Breaking Through Bottlenecks for Thermally Conductive Polymer Composites:A Perspective for Intrinsic Thermal Conductivity,Interfacial Thermal Resistance and Theoretics

Rapid development of energy,electrical and electronic technologies has put forward higher requirements for the thermal conductivities of polymers and their composites.However,the thermal conductivity coefficient(λ)values of prepared thermally conductive polymer composites are still difficult to achieve expectations,which has become the bottleneck in the fields of thermally conductive polymer composites.Aimed at that,based on the accumulation of the previous research works by related researchers and our research group,this paper proposes three possible directions for breaking through the bottlenecks:(1)preparing and synthesizing intrinsically thermally conductive polymers,(2)reducing the interfacial thermal resistance in thermally conductive polymer composites,and(3)establishing suitable thermal conduction models and studying inner thermal conduction mechanism to guide experimental optimization.Also,the future development trends of the three above-mentioned directions are foreseen,hoping to provide certain basis and guidance for the preparation,researches and development of thermally conductive polymers and their composites.

Ultraviolet‑Irradiated All‑Organic Nanocomposites with Polymer Dots for High‑Temperature Capacitive Energy Storage

Polymer dielectrics capable of operating efficiently at high electric fields and elevated temperatures are urgently demanded by next-generation electronics and electrical power systems.While inorganic fillers have been extensively utilized to improved high-temperature capacitive performance of dielectric polymers,the presence of thermodynamically incompatible organic and inorganic components may lead to concern about the long-term stability and also complicate film processing.Herein,zero-dimensional polymer dots with high electron affinity are introduced into photoactive allyl-containing poly(aryl ether sulfone)to form the all-organic polymer composites for hightemperature capacitive energy storage.Upon ultraviolet irradiation,the crosslinked polymer composites with polymer dots are efficient in suppressing electrical conduction at high electric fields and elevated temperatures,which significantly reduces the high-field energy loss of the composites at 200℃.Accordingly,the ultraviolet-irradiated composite film exhibits a discharged energy density of 4.2 J cm^(−3)at 200℃.Along with outstanding cyclic stability of capacitive performance at 200℃,this work provides a promising class of dielectric materials for robust high-performance all-organic dielectric nanocomposites.

Highly Thermally Conductive Polymer/Graphene Composites with Rapid Room‑Temperature Self‑Healing Capacity

Composites that can rapidly self-healing their structure and function at room temperature have broad application prospects.However,in view of the complexity of composite structure and composition,its self-heal is facing challenges.In this article,supramolecular effect is proposed to repair the multistage structure,mechanical and thermal properties of composite materials.A stiff and tough supramolecular frameworks of 2-[[(butylamino)carbonyl]oxy]ethyl ester(PBA)–polydimethylsiloxane(PDMS)were established using a chain extender with double amide bonds in a side chain to extend prepolymers through copolymerization.Then,by introducing the copolymer into a folded graphene film(FGf),a highly thermally conductive composite of PBA–PDMS/FGf with self-healing capacity was fabricated.The ratio of crosslinking and hydrogen bonding was optimized to ensure that PBA–PDMS could completely self-heal at room temperature in 10 min.Additionally,PBA–PDMS/FGf exhibits a high tensile strength of 2.23±0.15 MPa at break and high thermal conductivity of 13±0.2 W m^(−1)K^(−1);of which the self-healing efficiencies were 100%and 98.65%at room temperature for tensile strength and thermal conductivity,respectively.The excellent self-healing performance comes from the efficient supramolecular interaction between polymer molecules,as well as polymer molecule and graphene.This kind of thermal conductive self-healing composite has important application prospects in the heat dissipation field of next generation electronic devices in the future.

Efficient Preconstruction of Three‑Dimensional Graphene Networks for Thermally Conductive Polymer Composites

Electronic devices generate heat during operation and require efficient thermal management to extend the lifetime and prevent performance degradation.Featured by its exceptional thermal conductivity,graphene is an ideal functional filler for fabricating thermally conductive polymer composites to provide efficient thermal management.Extensive studies have been focusing on constructing graphene networks in polymer composites to achieve high thermal conductivities.Compared with conventional composite fabrications by directly mixing graphene with polymers,preconstruction of three-dimensional graphene networks followed by backfilling polymers represents a promising way to produce composites with higher performances,enabling high manufacturing flexibility and controllability.In this review,we first summarize the factors that affect thermal conductivity of graphene composites and strategies for fabricating highly thermally conductive graphene/polymer composites.Subsequently,we give the reasoning behind using preconstructed three-dimensional graphene networks for fabricating thermally conductive polymer composites and highlight their potential applications.Finally,our insight into the existing bottlenecks and opportunities is provided for developing preconstructed porous architectures of graphene and their thermally conductive composites.

