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     

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 and Mechanical Properties of Thermoplastic Polyurethane and Polytetrafluoroethylene Powder Composites

To determine the possibility of using polytetrafluoroethylene (PTFE) powder as reinforcing filler in the thermoplastic matrix, the thermoplastic polyurethane (TPU) as the matrix and PTFE powder as reinforcing filler were used to prepare a particulate reinforced composite, in order to determine testing data for electrical and mechanical properties of the composites according to the filler loading in respect to TPU polymer matrix. The TPU and PTFE powder composites were prepared by the milling TPU with 2.5, 5, 7.5, and 10 wt% of PTFE powder in a two roll mill and the milled material is compression moulded to make sheets. From the sheets, the test specimens were made and tested for electrical properties—dielectric strength, dielectric constant, surface, and volume resistivity; fire resistance—rate of burning; mechanical properties—tensile strength and elongation, impact strength, hardness; density and melt flow index. The incorporation of PTFE powder has significantly improved the electrical properties—dielectric strength, dielectric constant, surface and volume resistivity; and fire resistance—rate of burning of thermoplastic polyurethane. However, the tensile strength decreased from 24.91 to 14.71 MPa and tensile elongation increased from 620 to 772 percentage.     

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.     

集成电路封装用GNPs/CNTs/HDPE导热高分子复合材料的研究

本文以高密度聚乙烯(HDPE)为基体,以自制的h-G-C-2/1体系杂化填料为导热填料,制备了GNPs/CNTs/HDPE导热高分子复合材料,重点对比了杂化填料和复配填料对GNPs/CNTs/HDPE复合材料在导热、导电及力学性能方面的影响。结果表明,GNPs/CNTs/HDPE导热高分子复合材料的拉伸强度为31.9 MPa,冲击强度为22.1 kJ/m^2,体积电阻率为690 MΩ·cm,热导率为0.759 W/(m·K),满足集成电路封装用技术参数要求。杂化填料的分散性优于复配填料,杂化填料在提高复合材料的拉伸性能方面优于复配填料,复配填料在提高复合材料的热导率方面优于杂化填料。本文所获得的研究成果为制备新型综合性能优异的集成电路封装用导热高分子复合材料提供了一条新的思路。     

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     

Morphology and properties of shape memory thermoplastic polyurethane composites incorporating graphene‐montmorillonite hybrids

A novel hybrid containing graphene oxide (GO) and montmorillonite (MMT) was first synthesized by solution reaction. Then shape memory thermoplastic polyurethane (TPU) composites incorporating MMT–GO hybrid was fabricated via melt blending. Infrared spectra indicated that GO and MMT have been combined together through chemical hydrogen bonding. Tensile tests showed that MMT‐GO hybrids provided substantially greater mechanical property enhancement than using MMT or GO as filler alone. With only 0.25 wt % loading of MMT–GO hybrid (the mass ratio of MMT:GO is 1:1), there was a relatively high improvement in tensile properties of TPU composites, compared with those of TPU/GO and TPU/MMT composites at the same filler content. Thermal analysis indicated that MMT‐GO hybrids enhanced the thermal decomposition temperatures of TPU composites. Shape memory property tests showed that the shape fixing rate of TPU composites was effectively enhanced by incorporating MMT–GO hybrid. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46149.     

Control of Conductive and Mechanical Performances of Poly(Amide‐Imide) Composite Films Utilizing Synergistic Effect of Polyaniline and Multi‐Walled Carbon Nanotube

Functionalized multi‐walled carbon nanotubes (FMWCNTs) have been incorporated into binary composites of poly(amide‐imide) (PAI) and polyaniline (PANI) to improve their conductive and mechanical performances. The conductivity of PAI/PANI/FMWCNTs ternary composites significantly increased from 10^?3 to 8.3 S m^?1 with increasing the weight ratio of FMWCNTs from 0 to 10 wt%, which is much higher than that of the sum of PAI/PANI and PAI/FMWCNTs binary composites. The enhanced conductivity is mainly ascribed to be the more intensive conductive percolating network formed in the PAI/PANI/FMWCNTs ternary composites due to the hydrogen bond interaction among PAI, PANI and FMWCNTs. On the other hand, the tensile strength has been improved by 40% from 25 to 35 MPa. The self‐extinguishing property and phase transition of the ternary films have also been investigated by thermal gravimetric analysis and differential scanning calorimetry, respectively. It is found that the weight ratio of FMWCNTs and the special morphology are the two important factors that induce such unusual properties. POLYM. ENG. SCI., 59:E224–E230, 2019. © 2018 Society of Plastics Engineers     

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.     

