Ultralow Interfacial Thermal Resistance of Graphene Thermal Interface Materials with Surface Metal Liquefaction

Developing advanced thermal interface materials(TIMs)to bridge heat-generating chip and heat sink for constructing an efficient heat transfer interface is the key technology to solve the thermal management issue of high-power semiconductor devices.Based on the ultra-high basal-plane thermal conductivity,graphene is an ideal candidate for preparing high-performance TIMs,preferably to form a vertically aligned structure so that the basal-plane of graphene is consistent with the heat transfer direction of TIM.However,the actual interfacial heat transfer efficiency of currently reported vertically aligned graphene TIMs is far from satisfactory.In addition to the fact that the thermal conductivity of the vertically aligned TIMs can be further improved,another critical factor is the limited actual contact area leading to relatively high contact thermal resistance(20-30 K mm^(2) W^(−1))of the“solid-solid”mating interface formed by the vertical graphene and the rough chip/heat sink.To solve this common problem faced by vertically aligned graphene,in this work,we combined mechanical orientation and surface modification strategy to construct a three-tiered TIM composed of mainly vertically aligned graphene in the middle and micrometer-thick liquid metal as a cap layer on upper and lower surfaces.Based on rational graphene orientation regulation in the middle tier,the resultant graphene-based TIM exhibited an ultra-high thermal conductivity of 176 W m^(−1) K^(−1).Additionally,we demonstrated that the liquid metal cap layer in contact with the chip/heat sink forms a“liquid-solid”mating interface,significantly increasing the effective heat transfer area and giving a low contact thermal con-ductivity of 4-6 K mm^(2) W^(−1) under packaging conditions.This finding provides valuable guidance for the design of high-performance TIMs based on two-dimensional materials and improves the possibility of their practical application in electronic thermal management.

Smart materials for safe lithium-ion batteries against thermal runaway

In recent years,the new energy storage system,such as lithium ion batteries(LIBs),has attracted much attention.In order to meet the demand of industrial progress for longer cycle life,higher energy density and cost efficiency,a quantity of research has been conducted on the commercial application of LIBs.However,it is difficult to achieve satisfying safety and cycling performance simultaneously.There may be thermal runaway(TR),external impact,overcharge and overdischarge in the process of battery abuse,which makes the safety problem of LIBs more prominent.In this review,we summarize recent progress in the smart safety materials design towards the goal of preventing TR of LIBs reversibly from different abuse conditions.Benefiting from smart responsive materials and novel structural design,the safety of LIBs can be improved a lot.We expect to provide a comprehensive reference for the development of smart and safe lithium-based battery materials.

Emerging low-density polyethylene/paraffin wax/aluminum composite as a form-stable phase change thermal interface material

Thermal interface materials(TIMs) play a vital role in the thermal management of electronic devices and can significantly reduce thermal contact resistance(TCR). The TCR between the solid–liquid contact surface is much smaller than that of the solid–solid contact surface, but conventional solid–liquid phase change materials are likely to cause serious leakage. Therefore, this work has prepared a new formstable phase change thermal interface material. Through the melt blending of paraffin wax(PW) and low-density polyethylene(LDPE), the stability is improved and it has an excellent coating effect on PW. The addition of aluminum(Al) powder improves the low thermal conductivity of PW/LDPE, and the addition of 15wt% Al powder improves the thermal conductivity of the internal structure of the matrix by 67%. In addition, the influence of the addition of Al powder on the internal structure, thermal properties, and phase change behavior of the PW/LDPE matrix was systematically studied. The results confirmed that the addition of Al powder improved the thermal conductivity of the material without a significant impact on other properties, and the thermal conductivity increased with the increase of Al addition. Therefore, morphologically stable PW/LDPE/Al is an important development direction for TIMs.

Research progress on solder thermal interface materials

Down to the road of miniaturization and high power density,the heat dissipation is becoming one of the critical factors restricting further development of advanced microelectronic devices.Traditional polymer-based thermal interface materials(TIMs) are not competitive for the high efficiency thermal management,mainly due to their low intrinsic thermal conductivity and high interface thermal resistance.Solder-based TIM is one of the best candidates for the next generation of thermal interface materials.This paper conducts a perspective review of the state of the art of solder TIM,including low melting alloy solder TIM,composite solder TIM and nanostructured solder TIM.The microstructure,process parameters,thermal performance and reliability of different TIMs are summarized and analyzed.The future trends of advanced TIMs are discussed.

