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.     

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.     

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     

Fabrication of electrical and thermal conductive thermoplastic polyurethanes-based nanocomposite with azide polyurethane as interfacial compatibilizer

Electrical and thermal conductive polymers have aroused extensive interest in research recently due to their hi-tech applications in the fields of novel electronics. A novel electrical and thermal conductive nanocomposite (MWCNTs@PU/TPU) made with multiwall carbon nanotubes (MWNTs) and thermoplastic polyurethanes (TPU) by using azide polyurethane (PU) as interfacial compatibilizer. The MWNTs could form well-developed electrical and thermal conductive networks in the TPU matrix. The developed nanocomposite inherited advantageous properties from its constituents, namely the high conductivity and diathermancy from MWNTs, and the high mechanical properties from the TPU. Conductivity tests showed that, compared with neat MWCNTs/TPU, the electrical conductivity of MWCNTs@PU/TPU was significantly enhanced (up to 3.4 × 10⁻⁶ S/cm), with incorporating only 3.0 wt% MWCNTs@PU. And most importantly, the thermal conductivity was greatly improved by about 46.4% when the MWCNTs@PU loading was 6.0 wt%.     

Constructing the core–shell structured island domain in polymer blends to achieve high dielectric constant and low loss

Carbon nanotubes (CNTs) and barium titanate (BaTiO₃) (BT) were simultaneously introduced into the immiscible blend poly(ethylene‐co‐vinyl acetate)/thermoplastic urethane (EVA/TPU), and the EVA/TPU/CNT/BT quaternary polymer composite blends with core–shell structured island TPU domain were successfully prepared, in which CNTs in the TPU domain act as the core and the BT spheres at the interface of the TPU and EVA act as the shell. A core–shell structured island can lead to the formation of micro‐capacitors and further accumulate electron storage owing to the incorporation of CNTs and BT; on the other hand, a BT shell can be assembled along the TPU spheres, reducing the possibility of formation of a conductive CNT network, resulting in suppressed dielectric loss. Therefore, CNTs and BT were tailor‐made into blend composites with a core–shell structured domain, which can achieve an increased dielectric constant by 176% and decreased low dielectric loss by 80% compared with the blend composites with only CNTs in the TPU domain. © 2019 Society of Chemical Industry     

Segregated highly conductive linear low-density polyethylene/graphene nanoplatelet composite through aqueous dispersing and self-leveling method

Construction of segregated structure is an effective way of preparing highly conductive composite. Here, we report an environmentally friendly method to prepare highly conductive linear low-density polyethylene/graphene nanoplatelets composite with segregated structure (s-LLDPE/GN) and low GN content. Firstly, GN coated LLDPE granules are prepared through aqueous dispersing and gradually drying. Then, the s-LLDPE/GN composites are obtained by melting and self-leveling without extra pressure. This method not only favors the forming of GN segregated network, but also allows certain fusing of the polymer at the interfaces that contribute to good mechanical strength of the composite. The electrical conductivity of the composite increases to 4.5 S/m when the GN content is 1.0 wt%. The composite with 0.5 wt% GN shows 10⁻¹ S/m electrical conductivity, and retains 82% of the tensile strength of pure LLDPE. The facile and green process in this method can be applied in many other polymer composites and show high potential for industrial application.     

Highly sensitive flexible strain sensor based on carbon nanotube/styrene butadiene styrene@ thermoplastic polyurethane fiber with a double percolated structure

The combination of a high sensitivity and a wide strain detection range in conductive polymer composites-based flexible strain sensors is still challenging to achieve. Herein, a double-percolation structural fiber strain sensor based on carbon nanotubes (CNT)/styrene butadiene styrene (SBS)@thermoplastic polyurethane (TPU) composite was fabricated by a simple melt mixing and fused filament fabrication strategy, in which the CNT/SBS and TPU were the conductive and insulating phases, respectively. Compared with the sensor without the double percolated structure, the CNT/SBS@TPU sensor achieved a lower percolation threshold (from 2.0 to 0.5 wt%, a reduction of 75%), and better electrical and sensing performance. It is shown that the strain detection range of the CNT/SBS@TPU sensor increases with increasing CNT loading. An opposite trend was observed for the sensitivity. The 1%-CNT/SBS@TPU sensor exhibited a high conductivity (1.08 × 10⁻³ S/m), high sensitivity (gauge factor of 2.65 × 10⁶ at 92% strain), wide strain detection range (0.2%–92% strain), high degree of linearity (R² = 0.954 at 0–10% strain), broad monitoring frequencies (0.05–0.5 Hz), and excellent stability (2000 cycles). Moreover, the CNT/SBS@TPU sensor was shown to successfully monitor a range of human physiological activities and to be capable of tactile perception and weight distribution sensing.     

