Economical conductive graphite-filled polymer composites via adjustable segregated structures: Construction,low percolation threshold,and positive temperature coefficient effect

The economical graphite-filled thermoplastic urethane/ultra-high molecular weight polyethylene (TPU/UHMWPE) composites with the segregated structure were constructed by the combination of mechanical crushing and melt blending method. The low percolation threshold of 1.89 wt% graphite in the adjustable segregated composites was obtained and high electrical conductivity was about 10⁻¹ S m⁻¹ at 10 wt% graphite loadings owing to the formation of three-dimensional conductive networks. Moreover, when the graphite loadings were over the percolation threshold, the remarkable positive temperature coefficient (PTC) effect of electrical resistivity for TPU/UHMWPE-Graphite composites were achieved, originating from the combined thermal motion of TPU and UHMWPE. Meanwhile, the outstanding repeatability of PTC effects was obtained after 5-time cycles. Therefore, economical conductive polymer composites were still the promising field in the practical application of PTC materials.     

Morphological and physical properties of a thermoplastic polyurethane reinforced with functionalized graphene sheet

BACKGROUND: Functionalized graphene sheet (FGS) was recently introduced as a new nano‐sized conductive filler, but little work has yet examined the possibility of using FGS as a nanofiller in the preparation of polymer nanocomposites. In particular, there are currently no published papers that evaluate polyurethane/FGS nanocomposites. The purpose of this study was to prepare a polyurethane/FGS nanocomposite and examine the morphological and physical properties of the material. RESULTS: A cast nanocomposite film was prepared from a mixture of thermoplastic polyurethane (TPU) solution and FGS suspended in methyl ethyl ketone. The FGS dispersed on the nanoscale throughout the TPU matrix and effectively enhanced the conductivity. A nanocomposite containing 2 parts of FGS per 100 parts of TPU had an electrical conductivity of 10^?4 S cm^?1, a 10⁷ times increase over that of pristine TPU. The dynamic mechanical properties showed that the FGS efficiently reinforced the TPU matrix, particularly in the temperature region above the soft segment melt. CONCLUSION: Our results show that FGS has a high affinity for TPU, and it could therefore be used effectively in the preparation of TPU/FGS nanocomposites without any further chemical surface treatment. This indicates that FGS is an effective and convenient new material that could be used for the modification of polyurethane. It could also be used in place of other nano‐sized conductive fillers, such as carbon nanotubes. Copyright © 2009 Society of Chemical Industry     

Electrical,rheological and electromagnetic interference shielding properties of thermoplastic polyurethane/carbon nanotube composites

Electrically conducting rubbery composites based on thermoplastic polyurethane (TPU) and carbon nanotubes (CNTs) were prepared through melt blending using a torque rheometer equipped with a mixing chamber. The electrical conductivity, morphology, rheological properties and electromagnetic interference shielding effectiveness (EMI SE) of the TPU/CNT composites were evaluated and also compared with those of carbon black (CB)‐filled TPU composites prepared under the same processing conditions. For both polymer systems, the insulator–conductor transition was very sharp and the electrical percolation threshold at room temperature was at CNT and CB contents of about 1.0 and 1.7 wt%, respectively. The EMI SE over the X‐band frequency range (8–12 GHz) for TPU/CNT and TPU/CB composites was investigated as a function of filler content. EMI SE and electrical conductivity increased with increasing amount of conductive filler, due to the formation of conductive pathways in the TPU matrix. TPU/CNT composites displayed higher electrical conductivity and EMI SE than TPU/CB composites with similar conductive filler content. EMI SE values found for TPU/CNT and TPU/CB composites containing 10 and 15 wt% conductive fillers, respectively, were in the range ?22 to ?20 dB, indicating that these composites are promising candidates for shielding applications. © 2013 Society of Chemical Industry     

Poly(vinylidene fluoride)/thermoplastic polyurethane flexible and 3D printable conductive composites