Experimental investigation of high temperature thermal contact resistance with interface material

Thermal contact resistance plays a very important role in heat transfer efficiency and thermomechanical coupling response between two materials,and a common method to reduce the thermal contact resistance is to fill a soft interface material between these two materials.A testing system of high temperature thermal contact resistance based on INSTRON 8874 is established in the present paper,which can achieve 600 C at the interface.Based on this system,the thermal contact resistance between superalloy GH600 material and three-dimensional braid C/C composite material is experimentally investigated,under different interface pressures,interface roughnesses and temperatures,respectively.At the same time,the mechanism of reducing the thermal contact resistance with carbon fiber sheet as interface material is experimentally investigated.Results show that the present testing system is feasible in the experimental research of high temperature thermal contact resistance.

Exploring Trade-offs in Thermal Interface Materials:The Impact of Polymer-Filler Interfaces on Thermal Conductivity and Thixotropy

Effective thermal transport across solid-solid interfaces which is essential in thermal interface materials(TIMs),necessitates both optimal thixotropy and high thermal conductivity.The role of filler surface modification,a fundamental aspect of TIM fabrication,in the influence of these properties is not fully understood.This study employs the use of a silane coupling agent(SCA)to modify alumina,integrating experimental approaches with molecular dynamics simulations,to elucidate the interface effects on thixotropy and thermal conductivity in polydimethylsiloxane(PDMS)-based TIMs.Our findings reveal that the variations of SCAs modify both interface binding energy and transition layer thickness.The interface binding energy restricts macromolecular segmental relaxation near the interface,hindering desirable thixotropy and bond line thickness.On the contrary,the thickness of the transition layer at the interface positively influences thermal conductivity,facilitating the transport of phonons between the polymer and filler.Consequently,selecting an optimal SCA allows a balance between traditionally conflicting goals of high thermal conductivity and minimal bond line thickness,achieving an impressively low interface thermal resistance of just 2.45-4.29 K·mm^(2)·W^(-1)at275.8 kPa.

High-performance thermal interface materials enabled by vertical alignment of lightweight and soft graphene foams

High-performance thermal interface materials (TIMs) are highly sought after for modern electronics. Two-dimensional (2D) materials as vertical aligned fillers can optimize the out-plane thermal conductivity (k ⊥), but their excessively high content or intrinsic rigidness deteriorate TIMs softness, leading to worsening for thermal contact resistance (R contact). In this study, 2D graphene materials are fabricated into lightweight and soft graphene foams (GFs) with high-orientation, acting as vertical filler frameworks to optimize the k ⊥ and R contact for vertical GF (VGF) TIMs. The VGF-TIM has a high k ⊥ of 47.9 W·m^(−1)·K^(−1) at a low graphene content of 15.5 wt.%. Due to the softness and low filler contents of GFs, the VGF-TIM exhibits a low compressive module (4.2 MPa), demonstrating excellent compressibility. The resulting TIM exhibit a low contact resistance of 24.4 K·mm2·W^(−1), demonstrating 185.1% higher cooling efficiency in practical heat dissipating scenario compared to commercial advanced TIMs. This work provides guidelines for the design of advanced TIMs and their applications in thermal management.

Understanding the Thermal Impedance of Silicone Rubber/Hexagonal Boron Nitride Composites as Thermal Interface Materials

Silicone rubber(SR) composites are most widely used as thermal interface materials(TIMs) for electronics heat dissipation. Thermal impedance as the main bottleneck limiting the performance of TIMs is usually neglected. Herein, the thermal impedance of SR composites loaded with different levels of hexagonal boron nitride(h-BN) as TIMs was elaborated for the first time by the ASTM D 5470 standard test and finite element analysis. It was found that elastic modulus and surface roughness of SR composites increased with the increase of h-BN content, indicating that the conformity was reduced. When the assembly pressure was 0.69 MPa, there existed an optimal h-BN content at which the contact resistance was minimum(0.39 K·cm^(2)·W^(-1)). Although the decreased bond line thickness(BLT) by increasing the assembly pressure was beneficial to reduce the thermal impedance, the proper assembly pressure should be selected to prevent the warpage of the contact surfaces and the increase in contact resistance, according to the compression properties of the SR composites. This study provides valuable insights into fabrication of high-performance TIMs for modern electronic device applications.

Fabrication and Excellent Properties of Polyvinylidene fluoride/Graphene Composite Films as Thermal Interface Materials

The growing concern about thermal conductivityand electromagnetic shielding inelectronic equipment has promoted the development of interfacial film materials.In this work,polyvinylidene fluoride(PVDF)/graphene composite films with different graphene contents were fabricated by high-energy ball milling,cold isostatic pressing,scraping and coating,successively.High-energy ball milling is beneficial to the dispersion of graphene powder,while cold isostatic pressing can greatly enhance thermal conductivity and mechanical strength by reducing the voids in the film and increasing the contact area of graphene sheets.The thermal conductivity,tensile strength and electromagnetic shielding properties of the films were carefully investigated and compared.It was demonstrated that the thermal conductivity increased from 0.19 Wm-1.K-1 for pure PVDF to 103.9 W-m-1.K-1 for the composite film with PVDF:graphene=1:3.Meanwhile the electromagnetic shielding efficiency can reach 36.55 dB.The prepared PVDF/graphene composite films exhibit outstanding overall performance and have the potential for practical applications.