CNTs表面包覆PPy对PVC复合材料电导率的影响

为促进碳纳米管(CNTs)更为有效地应用于聚合物抗静电复合材料,采用原位聚合在CNTs表面生成聚吡咯(PPy)包覆层得到CNT-PPy,其组成通过傅立叶变换红外光谱分析和热重分析确认。CNT-PPy作为导电剂添加到聚氯乙烯(PVC)中制备PVC/CNT-PPy复合材料,对比分析PVC/CNT-PPy复合材料电导率的变化规律可得:PPy修饰CNTs可降低PVC/CNT-PPy复合材料中CNTs的逾渗阈值;当PPy包覆层在CNT-PPy中质量分数约为51.1%,CNT-PPy在复合材料中的质量分数为3%时,制得PVC复合材料的电导率可达到10–7 S/cm量级。由此可知,CNTs表面可控的PPy修饰量对PVC/CNTs复合材料抗静电性能起到显著的提升作用,为CNTs作为高性能导电剂应用提供更多的空间。     

Enhanced electrical conductivity of nylon 6 composite using polyaniline-coated multi-walled carbon nanotubes as additives

Aggregation in polymer composites is one of the major obstacles in the carbon nanotubes (CNTs) applications. Authentic CNTs are known to have very good electrical conductivity and mechanical strengths. Surface functionalization can avoid aggregation and help dispersion of CNTs, but reduces CNT’s electrical conductivities and mechanical strengths dramatically. It needs a good way to resolve the above dilemma situation; i.e., poor dispersion-good conductivity vs. good dispersion-poor conductivity. Herein, we demonstrate that in-situ polymerized polyaniline (PANI)-coated CNTs have good polymer matrix compatibility, and are superior electrically conductive fillers to nylon 6 composites. In this report, multi-walled CNTs (MWCNTs) were surface-modified with poly(acrylic acids) (PAA), followed by further coating with PANI. The electrical conductivity of (PANI-MWCNTs)-nylon 6 composite thin film was increased from 10⁻¹² to 7.3 × 10⁻⁵ S/cm in the presence of 1 wt% PANI-coated MWCNTs prepared by physical mixing of PANI and PAA-grafted MWCNTs. When in-situ polymerized PANI-coated MWCNTs were added, the electrical conductivity of MWCNTs-nylon 6 composite was further enhanced by 3 orders to be 3.4 × 10⁻² S/cm at the same 1 wt% loading of MWCNTs. Both Fourier-transformed infrared and uv-visible absorption spectra indicate that there exist very strong site-specific charge transfer interactions between the quinoid rings of PANI and MWCNTs, which results in the superior electrical conductivity of MWCNT-nylon 6 composite.     

Carbon nanotube/polypropylene/polycarbonate conductive nanocomposite films: Preparation and characterization

In this study, CNT/PP/PC conductive composite films were prepared by compounding PP (polypropylene)/PC (polycarbonate) (1:1) and carbon nanotubes (CNT) using a physical blending and hot pressing method. Next, Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, and water contact angle measurement are conducted in order to characterize the properties of CNT/PP/PC conductive films. The results showed there is no chemical reaction inside the PP/PC composite film with the addition of CNT. Neither the CNT composite film containing 3 wt% nor the control film decomposed thermally within 220°C. The water contact angle increased from 88.5° for the control film to 110.99° for the composite film containing 3 wt% CNT. This indicates that the film has good thermal stability and hydrophobic properties. The percolation threshold was obtained when the content of CNT was 3 wt%, and the best conductivity of the CNT/PP/PC composite film was 5.53 S/m at this time. In order to improve the tensile properties of the film, a small amount of polyurethane (TPU) was added to the film, and the maximum tensile strength was 24.91 Mpa when the content of TPU was 6.7%. This study can provide a strategy for the practical application of flexible electronic devices.     