This work focus on the development of polymeric blends to produce multifunctional materials for 3D printing with enhanced electrical and mechanical properties. In this context, flexible and highly conductive materials comprising poly(vinylidene fluoride)/thermoplastic polyurethane (PVDF/TPU) filled with carbon black-polypyrrole (CB-PPy) were prepared by compression molding, filament extrusion and fused filament fabrication. In order to achieve an optimal compromise between electrical conductivity, mechanical properties and printability, blends composition was optimized and different CB-PPy content were added. Overall, the electrical conductivities of PVDF/TPU 50/50 vol% co-continuous blend were higher than those found for PVDF/TPU 50/50 wt% (i.e., 38/62 vol%) composites at same filler content. PVDF/TPU/CB-PPy 3D printed samples with 6.77 vol% filler fraction presented electrical conductivity of 4.14 S m⁻¹ and elastic modulus, elongation at break and maximum tensile stress of 0.43 GPa, 10.3% and 10.0 MPa, respectively. These results highlight that PVDF/TPU/CB-PPy composites are promising materials for technological applications.     

Selective Laser Sintering 3D Printing: A Way to Construct 3D Electrically Conductive Segregated Network in Polymer Matrix

Selective laser sintering (SLS), which can directly turn 3D models into real objects, is employed to prepare the flexible thermoplastic polyurethane (TPU) conductor using self‐made carbon nanotubes (CNTs) wrapped TPU powders. The SLS printing, as a shear‐free and free‐flowing processing without compacting, provides a unique approach to construct conductive segregated networks of CNTs in the polymer matrix. The electrical conductivity for the SLS processed TPU/CNTs composite has a lower percolation threshold of 0.2 wt% and reaches ≈10⁻¹ S m⁻¹ at 1 wt% CNTs content, which is seven orders of magnitude higher than that of conventional injection‐molded TPU/CNTs composites at the same CNTs content. The 3D printed TPU/CNTs specimen can maintain good flexibility and durability, even after repeated bending for 1000 cycles, the electrical resistance can keep at a nearly constant value. The flexible conductive TPU/CNTs composite with complicated structures and shapes like porous piezoresistors can be easily obtained by this approach.     

One pot synthesis of multiwalled carbon nanotubes reinforced polybenzimidazole hybrids: Preparation,characterization and properties

Poly[2,2^′-(p-oxydiphenylene)-5,5^′-bibenzimidazole] (OPBI) nanocomposites containing 0.1–1 wt% multi wall carbon nanotubes (MWNTs) have been synthesized via “one pot synthesis” which combines the in situ modification of MWNTs and in situ polymerization of OPBI in one reaction pot, a technique that is particularly suitable for large scale production. Raman spectroscopy, NMR, XPS and XRD characterizations of OPBI grafted MWNTs (MWNT-g-OPBI), purified from the MWNT-g-OPBI/OPBI hybrid, reveal that the OPBI chains are successfully attached to the surface of MWNTs in the process of one pot synthesis method. Fracture morphology of the nanocomposites reveals very efficient distribution of the MWNTs within the OPBI matrix with good interfacial interaction. The mechanical properties (including tensile and yield strength, Young's modulus, etc.) are obviously increased even at 0.1 wt% MWNTs loading, and further improvement is observed at higher filler contents. The thermal stability and electrical conductivity are also improved with the incorporation of MWNTs.     

Enhanced mechanical and anisotropic thermal conductive properties of polyimide nanocomposite films reinforced with hexagonal boron nitride nanosheets