Regulatable Orthotropic 3D Hybrid Continuous Carbon Networks for Efficient Bi-Directional Thermal Conduction

Vertically oriented carbon structures constructed from low-dimen-sional carbon materials are ideal frameworks for high-performance thermal inter-face materials(TIMs).However,improving the interfacial heat-transfer efficiency of vertically oriented carbon structures is a challenging task.Herein,an orthotropic three-dimensional(3D)hybrid carbon network(VSCG)is fabricated by depositing vertically aligned carbon nanotubes(VACNTs)on the surface of a horizontally oriented graphene film(HOGF).The interfacial interaction between the VACNTs and HOGF is then optimized through an annealing strategy.After regulating the orientation structure of the VACNTs and filling the VSCG with polydimethylsi-loxane(PDMS),VSCG/PDMS composites with excellent 3D thermal conductive properties are obtained.The highest in-plane and through-plane thermal conduc-tivities of the composites are 113.61 and 24.37 W m^(-1)K^(-1),respectively.The high contact area of HOGF and good compressibility of VACNTs imbue the VSCG/PDMS composite with low thermal resistance.In addition,the interfacial heat-transfer efficiency of VSCG/PDMS composite in the TIM performance was improved by 71.3%compared to that of a state-of-the-art thermal pad.This new structural design can potentially realize high-performance TIMs that meet the need for high thermal conductivity and low contact thermal resistance in interfacial heat-transfer processes.

Quantitative analysis on influencing factors for interface propagation-based thermal conductivity measurement method during solid-liquid transition

The recently proposed interface propagation-based method has shown its advantages in obtaining the thermal conductivity of phase change materials during solid-liquid transition over conventional techniques. However, in previous investigation, the analysis on the measurement error was qualitative and only focused on the total effects on the measurement without decoupling the influencing factors. This paper discusses the effects of influencing factors on the measurement results for the interface propagation-based method. Numerical simulations were performed to explore the influencing factors, namely model simplification, subcooling and natural convection, along with their impact on the measurement process and corresponding measurement results. The numerical solutions were provided in terms of moving curves of the solid-liquid interface and the predicted values of thermal conductivity. Results indicated that the impact of simplified model was strongly dependent on Stefan number of the melting process. The degree of subcooling would lead to underestimated values for thermal conductivity prediction. The natural convection would intensify the heat transfer rate in the liquid region, thereby overestimating the obtained results of thermal conductivity. Correlations and experimental guidelines are provided. The relative errors are limited in ±1.5%,±3%and ±2% corresponding to the impact of simplified model, subcooling and natural convection, respectively.

Roadmap towards new generation liquid metal thermal interface materials

As electronic devices continue to evolve toward miniaturization and integration,traditional thermal interface materials(TIMs)are no longer able to meet the ever-tougher thermal management challenges.Owing to their high thermal conductivity and excellent conformability within a highly confined space,liquid metals have great potential for advanced thermal management in various cutting-edge devices and have become a key candidate for next-generation high-performance TIMs.In addition to already known materials,such as liquid metal alloy TIMs,particle-filled liquid metal TIMs,and liquid metal-filled TIMs,more TIMs are still being developed.This review presents a systematic classification of the liquid metal TIMs developed thus far,interprets the fundamental mechanisms underlying material innovation and in-situ heat transfer enhancement,and comparatively evaluates their respective advantages and shortcomings.Subsequently,a series of representative theoretical models for characterizing the thermal conductivities of composites are summarized,and the limits of the thermal conductivity of liquid metal TIMs are predicted to guide practical R&D efforts.To address the urgent need for higher-performance TIMs to overcome future thermal management challenges of electronic devices,a roadmap is outlined for the development of high-performance liquid metal TIMs,and a strategy for running these technologies is demonstrated.

Corrugated Graphene Paper Reinforced Silicone Resin Composite for Efficient Interface Thermal Management