Microfluidic‐Spinning‐Directed Conductive Fibers toward Flexible Micro‐Supercapacitors

The large‐scale fabrication of the flexible fiber‐shaped micro‐supercapacitors has received major attention from both industrial and academic researchers. Herein, conductive and robust polyaniline‐wrapped multiwall carbon tubes reduced graphene oxide/thermoplastic polyurethane (PANI/MCNTs‐rGO/TPU) composite fibers are successfully fabricated on a large scale via the combination of facile microfluidic‐spinning process and in situ polymerization of aniline. Initially, MCNTs‐rGO/TPU fibers are formed in a T‐shape microfluidic chip, relying on the fast material diffusion and exchange in the microfluidic channel. Then, PANI/MCNTs‐rGO/TPU hybrid fibers are synthesized through an in situ chemical oxidative polymerization of aniline. With the assistance of polyaniline, these PANI/MCNTs‐rGO/TPU hybrid fibers exhibit enhanced electrochemical properties in comparison with pure MCNTs‐rGO/TPU fibers, especially in high specific capacitance, which is dramatically increased from 42.1 to 155.5 mF cm^?2. Moreover, the PANI/MCNTs‐rGO/TPU hybrid fibers can endure various blending stresses, contributing to its outperforming flexibility and weavability. The best of the excellent electrochemical and mechanical properties of these conductive fibers is made to construct the flexible supercapacitors and various complicated functional fabrics.     

Thermal conductive performance of organosoluble polyimide/BN and polyimide/(BN + ALN) composite films fabricated by a solution‐cast method

Organosoluble polyimide (PI)/ceramic composite films with different BN or (BN + AlN) contents were under investigation for their thermal conductive performances. The chosen polyimide constituted by 4,4′‐oxydiphthalic dianhydride/2,2‐bis(3‐amino‐4‐hydroxyphenyl)hexafluor opropane could be dissolved and cast into thin films at room temperature. The commercially available BN and AlN fillers up to a volume ratio of 0.6 were added to the polyimide and their thermal conductive performances were measured. BN powders needed a surface precoating treatment to avoid sedimentation. The dense and flexible PI/BN composite films, after a drying treatment at 200°C, showed high thermal conductivity of 2.3 W/m·K⁻¹ at a BN volume ratio of 0.6, as compared with 0.13 W/m·K⁻¹ for pristine polyimide. However, in the case of PI/(BN + AlN) composite films, thermal conductive performance degraded because the films became highly porous at the higher AlN content. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

The use of a carbon nanotube layer on a polyurethane multifilament substrate for monitoring strains as large as 400%

A noninvasive approach is used to fabricate electronically conductive and flexible polymer fibers by fixing carbon nanotube (CNT) networks as a thin layer on thermoplastic polyurethane (TPU) multifilaments. The anchoring of the CNT layer is achieved by partially embedding or penetrating CNTs from the dispersion into the swollen multifilament surface. Thus a stable and high conductivity (up to 10² S/m at 10 wt.% CNT loading) of the resulting CNTs–TPU fibers is realized while the mechanical properties of the TPU multifilament, especially the strain to failure of >1500%, are not affected by increasing the thickness of the CNT layer. Real time analysis of the resistance of the CNTs–TPU fibers during incremental tensile loading tests reveal that the increase of resistance as a function of the strain is attributed to stretching-induced deformation, alignment, and, at high strains, destruction of the conducting network. Moreover, the changes in resistance are highly reversible under cyclic stretching up to a strain deformation of 400%.     