Influences of dielectric and conductive fillers on dielectric and mechanical properties of solid silicone rubber composites

Dielectric elastomers are materials being used for electromechanical transduction applications. Their electromechanical response depends on permittivity, Young’s modulus and electric breakdown strength. A factor that limits its application is high operating voltages that can be reduced through improvement in permittivity. One of the methods is by incorporating high permittivity fillers into polymer matrix to obtain dielectric–dielectric composites (DDC).These composites show high permittivity at the cost of reduced flexibility. An alternative solution is development of composites by incorporating organic or inorganic conductive fillers into polymer matrix. These composites show high permittivity with high dielectric loss and low breakdown strength. To overcome both the above limitations both dielectric and conductive fillers are incorporated into dielectric polymer matrix to obtain conductor–dielectric composites (CDC). In this study, high temperature vulcanized solid silicone rubber as matrix has been used to prepare DDC composites with barium titanate (BT) filler and CDC composites with both BT as dielectric and ketjenblack as conductive fillers, using Taguchi design of experiments. The effect of factors such as amount of fillers and curing agent, mixing time in roll mill and curing temperature on the dielectric and mechanical properties are reported. Lichtenecker model predicts the permittivity of the DDC composite more accurately. For the CDC composites permittivity increased by 390%, effective resistivity decreased by 80%, Young’s modulus increased by 368% and Shore A hardness increased by 90% as compared to those of reference matrix. Important interaction effects are observed among both the fillers that are uniformly dispersed without any aggregation.

     

A comparison of thermoplastic polyurethane incorporated with graphene oxide and thermally reduced graphene oxide: Reduction is not always necessary

Despite wide applications of reduced graphene-oxide (GO)-reinforced polymer-based composites, the necessity of the reduction procedure toward GO is still controversial. In this article, thermoplastic polyurethane (TPU) composites incorporated with GO and thermally reduced graphene oxide (TGO) were fabricated. GO and TGO exhibited different effects on crystallization behaviors, and mechanical and thermal properties of the TPU matrix. With 2.0 wt % filler loading, TPU composite reinforced by GO (TPU-GO-2 wt %) exhibited better thermal stability than that reinforced by TGO (TPU-TGO-2 wt %). The interfacial interaction between the nanofillers and the TPU matrix as well as their influence on the mobility of TPU chains were investigated, which proved that GO is superior to TGO in improving interface adhesion and maintaining crystallization of the TPU matrix. Compared with TPU-TGO-2 wt %, improved mechanical properties of TPU-GO-2 wt % were also evidenced owing to more oxygen-containing groups. This work demonstrates that the reduction of GO is not always necessary in fabricating polymer composites. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47745.     

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.     

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%.     

Vermicular Ni@RL-CS: Preparation,characterization and its applications in electromagnetic shielding

One-dimensional conductive materials are of great significance to the construction of conductive network in the polymer matrix due to their large aspect ratio. In this work, a nickel-plated rod-like calcium silicate composite (Ni@RL-CS) with unique vermicular structure was successfully fabricated by an electroless plating method. The structure and property of as-prepared Ni@RL-CS were characterized, and its electromagnetic shielding ability was evaluated through mixing with thermoplastic polyurethane (TPU). Results indicate that the Ni@RL-CS shows good electrical conductivity, magnetic property and strong dielectric loss ability. The Ni@RL-CS with a one-dimensional vermicular structure is easier to construct a continuous conductive network in TPU matrix, which greatly improves the electromagnetic shielding effectiveness of the TPU resin. TPU/Ni@RL-CS binary composite with 20 vol% Ni@RL-CS achieves ultrahigh specific EMI SE/thickness of 92.6 dB/mm in the frequency of X-band. By further hybridizing Ni@RL-CS with GNPs, the TPU/Ni@RL-CS/GNPs trinary composite exhibits excellent electromagnetic shielding performance. When the contents of Ni@RL-CS and GNPs are 10 vol% and 1.5 vol%, respectively, the specific EMI SE/thickness of the corresponding trinary composite reaches 74.6 dB/mm in the X-band owe to the dense conductive network, which is 56.5% higher than that of the binary TPU/Ni@RL-CS composite with the same content of 10 vol% Ni@RL-CS.. The synergistic effects of dielectric loss, magnetic loss, and the interfacial polarization loss are the main shielding mechanism. This work provides a strategy to prepare a functional filler based on an insulating inorganic material for electromagnetic shielding. The as-prepared Ni@RL-CS with the unique vermicular structure and outstanding electromagnetic shielding performance can serves as a functional filler to modify polymers for electromagnetic shielding applications.     

改性碳纳米管增强热塑性聚氨酯复合材料的性能研究

以碳纳米管（CNTs）和热塑性聚氨酯（TPU）为原料,通过硫酸（H₂SO₄）/硝酸（HNO₃）混合溶液处理碳纳米管颗粒表面以达到改性的效果,使用改性过后的碳纳米管熔融共混制备出TPU/CNTs复合材料。研究了不同含量的CNTs对TPU基体的流变、力学、耐磨性以及热性能的影响。结果表明, 改性过后的CNTs在TPU基体中形成了良好的分散性和相容性;TPU/CNTs复合材料在高频剪切下保留了复合材料的加工流动性,并且复合材料的拉伸强度以及耐磨性相较于TPU有明显的增强,其中在改性碳纳米管含量较低时,复合材料的力学性能改善较为明显;改性CNTs的加入提高了TPU基体的熔融温度和结晶度;改性CNTs的加入提高了复合材料的热降解温度,提高了TPU基体的热稳定性。     