To attain thermally conductive but electrically insulating polymer films, in this study, polyimide (PI) nanocomposite films with 1–30 wt% functionalized hexagonal boron nitride nanosheets (BNNSs) were fabricated via solution casting and following imidization. The microstructures, mechanical and thermal conductive properties of PI/BNNS nanocomposite films were examined by taking account of the relative content, anisotropic orientation, and interfacial interaction of BNNS and PI matrix. The scanning electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and X-ray diffractometry data revealed that BNNSs with hydroxy and amino functional groups have specific molecular interactions with PI matrix and they form stacked aggregates in the nanocomposite films with high BNNS loadings of 10–30 wt%. The tensile mechanical strength/modulus, thermal degradation temperatures, and thermal conductivity of the nanocomposite films were found to be significantly enhanced with increasing the BNNS loadings. For the nanocomposite films with 1–30 wt% BNNS loadings, the in-plane thermal conductivity was measured to be 1.82–2.38 W/mK, which were much higher than the out-of-plane values of 0.35–1.14 W/mK. The significant anisotropic thermal conductivity of the nanocomposite films was found to be owing to the synergistic anisotropic orientation effects of both BNNS and PI matrix. It is noticeable that the in-plane and out-of-plane thermal conductivity values of the nanocomposite film with 30 wt% BNNS were ~1.31 and ~3.35 times higher than those of neat PI film, respectively.     

Effect of crosslink density on thermal conductivity of epoxy/carbon nanotube nanocomposites

The effect of the polymeric crosslink density on the thermal conductivity of an epoxy nanocomposite was investigated by adding two different diamine‐functionalized multiwalled carbon nanotubes (diamine‐MWNTs) to the epoxy resin as co‐curing agents and conducting fillers. Tetramethylenediamine (TMDA)‐MWNTs resulted in an epoxy nanocomposite with a higher crosslink density than octamethylenediamine (OMDA)‐MWNTs. Interestingly, epoxy/TMDA‐MWNT nanocomposites under 1.5 wt % nanotube concentration, showed a higher thermal conductivity than an epoxy/OMDA‐MWNT nanocomposite with the same concentration of nanotubes. In contrast, for higher diamine‐MWNT concentrations (over 2.0 wt %), the thermal conductivity of the epoxy/OMDA‐MWNT nanocomposite was higher than that with TMDA‐MWNTs. We observed that for low MWNT concentrations, where a percolating network was not formed, a high crosslink density enhanced the thermal conductivity via phonon transport. However, for high MWNT concentrations, a high crosslink density hinders the formation of a percolating network and lowers the thermal conductivity. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44253.     

Electrically and thermally conductive nylon 6,6

Increasing the thermal and electrical conductivity of typically insulating polymers, such as nylon 6,6, opens new markets. A thermally conductive resin can be used for heat sink applications. An electrically conductive resin can be used in static dissipative and Electromagnetic Interference/Radio Frequency Interference shielding applications. This research focused on adding various carbon based conductive fillers and a chopped glass fiber to nylon 6,6. These materials were extruded and injection molded into test specimens. Tensile tests as well as in-plane electrical resistivity, in-plane thermal conductivity, and through-plane thermal conductivity tests were conducted. One successful formulation consisted of 10% 3.2 mm chopped E-glass fiber/15% Thermocarb (high quality synthetic powdered graphite)/5% carbon black/70% nylon 6,6 (all % in wt%). For this formulation, the in-plane electrical resistivity was reduced from 10¹⁵ ohm-cm (neat nylon 6,6) to 15 ohm-cm. The through-plane thermal conductivity increased from 0.25 W/mK (neat nylon 6,6) to 0.7 W/mK. The tensile elongation at failure was 1.4%.     

Electromagnetic interference shielding behavior of chemically and thermally reduced graphene based multifunctional polyurethane nanocomposites: A comparative study

This article presents the effect of exfoliation, dispersion, and electrical conductivity of graphene sheets onto the electrical, electromagnetic interference (EMI) shielding, and gas barrier properties of thermoplastic polyurethane (TPU) based nanocomposite films. The chemically reduced graphene (CRG) and thermally reduced/annealed graphene (TRG) having Brunauer–Emmett–Teller surface areas of 18.2 and 159.6 m²/g, respectively, when solution blended with TPU matrix using N,N-dimethylformamide as a solvent. Graphene sheets based TPU nanocomposites have been evaluated and compared for EMI shielding in Ku band, electrical conductivity, and gas barrier property. TRG/TPU nanocomposite films showed excellent gas barrier against N₂ gas as compared to CRG/TPU. The EMI shielding effectiveness for neat CRG and TRG graphene sheets is found to be −80, −45 dB, respectively, at 2 mm thickness. The EMI shielding data revealed that TRG/TPU nanocomposites showed better shielding at lower concentration (10 wt %), while CRG displayed better attenuation at higher concentrations. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47666.     

