to be a more effective compatibilizer than EPC. Based on these results, it can be concluded that the tensile strength of the blends most on the adhesion between the two phases and the elongation at break depends most on the domain size of the dispersed component. © 1995 John Wiley & Sons, Inc.     

Modified preparation of HDPE/clay nanocomposite by in situ polymerization using a metallocene catalyst

In this study, preparation of high-density polyethylene (HDPE)/clay nanocomposite by in situ polymerization of ethylene using a zirconocene catalyst (bis-(cyclopentadienyl) zirconium dichloride (Cp₂ZrCl₂)) was investigated. To obtain higher efficiency, nanoclay particles (Na-montmorillonite) were modified by ammonia (NH₃), NH₃/methylaluminoxane (MAO), NH₃/dodecylamine (DDA), and NH₃/MAO/DDA systems. The results showed that the activity of the catalyst supported on the nanoclay particles modified by NH₃/MAO (762 g_p/mmol (Zr) t [atm]) was higher than that of the one supported on the unmodified nanoclay as well as the other prepared modified nanoclay-supported catalyst systems. The catalyst activities versus MAO concentration in NH₃/MAO treatment system and versus DDA concentration in NH₃/DDA system showed a maximum. Unexpectedly, a very low catalyst activity (180 g_p/mmol(Zr) t [atm]) was obtained using NH₃/MAO/DDA system. X-ray diffraction patterns showed that the HDPE/clay nanocomposites prepared by NH₃/MAO/DDA treatment system had less intercalated structure. Fourier transform infrared (FTIR) spectroscopy confirmed that water molecules of the nanoclay particles were reduced by NH₃ modification. DSC results revealed that crystallinity of the HDPE/clay nanocomposites increased with the modification of the nanoclay particles. The maximum degree of crystallinity of 80.8% was obtained for HDPE/clay nanocomposites prepared by the nanoclay modified by NH₃. In addition, nanoclay modification with NH₃, NH₃/MAO, and NH₃/DDA systems resulted in higher thermal decomposition temperature (~30 °C higher than 480 °C of the unmodified one). Such increase was not observed for the NH₃/MAO/DDA treatment system. Dynamic mechanical analysis showed an increase in the elastic modulus of the nanocomposite samples prepared by modified nanoclay particles, as well. Meanwhile, modification of the nanoclay particles by NH₃ led to the highest elastic behavior compared to the other modification systems. It was about 4.6 GPa which was 28% higher than the elastic modulus of the nanocomposite prepared by unmodified nanoclay particles.     

Toughness of HDPE/CaCO3 microcomposites prepared from masterbatch by melt blend method

In this study, a series of high‐density polyethylene and micro/nanocalcium carbonate polymer composites (HDPE/CaCO₃ nanocomposites) were prepared via melt blend technique using a twin screw extruder. Nanocomposite samples were prepared via injection molding for further testing. The effect of % loading of CaCO₃ on mechanical and fracture toughness of these composites has been investigated in details. The effect of precrack length variation on the fracture toughness of the composite samples was evaluated, and the morphology of the fractured samples was also observed using scanning electron microscopy (SEM). It was found that increasing the % of CaCO₃ and precrack length decreased the fracture toughness. Fracture surface examination by SEM indicated that the diminished fracture properties in the composites were caused by the aglomerization of CaCO₃ particles which acted as stress concentrators. A finite element analysis using ANSYS was also carried out to understand the effect of agglomeration size, interaction between the particles and crack tip length on the fracture properties of these composites. Finally, a schematic presentation of the envisioned fracture processes was proposed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

溶剂热法制备N-S共掺杂TiO_2/MWCNT复合材料及其光催化活性的研究

采用溶剂热法,以四氯化钛为前驱体,以硫脲为氮源和硫源,将纳米二氧化钛负载在多壁碳纳米管的表面,制备氮、硫共掺杂的纳米二氧化钛/碳纳米管复合材料,以盐酸土霉素的光催化降解为探针反应,研究复合材料的光催化降解活性。结果表明,溶剂热法制备的纳米二氧化钛以锐钛矿相存在,均匀、致密的包覆在多壁碳纳米管的管壁上,添加硫脲的复合材料比未添加硫脲的样品在紫外和可见光区域均有较好的光吸收性能。硫脲的添加增强了复合材料的光催化活性,当二氧化钛和硫脲的摩尔比为1∶6时,催化剂的光催化活性最好,用过的样品经洗涤、烘干再生后用于实验,仍具有较好的光催化活性。     

Functionalized polypropylene prepared by melt free radical grafting of low volatile oxazoline and its potential in compatibilization of PP/PBT blends

This article concerns the functionalization of polypropylene (PP) with oxazoline functionality by melt free radical grafting along with a low degree of degradation of PP in a batch mixer. A low volatile oxazoline, ricinoloxazoline maleinate (OXA), was used as the monomer. The grafting yield of OXA ranged from about 0.5 phr up to 1.5 phr (grams per 100 grams of PP) when its initial concentration and that of the peroxide ranged from 1.5 to 6.0 phr and 0.1 to 0.7 phr, respectively. The corresponding conversion of OXA to grafted OXA ranged from about 15 to 50%. Addition of styrene (St) as the comonomer did not enhance the grafting yield of OXA but markedly reduced the PP degradation. Also, little homo-and/or copolymers of OXA and/or St were found in the grafting system. This agrees with our finding that OXA and St did not copolymerize easily. The potential of using an OXA modified PP (PP-g-OXA) as the compatibilizer precursor in PP/PBT blends was examined as well. The presence of PP-g-OXA reduced the particle size of the dispersed phase (PBT) along with improved cohesion between the PP and PBT phases. This is consistent with a model kinetic study, which showed that the reaction between oxazoline and carboxylic functionalities was very fast. © 1996 John Wiley & Sons, Inc.