A Novel Technique for Preparation of Electrically Conductive ABS/Cu Polymeric Gradient Composites

A novel technique for preparing functionally gradient electrically conductive polymeric composites was developed by using of solution casting technique on the principle of Stokes＇ law. Acrylonitrile- butadiene-styrene/Cu （ABS/Cu） gradient polymeric composites were prepared successfully using this technique. The gradient structures, electrically conductive performance and mechanical properties of the ABS/Cu composites were investigated. Optical microscope observation shows that the gradient distribution of Cu particles in ABS matrix was formed along their thickness-direction. The electrically conductive testing results indicate that the order of magnitude of surface resistivity was kept in 10^15 Ω at ABS rich side, while that declined to 10^5 Ω at Cu particles rich side, and the percolation threshold was in the range of 2.82 vo1%- 4.74 vol% Cu content at Cu particles rich side. Mechanical test shows that the tensile strength reduced insignificantly as the content of Cu increases owing to the gradient distribution.

Incorporation of Ionic Conductive Polymers into Sulfide Electrolyte-Based Solid-State Batteries to Enhance Electrochemical Stability and Cycle Life

Sulfide-based inorganic solid electrolytes are promising materials for high-performance safe solid-state batteries.The high ion conductivity,mechanical characteristics,and good processability of sulfide-based inorganic solid electrolytes are desirable properties for realizing high-performance safe solid-state batteries by replacing conventional liquid electrolytes.However,the low chemical and electrochemical stability of sulfide-based inorganic solid electrolytes hinder the commercialization of sulfide-based safe solid-state batteries.Particularly,the instability of sulfide-based inorganic solid electrolytes is intensified in the cathode,comprising various materials.In this study,carbonate-based ionic conductive polymers are introduced to the cathode to protect cathode materials and suppress the reactivity of sulfide electrolytes.Several instruments,including electrochemical spectroscopy,X-ray photoelectron spectroscopy,and scanning electron microscopy,confirm the chemical and electrochemical stability of the polymer electrolytes in contact with sulfide-based inorganic solid electrolytes.Sulfide-based solid-state cells show stable electrochemical performance over 100 cycles when the ionic conductive polymers were applied to the cathode.

Ignition processes and characteristics of charring conductive polymers with a cavity geometry in precombustion chamber for applications in micro/nano satellite hybrid rocket motors

The arc ignition system based on charring polymers has advantages of simple structure,low ignition power consumption and multiple ignitions,which bringing it broadly application prospect in hybrid propulsion system of micro/nano satellite.However,charring polymers alone need a relatively high input voltage to achieve pyrolysis and ignition,which increases the burden and cost of the power system of micro/nano satellite in practical application.Adding conductive substance into charring polymers can effectively decrease the conducting voltage which can realize low voltage and low power consumption repeated ignition of arc ignition system.In this paper,a charring conductive polymer ignition grain with a cavity geometry in precombustion chamber,which is composed of PLA and multiwall carbon nanotubes(MWCNT)was proposed.The detailed ignition processes were analyzed and two different ignition mechanisms in the cavity of charring conductive polymers were revealed.The ignition characteristics of charring conductive polymers were also investigated at different input voltages,ignition grain structures,ignition locations and injection schemes in a visual ignition combustor.The results demonstrated that the ignition delay and external energy required for ignition were inversely correlated with the voltages applied to ignition grain.Moreover,the incremental depth of cavity shortened the ignition delay and external energy required for ignition while accelerated the propagation of flame.As the depth of cavity increased from 2 to 6 mm(at 50 V),the time of flame propagating out of ignition grain changed from 235.6 to 108 ms,and values of mean ignition delay time and mean external energy required for ignition decreased from 462.8 to 320 ms and 16.2 to 10.75 J,respectively.The rear side of the cavity was the ideal ignition position which had a shorter ignition delay and a faster flame propagation speed in comparison to other ignition positions.Compared to direct injection scheme,swirling injection provided a more favorable flow field environment in the cavity,which was beneficial to ignition and initial flame propagation,but the ignition position needed to be away from the outlet of swirling injector.At last,the repeated ignition characteristic of charring conductive polymers was also investigated.The ignition delay time and external energy required for ignition decreased with repeated ignition times but the variation was decreasing gradually.

The Development of Thermal Conductive Polymer Composites for Heat Sink

The thermal and mechanical properties of the polyamide 6/boron nitride and polyphenylene sulfide/graphite composites have been investigated as a function of composition and size of fillers. The addition of highly thermal conductive h-BN and graphite gives rise to large increase （about 2 times） of thermal conductivity of individual polymer. In PPS/graphite system, the higher conductivity value was obtained when smaller graphites were added. Meanwhile, the tensile and flexural strength are reduced upon increasing filler loading.