Filler reaggregation and network formation time scale in extruded high‐density polyethylene/multiwalled carbon nanotube composites

A high‐density polyethylene (HDPE) masterbatch containing 20.2 wt% multiwalled carbon nanotubes (MWNTs) was melt diluted with neat HDPE using two different methods: a twin screw microcompounder and a single‐screw extruder. The electrical properties of these composites were assessed using bulk electrical conductivity measurements, their mechanical properties were evaluated using tensile tests and dynamic mechanical analysis (DMA), and percent crystallinity was determined by wide angle x‐ray diffraction (WAXD) and differential scanning calorimetry (DSC). A percolation threshold (p_c) of 4.5 wt% MWNTs was found in compression‐molded samples. Extruded samples were prepared with nanotube concentrations below and above the compression‐molded percolation threshold (2 and 7 wt% MWNTs) and passed through the extruder twice before entering a low‐shear melt annealing zone. Different melt annealing times were used and their effects on the electrical and mechanical properties of the resulting quench‐cooled composites were evaluated. Results showed that extruded composites were nonconductive, indicating that a conductive nanotube network did not form on the time scale of these experiments. Annealing time also did not affect significantly the mechanical properties of the resulting solid composites. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Cellulose nanocrystal-mediated assembly of graphene oxide in natural rubber nanocomposites with high electrical conductivity

This study reports a green and powerful strategy for preparing cellulose nanocrystal (CNC)/graphene oxide (GO)/natural rubber (NR) nanocomposites hosting a 3D hierarchical conductive network. Due to good dispersibility and amphiphilic nature of CNC, well dispersed CNC/GO nanohybrids were prepared. Hydrogen bonding interactions between CNC and GO greatly enhanced the stability of the CNC/GO nanohybrids. CNC/GO nanohybrids were introduced into NR latex under sonication and the mixture was cast. Self-assembled CNC/GO nanohybrids preferentially dispersed in the interstice between latex microspheres allowing the construction of a 3D hierarchical conductive network. By combining strong hydrogen bonds and 3D conductive network, both electrical conductivity and mechanical properties (tensile strength and modulus) have been significantly improved. The electrical conductivity of the nanocomposite with 4 wt% GO and 5 wt% CNC exhibited an increase of nine orders of magnitude compared to the nanocomposite with only 4 wt% GO; meanwhile, the electrical percolation threshold was 3-fold lower than for NR/GO composites.     

The synergistic effects on enhancing thermal conductivity and mechanical strength of hBN/CF/PE composite

In this work, a simple and novel method was applied to prepare polymer composites by taking the advantage of melt flow shear force driving orientation of the fillers. By using this method, hexagonal boron nitride/polyethylene (hBN/PE) and hexagonal boron nitride/carbon fibers/polyethylene (hBN/CF/PE) composites were fabricated to be possessed of high thermal conductivity and mechanical properties. A high thermal conductivity of 3.11 W/mK was realized in the composite containing 35 wt% hBN and 5 wt% CF, which was over 1,200% higher than that of unfilled PE matrix. Under this component, the compressive strength and modulus of hBN/CF/PE composite were determined to be 30.1 and 870.9 MPa, respectively, which were far higher than that of unfilled PE accordingly. The bending performance was also somewhat enhanced. Meanwhile, the bulk resistivity of the composite material reached 2.55 × 10¹¹ Ω·cm, which was basically the same as that of pure PE. The novel composites with high thermal conductivity, excellent mechanical properties, and controllable electrical insulation could be a potential thermal management material for electrical and electronics industries.     