3D printing of copper particles and poly(methyl methacrylate) beads containing poly(lactic acid) composites for enhancing thermomechanical properties

Poly(lactic acid) (PLA) composite filaments with different copper (Cu) contents as high as 40 and 20 wt% of poly(methyl methacrylate) (PMMA) beads have been fabricated by twin-screw extruder for 3D printing. A fused-deposition modeling (FDM) 3D printing technology has been used to print the PLA composites containing hybrid fillers of Cu particles and PMMA beads. The morphology, mechanical, and thermal properties of the printed PLA composites were investigated. The tensile strength was slightly decreased, but storage modulus and thermal conductivity of PLA composites were significantly improved by adding Cu particles in the presence of PMMA beads. The PLA composites with hybrid fillers of 40 wt% of Cu particles and 20 wt% of PMMA beads resulted in thermal conductivity of 0.49 W m⁻¹ K⁻¹ which was three times higher than that of the bare PLA resin. The facilitation of the segregated network of high-thermally conductive Cu particles with the PMMA beads in PLA matrix provided thermally conductive pathways and resulted in a remarkable enhancement in thermal conductivity.     

Strong and Flexible Carbon Fiber Fabric Reinforced Thermoplastic Polyurethane Composites for High‐Performance EMI Shielding Applications

Electromagnetic shielding materials play a significant role in solving the increasing environmental problem of electromagnetic pollutions. The commonly used metal‐based electromagnetic materials suffer from high density, poor corrosion resistance, and high processing cost. Polymer composites exhibit unique combined properties of lightweight, good shock absorption, and corrosion resistance. In this study, a novel high angle sensitive composite is fabricated by combining carbon fiber (CF) fabric with thermoplastic polyurethane elastomer (TPU). The effect of stacking angle of CF fabric on EMI shielding performance of composite is studied. When the stacking angle of CF fabric changed, the electromagnetic interference (EMI) shielding effectiveness (SE) of CF fabric/TPU composite can reach a maximum of 73 dB, and the tensile strength can reach 168 MPa. In addition, the composite has anisotropic conductivity, which is conductive along the plane direction and nonconductive along the thickness direction. Moreover, the CF fabric/TPU composite manifests exceptional EMI‐SE/density/thickness value of 383 dB cm² g^?1, which is higher than most of current EMI shielding composites reported in literature. In summary, CF fabric/TPU composite is an excellent EMI shielding material that is lightweight, highly flexible, and mechanically robust, which can be applied to the field of aerospace and some intelligent electronic devices.     

Electromagnetic Interference Shielding Foams Based on Poly(vinylidene fluoride)/Carbon Nanotubes Composite

Polymeric electromagnetic interference (EMI) shielding foaming materials are found and applied in many frontier fields such as aerospace, transportation, and portable electronics. In this paper, a foam based on a composite system of poly(vinylidene fluoride) (PVDF) filled with carbon nanotubes (CNTs) is prepared for EMI shielding properties by using a solid-state supercritical CO₂ foaming strategy. PVDF is chosen as the matrix because of its excellent chemical resistance, thermal stability, and flame retardancy. The inclusion of CNTs renders this composite system enhanced complex viscosity and storage modulus by about two orders of magnitude. The electrical conductivity and EMI specific shielding effectiveness of obtained foams can be adjusted and reached the optimum value of 0.024 S m⁻¹ and 29.1 dB cm³ g⁻¹, respectively, originating from the gradual development of interconnected CNTs and conductive CNTs network as well as the introduction of cell structure in PVDF matrix. Interestingly, the reorientation of CNTs caused by foaming process results in electrical conductivity percolation threshold of PVDF/CNTs foams markedly decreases, in comparison to their unfoamed samples. This study provides a facile, efficient, green, and economic route for the preparation of EMI shielding foams consisted of fluorinated polymers and carbonaceous fillers.     