Wearable and stretchable conductive polymer composites for strain sensors:How to design a superior one?

Wearable and stretchable strain sensors have potential values in the fields of human motion and health monitoring,flexible electronics,and soft robotic skin.The wearable and stretchable strain sensors can be directly attached to human skin,providing visualized detection for human motions and personal healthcare.Conductive polymer composites(CPC)composed of conductive fillers and flexible polymers have the advantages of high stretchability,good flexibility,superior durability,which can be used to prepare flexible strain sensors with large working strain and outstanding sensitivity.This review has put forward a comprehensive summary on the fabrication methods,advanced mechanisms and strain sensing abilities of CPC strain sensors reported in recent years,especially the sensors with superior performance.Finally,the structural design,bionic function,integration technology and further application of CPC strain sensors are prospected.

CONDUCTIVE COMPOSITES FROM POLYPYRROLE ELECTROPOLYMERIZED IN A POLYURETHANE MATRIX

In order to improve the mechanical properties of polypyrrole, composites were made by electropolymerizing polypyrrole in a polyurethane matrix. Polypyrrole/polyurethane (PPY/PU) composite films containing CLO_4^-, BF_4^- or CH_3-C_6H_4-SO_3^- counter ions were made in a variety of solvent systems and characterized by SEM, electronic conductivity, FTIR, and mechanical properties. Composite films showing much greater fiexibility than pure polypyrrole were obtained, but their electronic conductivities were substantially lower. Measured eonductivities ranged from 0.001 to 8 S/cm, tensile strengths from 44 to 592 psi, and elongation to failure from 3 to 70%.

Effects of carbonaceous conductive fillers on electrical and thermal properties of asphalt-matrix conductive composites

The relationship between thermal/electrical conductivity enhancement in asphalt-matrix mixtures and the properties of filling conductive particles is studied. The thermal properties with filling the carbon fiber, graphite conductive particles in asphalt-matrix mixtures are investigated. Based on the generalized effective medium theory （ EMT ）, the effective thermal and electrical conductivity of carbon fiber/asphalt and graphite/asphalt composites are theoretically elucidated. The theoretical results are found to be in reasonably well agreement with the experimental data. Moreover, the theoretical and experimental results show that the large-aspect-ratio shape of particles can help to achieve a large enhancement of effective conductivity, and the use of disk-like high conductivity particles can limit the additive contents for preserving the volumetric properties and mechanical properties of asphalt composites. The generalized effective medium theory model can be used for predicting the thermal and electrical properties of asphaltmatrix composites, which is still available for most of the thermal/electrical modifications in two-phase composites.

Thermal conductivity model of filled polymer composites

Theoretical and empirical models for predicting the thermal conductivity of polymer composites were summarized since the 1920s.The effects of particle shape,filler amount,dispersion state of fillers,and interfacial thermal barrier on the thermal conductivity of filled polymer composites were investigated,and the agreement of experimental data with theoretical models in literatures was discussed.Silica with high thermal conductivity was chosen to mix with polyvinyl-acetate （EVA） copolymer to prepare SiO2/EVA co-films.Experimental data of the co-films＇ thermal conductivity were compared with some classical theoretical and empirical models.The results show that Agari＇s model,the mixed model,and the percolation model can predict well the thermal conductivity of SiO2/EVA co-films.

A Perspective for Developing Polymer-Based Electromagnetic Interference Shielding Composites

The rapid development of aerospace weapons and equipment,wireless base stations and 5G communication technologies has put forward newer and higher requirements for the comprehensive performances of polymer-based electromagnetic interference(EMI)shielding composites.However,most of currently prepared polymer-based EMI shielding composites are still difficult to combine high performance and multi-functionality.In response to this,based on the research works of relevant researchers as well as our research group,three possible directions to break through the above bottlenecks are proposed,including construction of efficient conductive networks,optimization of multi-interfaces for lightweight and multifunction compatibility design.The future development trends in three directions are prospected,and it is hoped to provide certain theoretical basis and technical guidance for the preparation,research and development of polymer-based EMI shielding composites.

A Novel Method for Preparing Polyurethane Based Conductive Composites with Low Percolation Threshold

A novel method for preparing conductive carbon black fllled polymer composites with low percolation threshold from polyurethane emulsion are reported in this paper. The experimental results indicate that with a rise in carbon black concentration the insulator-conductor transition in the emulsion blended composites occurs at 0.8-1.4vol%. In contrast, the solution blended composites exhibit drastic increase in conductivity at conducting filler fraction as high as 12.3-13.3vol%. It is demonstrated that the composites microstructure rather than chemical structure of the matrix polymer predominantly determines the electrical conduction performance of the composites.