Physicochemical characteristics of bio-based thermoplastic polyurethane/graphene nanocomposite for piezoresistive strain sensor

Herein, we report the physicochemical characteristics and piezoresistive strain sensing performance of flexible thin film comprising graphene and bio-based thermoplastic polyurethane (TPU) prepared by solution cast method. A detailed analysis was carried to study the influence of graphene nanoplatelets on the morphological, thermal, mechanical, and electrical properties of TPU nanocomposite. Upon increasing the graphene nanoplatelets loading, the thermal stability and tensile properties improved remarkably, while glass transition temperature decreased slightly. Owing to better dispersion of graphene, the electrical conductivity was significantly increased, which broaden the utilization of the nanocomposite for various applications. The piezoresistive sensor was able to respond to various stress modes such as tapping, bending, and finger touch. The piezoresistive sensor was sensitive and achieved a gauge factor of 11. Sensor attached to finger, showed distinctive response upon bending at different angles and showed high stability and reproducibility even after >10,000 cycles under repetitive constant load. Also, the nanocomposite was able to detect any breakage or fracture in the form of change in electrical resistance. A combination of bio-based TPU and graphene offered improved physical properties and high sensing performance, which could be a potential material in flexible electronics and structural health monitoring systems.     

Ultralight and Flexible MWNTs/Polyimide Hybrid Aerogels for Elastic Conductors

Aerogels have showed tremendous potential applications because of its unique and outstanding properties. Herein, a novel two‐step approach to form self‐assembly nanocomposite aerogels driven by the strong interactions between water‐soluble polyimide (PI) precursor polyamic acid salt (PAAs) and hydroxyl multiwalled carbon nanotubes (MWNTs‐OH) is reported. The PI therein constitutes the framework of the nanocomposite and raises the strength of the cell walls, which endows aerogels with superelasticity and robustness. The MWNTs‐OH is distributed uniformly into water via physical ultrasonic method followed by blending with PAA molecular. During the imidization process, electrically insulating polyamic acid (PAA)/MWNTs‐OH aerogels are converted to conductive PI/MWNTs‐OH nanocomposite aerogels owning to the removal of their oxygenic functional groups of  OH functionalized MWNTs. Moreover, adding multi‐walled carbon nanotube (MWNTs) contributes to the reduction of shrinkage notably, which can be evidenced by scanning electron microscopy measurement and density data. The nanocomposite aerogels display a high elastic modulus, high compressive stress, superior robustness, and high stress‐sensitive electrical conductivity. Interestingly, the variation trend of the electric resistance with compressive strain (R /R ₀–ε) plots is consistent with the compressive stress–strain (σ–ε) curves, which can be explained by the “interface contact spots” theory. And this finding could facilitate the development of polymer‐based nanocomposite aerogels as elastic conductors for various applications.

     

Self-healable and reprocessible liquid crystalline elastomer and its highly thermal conductive composites by incorporating graphene via in-situ polymerization

The booming of modern electronic devices featuring increasing power and multi-functionalization demands novel high thermal conductive materials with various functions, such as self-healing property and high deformability, while traditional polymer-based or metallic-based materials could hardly provide. Therefore, we report a high thermal conductive and disulfide-based self-healable and reprocessible liquid crystalline elastomer (SHLCE) composite by incorporating graphene nanoplates (GNPs) fillers. The obtained GNPs/SHLCE composites exhibited desired thermal conductivity (5.08 Wm⁻¹ K⁻¹) when the content of GNPs was 20 wt% to the composites. Moreover, the GNPs/SHLCE composites showed intriguing recycled performance (Tensile strength after recycle could maintain over 93% compared with that of original composites). Furthermore, we concluded that the improved thermal conductivity of GNPs/SHLCE composites was beneficial to the thermal induced reprocessible and shelf-healable systems.     