Polydopamine-Assisted Bi-Functional Modification of NiO Anode for Enhanced Lithium-Ion Storage Performance

The blooming requirement of high-performance energy storage systems has aroused the thirst for advanced energy storage materials. As a high capacity anode, however, the application of NiO nanoparticles (NiO NPs) is hindered by intractable issues of dramatic volume change, intrinsic low electronic conductivity, and severe aggregation tendency during lithiation/delithiation. Herein, a polydopamine (PDA) assisted bi-functionalization strategy for fabricating of PDA@NiO-CNT composites for fast and durable lithium storage is reported. In this composite, CNTs intertwine to form a network to ensure sufficient electrolyte infiltration and act as a highly conductive system to motivate fast charge transmission. The strong binding affinity of PDA facilitates bonding between NiO NPs and CNTs, which not only forms uniform and flexible PDA coating but also ensures homogeneous distribution of NiO NPs on CNTs network. Therefore, the bi-functional modified PDA@NiO-CNT electrode possesses high conductivity, alleviates volume change and aggregation of NiO NPs during cycling, achieves a reversible capacity of 1326 mAh g⁻¹ at 100 mA g⁻¹, a rate capability of 215 mAh g⁻¹ at 2000 mA g⁻¹ and a cycling stability with 78% capacity retention after 250 cycles. This bi-functional modification approach manifests its prospective potential for architecting other electrode materials toward high-performance electrochemical devices.     

A bio-based compatibilizer for improved interfacial compatibility in thermally conductive and electrically insulating graphite/high density poly(ethylene) composites

Graphite is a thermally conductive filler. However, when dispersed into high density poly(ethylene) (HDPE) resin, graphite particles tend to agglomerate and requires a compatibilizer to achieve desired thermal/physical properties. In this study, oleic acid (OA), a bio-based additive and polyethylene-polyamines (PEPA) were used to synthesize a new compatibilizer, PEPA-g-OA, containing numerous  NR₂ groups. The experimental results showed that PEPA-g-OA can significantly improve the compatibility between graphite particles and the HDPE matrix due to uniform dispersion of graphite in the HDPE matrix. When the graphite content was 25 wt%, the thermal conductivity of the composite recorded 1.2 W m⁻¹ K⁻¹ (three times that of neat HDPE) and the volume resistivity was 1.8 × 10⁹ Ω cm, indicating excellent electrical insulation. Compared to the composites with no graphite content, the properties of the composites with 25 wt% graphite content exhibited narrower melting and crystallization peaks, more stable mechanical properties, and higher ultraviolet aging resistance. Synthesized new bio-based compatibilizer and thermally conductive and electrically insulating composites developed in this study can be useful in different industrial fields for the preparation of the next generation composites.     

Effect of annealing treatment on the structure and properties of polyurethane/multiwalled carbon nanotube nanocomposites

The thermoplastic polyurethane/multiwalled carbon nanotube (TPU/CNT) nanocomposites with high conductivity and low percolation threshold value were prepared by melting blending and annealing treatment. The effect of annealing process on the microphase structure and the properties of TPU/CNT nanocomposites was studied. It has been shown that CNT flocculation can occur in TPU/CNT nanocomposites during the annealing process. At a critical CNT content, which defined the percolation threshold, CNTs could form conductivity network. The conductive percolation threshold value of TPU/CNT nanocomposites was decreased from 10 to 4% after annealing process, and the conductivity of TPU/CNT nanocomposites with 10 vol % of CNT could reach 1.1 S/m after an annealing time of 1 h. The significant enhancement of electrical conductivity was influenced by the annealing time and the content of CNTs. The formation of CNT networks was also verified by dynamic viscoelastic characterization. The results of X‐ray diffraction and differential scanning calorimetry indicated that annealing process reinforced the microphase separation of the nanocomposites. Mechanical properties test showed that the annealing treatment was in favor of improving the mechanical properties; however, further increase in the annealing time has negative effect on the mechanical properties. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermoplastic Polyurethane Nanocomposites Produced via Impregnation of Long Carbon Nanotube Forests

TPU was infiltrated into vertically aligned, 3.5 mm‐long MWNT forests to produce continuously reinforced anisotropic nanocomposites, and thermomechanical and electrical testing has revealed multifunctionality which shows promise for numerous applications. A 1000% increase in the storage modulus at 70 °C was observed as compared to the neat TPU, and these continuously aligned composites showed electrical conductivity two orders‐of‐magnitude greater (≈1.5 S · cm^?1) than randomly aligned composites prepared using CNTs from these forests. The heightened improvement for the continuously reinforced composite appears to be owed to the extremely high aspect ratio of these CNTs and the interconnected network which remains after infiltration.