Structural Design Strategies of Polymer Matrix Composites for Electromagnetic Interference Shielding:A Review

With the widespread application of electronic communication technology,the resulting electromagnetic radiation pollution has been significantly increased.Metal matrix electromagnetic interference(EMI)shielding materials have disadvantages such as high density,easy corrosion,difficult processing and high price,etc.Polymer matrix EMI shielding composites possess light weight,corrosion resistance and easy processing.However,the current polymer matrix composites present relatively low electrical conductivity and poor EMI shielding performance.This review firstly discusses the key concept,loss mechanism and test method of EMI shielding.Then the current development status of EMI shielding materials is summarized,and the research progress of polymer matrix EMI shielding composites with different structures is illustrated,especially for their preparation methods and evaluation.Finally,the corresponding key scientific and technical problems are proposed,and their development trend is also prospected.

Photoconductive Properties of MEH-PPV/CuS-Nanoparticle Composites

Photoconductive properties of photodiodes based on composites of CuS nanoparticles and Poly[2-methoxy,5- （2＇-ethylhexyloxy）-p-phenylenevlnylene] （MEH-PPV） are investigated. By comparing composite devices with different MEH-PPV：CuS weight ratios of l：l （D2-1）, 1：1.25 （D2-2）, 1：2.5 （132-3） and 1：5 （D2-4）, it is found that the device D2 3 exhibited the best performance： the short-circuit current density of 17μA/cm^2 with the light intensity of 16.7mW/cm^2, the highest open-circuit voltage of 0,83 V, and the photosensitivity of 132 at reverse bias of - 1 V. The photosensitivity is improved by a factor of 5 compared with the undoped MEH-PPV device.

Preparation of Laminin-apatite-polymer Composites Using Metastable Calcium Phosphate Solutions

A synthetic polymer with a laminin-apatite composite layer on its surface would be useful as a percutaneous device. The preparation of such a composite was attempted in the present study using poly（ ethylene terephthalate ） （PET） and polyethylene （PE） as the synthetic polymer. PET and PE plates and those pretreated with an oxygen plasma were alternately dipped in calcium and phosphate ion solutions, and then immersed in a metastable calcium phosphate solution supplemented with laminin （ LCP solution ）. The PET and PE plates pretreated with an oxygen plasma formed a uniform and continuous layer of a laminin-apatite composite on their surfaces. In contrast, the PET and PE plates that had not been pretreated with an oxygen plasma did not form a continuous layer of a laminin-apatite composite on their surfaces. The hydrophilic functional groups on the PET and PE surfaces introduced by the plasma treatment were responsible for the successful laminin-apatite coruposite coating.

Microstructure of Steel Fiber Reinforced Polymer-cement-based Composites

Mercury intrusion porosimetry was used to measure the pore structure of steel fiber reinforced polymer-cement-based composite. The results indicate that the large pore volume decreases by 57. 8% - 51.2% and by 87. 1% - 88% with the addition of steel fibers and polymers respectively. When both steel fibers and polymers are simultaneously added, the large pore volume decreases by 88.3% - 90.1% . As a surface active material , polymer has a favorable water-reduced and forming-film effect, which is contributed to the decrease of the thickness of water film and the improvement of the conglutination between the fibers and the matrix. Polymers could form a microstructure network. This network structure and the bone structure of cement hydration products penetrate each other and thus the interpenetrating network with sticky aggregate and steel fiber inside forms.

Mussel‑Inspired Redox‑Active and Hydrophilic Conductive Polymer Nanoparticles for Adhesive Hydrogel Bioelectronics

Conductive polymers(CPs)are generally insoluble,and developing hydrophilic CPs is significant to broaden the applications of CPs.In this work,a mussel-inspired strategy was proposed to construct hydrophilic CP nanoparticles(CP NPs),while endowing the CP NPs with redox activity and biocompatibility.This is a universal strategy applicable for a series of CPs,including polyaniline,polypyrrole,and poly(3,4-ethylenedioxythiophene).The catechol/quinone contained sulfonated lignin(LS)was doped into various CPs to form CP/LS NPs with hydrophilicity,conductivity,and redox activity.These CP/LS NPs were used as versatile nanofillers to prepare the conductive hydrogels with long-term adhesiveness.The CP/LS NPs-incorporated hydrogels have a good conductivity because of the uniform distribution of the hydrophilic NPs in the hydrogel network,forming a well-connected electric path.The hydrogel exhibits long-term adhesiveness,which is attributed to the mussel-inspired dynamic redox balance of catechol/quinone groups on the CP/LS NPs.This conductive and adhesive hydrogel shows good electroactivity and biocompatibility and therefore has broad applications in electrostimulation of tissue regeneration and implantable bioelectronics.