Mechanical properties and electrical conductivity in a carbon nanotube reinforced silicon nitride composite

The influence of carbon nanotubes (CNTs) addition on basic mechanical, thermal and electrical properties of the multiwall carbon nanotube (MWCNT) reinforced silicon nitride composites has been investigated. Silicon nitride based composites with different amounts (1 or 3 wt%) of carbon nanotubes have been prepared by hot isostatic pressing. The fracture toughness was measured by indentation fracture and indentation strength methods and the thermal shock resistance by indentation method. The hardness values decreased from 16.2 to 10.1 GPa and the fracture toughness slightly decreased by CNTs addition from 6.3 to 5.9 MPa m^1/2. The addition of 1 wt% CNTs enhanced the thermal shock resistance of the composite, however by the increased CNTs addition to 3 wt% the thermal shock resistance decreased. The electrical conductivity was significantly improved by CNTs addition (2 S/m in 3% Si₃N₄/CNT nanocomposite).     

Properties and structure of MWNTs/cellulose composite fibers prepared by Lyocell process

Lyocell fiber is a new kind of regenerated cellulose fiber and expected to replace the Rayon fiber to be not only used in the textile field but also used in the fields of industry and aerospace after being modified. In this work, the multi‐walled carbon nanotubes (MWNTs)/Lyocell composite fibers were prepared under different draw ratios by dry‐wet spinning and their electrical properties, mechanical properties, and structure were investigated. It was found that an appropriate amount of MWNTs could be dispersed homogeneously in the Lyocell matrix and could improve the mechanical and thermal properties of composite fiber. The results of wide angle X‐ray diffraction (WAXD) showed that the MWNTs in the composite fiber almost aligned along the axis of the fibers and the orientation of MWNTs increased with the increasing draw ratio. Furthermore, it was found that more MWNTs content and lower draw ratio could improve the electrical conductance of the composite fiber. The composite fiber containing 5 wt % MWNTs has a volume conductivity of 8.8 × 10^?4 S/cm, which is five orders higher than that of pure Lyocell fiber. These results indicate that the MWNTs/Lyocell composite fiber has potential applications in the areas of precursor of carbon fiber and conductive fiber. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis of cellulose/reduced graphene oxide/polyaniline nanocomposite and its properties

A series of conductive nanocomposites cellulose/reduced graphene oxide/polyaniline (cellulose/RGO/PANi) were synthesized via in situ oxidative polymerization of aniline on cellulose/RGO with different RGO loading to study the effect of RGO on the properties of nanocomposites. The results showed that when RGO is inserted into cellulose/PANi structure, its thermal stability and conductivity are increased. So that adding of only 0.3 wt% RGO into the cellulose/PANi structure, its conductivity is increased from 1.1 × 1 10^?1 to 5.2 × 110^?1 S/cm. Scanning electron microscopy results showed that the PANi nanoparticles are formed a continuous spherical shape over the cellulose/RGO template; this increases the thermal stability of nanocomposite.     

Lightweight and thermally conductive thermoplastic polyurethane/hollow glass bead/boron nitride composites with flame retardancy

Polymeric composites with low density and high thermal conductivity (TC) are greatly demanded in some specific applications such as aeronautics, astronautics, and deep-sea exploration. It is a great challenge to obtain lightweight and thermally conductive polymer composites because the heat fillers have high density (>2 g/cm³) Herein, lightweight and thermally conductive thermoplastic polyurethane/hollow glass bead/boron nitride composites (TPU/HGB/BN) were prepared with the construction of a 3D BN network under the assistance of ultralightweight HGB by a solution-mixing and hot-pressing method. A 3D BN heat network has been constructed in the TPU matrix due to the alignment of the BN platelets along with the HGB microspheres during hot-pressing, which leads to a higher TC (5.34 W/mK) of the TPU/HGB/BN composites with a low density of 1.23 g/cm³, which is close to the density of pure TPU (1.20 g/cm³). In addition, the TPU/HGB/BN composites show good thermal stability with TC losses of 4.24% and 2.22%, respectively, even after treated for 50 hot-cold cycles and heated at 80 °C for 50 h. Moreover, the limiting oxygen index (LOI) of the TPU/HGB/BN composites is 51%, and they can extinguish in 8 s after ignition and exhibit enhanced flame retardancy. This work presents a simple method to design and prepare lightweight, flame retardant and thermally conductive composite materials, which can be used as lightweight thermal management materials.