Influence of filler type and content on thermal conductivity and mechanical properties of thermoplastic compounds

Combining thermal conductivity with electrical isolation is a very interesting topic for electronic applications in order to transfer the generated heat. Typical approaches combine thermally conductive fillers with a thermoplastic matrix. The aim of this work was to investigate the influence of different fillers and matrices on the thermal conductivity of the polymer matrix composites. In this study, various inorganic fillers, including aluminum oxide (Al₂O₃), zinc oxide (ZnO), and boron nitride (BN) with different shapes and sizes, were used in matrix polymers, such as polyamide 6 (PA6), polypropylene (PP), polycarbonate (PC), thermoplastic polyurethane (TPU), and polysulfone (PSU), to produce thermally conductive polymer matrix composites by compounding and injection molding. Using simple mathematical models (e.g., Agari model, Lewis–Nielson model), a first attempt was made to predict thermal conductivity from constituent properties. The materials were characterized by tensile testing, density measurement, and thermal conductivity measurement. Contact angle measurements and the calculated surface energy can be used to evaluate the wetting behavior, which correlates directly with the elastic modulus. Based on the aforementioned evaluations, we found that besides the volume fraction, the particle shape in combination with the intrinsic thermal conductivity of the filler has the greatest influence on the thermal conductivity of the composite.     

石墨烯导热高分子复合材料的制备、性能与机理

石墨烯是一种具有超大的比表面积、良好的热和化学稳定性、超高的热导率以及易于化学修饰的蜂窝状单层碳材料,已作为填料广泛应用于导热高分子复合材料领域。近年来石墨烯导热高分子材料的研究重点是改善石墨烯在聚合物基体中的界面相容性和分散性能。阐述了近年来石墨烯导热高分子复合材料的制备方法及其热性能,并重点对石墨烯导热高分子复合材料的导热机理进行综述,同时结合研究现状对石墨烯导热高分子复合材料的研究方向进行展望。     

Dielectric property and electromagnetic interference shielding effectiveness of ethylene vinyl acetate‐based conductive composites: Effect of different type of carbon fillers

Carbon black, short carbon fiber (SCF), and multiwall carbon nano‐tube (MWNT)‐filled conductive composites were prepared from ethylene vinyl acetate copolymer. The dielectric property and electromagnetic interference (EMI) shielding of carbon black, MWNT, and SCF‐filled composites were studied with different filler loadings. The dielectric constant and loss of filled polymer composites is due to the formation of interfacial polarization in the polymer matrix. It was found that the dielectric constant, dielectric loss, and EMI shielding of filled composites depends on amount and type of filler loading. The results of different experiments have been discussed in the light of break down and formation of continuous conductive network in polymer matrix. The results indicate that these composites can be used as effective EMI shielding materials. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers.     

Addition of precipitated calcium carbonate filler to thermoplastic polyurethane adhesives

Precipitated calcium carbonate filler (PCC) was added to a thermoplastic polyurethane adhesive (TPU). The addition of PCC produced a moderate increase in the rheological and viscoelastic properties of TPU due to the poor dispersion of filler (i.e. found to be clusters) and the weak interactions between the PCC nanoparticles and the polymer chains. The interactions were noticed by ATR-IR spectroscopy by displacement of the bands at 3326, 1729 and 1061 cm⁻¹ to higher wave number of the polyurethane. Furthermore, the first glass transition temperature of the polyurethane was found to decrease by adding PCC filler. The crystallinity of the soft segments in the TPU was decreased by adding PCC because of the disruption of the degree of phase separation in the polymer. The initial adhesive strength in PVC/TPU adhesive/PVC joints increased noticeably by adding PCC filler, the greater the amount of filler in the TPU, the greater the initial adhesive strength found. Finally, the highest final adhesive strength (72 h after joint formation) was obtained in the joint produced with the TPU containing 10 wt% PCC.     

3D interconnected high aspect ratio tellurium nanowires in epoxy nanocomposites: serving as thermal conductive expressway

Heat removal via thermal management materials is attracting more and more attention in the electronic industry. Conventional particle/polymer thermal conductive composites require a high filler loading ratio (>30 vol %), which cause severe thermal interfacial resistance and mechanical issue. In this work, we fabricate tellurium nanowires (NWs)/epoxy nanocomposites via a facile bar coating method. According to Agari model and Maxwell–Eucken model, the as-synthesized ultra-long NWs with high aspect ratio (>100) construct the 3D interconnected thermal conductive network better in resin matrix to facilitate the heat transfer process. The results show that at a low loading ratio of 2.4 vol %, this nanocomposite exhibits the out-of-plane and in-plane thermal conductivity of 0.378 and 1.63 W m⁻¹ K⁻¹, respectively, which is 189 and 715% higher than that of pure epoxy resin. Importantly, good stability, and flexibility of nanocomposites are well maintained. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47054.