With the rapid development of high-power-density electronic devices,interface thermal resistance has become a critical barrier for effective heat management in high-performance electronic products.Therefore,there is an urgent demand for advanced thermal interface materials(TIMs)with high cross-plane thermal conductivity and excellent compressibility to withstand increasingly complex operating conditions.To achieve this aim,a promising strategy involves vertically arranging highly thermoconductive graphene on polymers.However,with the currently available methods,achieving a balance between low interfacial thermal resistance,bidirectional high thermal conductivity,and large-scale production is challenging.Herein,we prepared a graphene framework with continuous filler structures in in-plane and cross-plane directions by bonding corrugated graphene to planar graphene paper.The interface interaction between the graphene paper framework and polymer matrix was enhanced via surface functionalization to reduce the interface thermal resistance.The resulting three-dimensional thermal framework endows the polymer composite material with a cross-plane thermal conductivity of 14.4 W·m^(-1)·K^(-1)and in-plane thermal conductivity of 130W·m^(-1)·K^(-1)when the thermal filler loading is 10.1 wt%,with a thermal conductivity enhancement per 1 wt%filler loading of 831%,outperforming various graphene structures as fillers.Given its high thermal conductivity,low contact thermal resistance,and low compressive modulus,the developed highly thermoconductive composite material demonstrates superior performance in TIM testing compared with TFLEX-700,an advanced commercial TIM,effectively solving the interfacial heat transfer issues in electronic systems.This novel filler structure framework also provides a solution for achieving a balance between efficient thermal management and ease of processing.

Effects of Yttrium on the Microstructures and Interfaces in a Low Expansion Superalloy

The forms and structures of the phases in Fe-Ni-Co-Nb-Ti-Si low expansion superal-loys have been studied using analytical electron microscopy, high resolution electron microscopy, chemical phase analysis, X-ray diffraction, etc. The effects of yttrium on the microstructures and properties in the superalloys have also been investigated. The results reveal that trace yttrium mainly located in the platelet precipitates makes the crystal structure changed. The platelet precipitates become smaller, denser and rather homogeneous with appropriate yttrium addition. Compared with the conventional low expansion superalloy, the misfit of the platelet phase with the matrix in the yttrium-containing low expansion superalloy decreases from 0.7% to 0.07%, which indicates very low stress at the interface.

Encapsulated carbon nanotube array as a thermal interface material compatible with standard electronics packaging

Vertically aligned carbon nanotubes arrays(VACNTs)are a promising candidate for the thermal interface material(TIM)of next-generation electronic devices due to their attractive thermal and mechanical properties.However,the environment required for synthesizing VACNTs is harsh and severely incompatible with standard device packaging processes.VACNTs’extremely low in-plane thermal conductivity also limits its performance for cooling hot spots.Here,using a transfer-and-encapsulate strategy,a two-step soldering method is developed to cap both ends of the VACNTs with copper microfoils,forming a standalone Cu-VACNTs-Cu sandwich TIM and avoiding the need to directly grow VACNTs on chip die.This new TIM is fully compatible with standard packaging,with excellent flexibility and high thermal conductivities in both in-plane and through-plane directions.The mechanical compliance behavior and mechanism,which are critical for TIM applications,are investigated in depth using in situ nanoindentation.The thermal performance is further verified in an actual light emitting diode(LED)cooling experiment,demonstrating low thermal resistance,good reliability,and achieving a 17℃ temperature reduction compared with state-of-the-art commercial TIMs.This study provides a viable solution to VACNTs’longstanding problem in device integration and free-end contact resistance,bringing it much closer to application and solving the critical thermal bottleneck in next-generation electronics.

碳纳米管/天然橡胶热界面材料制备及热管理性能研究

热界面材料是解决现代高功率和高集成化电子器件热量聚集和耗散的有效手段。基于三维网络结构调控导热性能的策略,以三聚氰胺泡沫(MF)为骨架,采用化学表面改性制备碳纳米管三维网络结构(CNT),并采用真空浸润法制备碳纳米管/天然橡胶热界面复合材料(CNT/NR),研究CNT含量对材料微观结构、导热性能和热管理性能的影响。结果表明,当CNT的含量为2.2%(质量分数)时,CNT可附着于MF骨架并呈现完整连续的三维网络结构,其热界面复合材料垂直面外的导热率为1.58 W m^(-1) K^(-1),拉伸强度为12.9 MPa,断裂伸长率为489%,并具有显著的热管理性能,这表明CNT/NR热界面复合材料有望成为一种机具应用价值的热管理材料。

Thermal Performance of Low-Melting-Temperature Alloy Thermal Interface Materials

Thermal resistance of low-melting-temperature alloy （LMTA） thermal interface materials （TIMs） was measured by laser flash method before and after different stages of heating. The results showed that the thermal performance of the LMTA TIMs was degraded during the heating process. It is suggested that the degradation may mainly be attributed to the interfacial reaction between the Cu and the molten LMTAs. Due to the fast growth rate of intermetallic compound （IMC） at the solid-liquid interface, a thick brittle IMC is layer formed at the interface, which makes cracks easy to initiate and expand. Otherwise, the losses of indium and tin contents in the LMTA during the interfacial reaction will make the melting point of the TIM layer increase, and so, the TIM layer will not melt at the operating temperature.

液态金属在电子热控中的应用进展与挑战

液态金属作为当下科学和工业前沿的璀璨明珠,不仅是实际应用中不可或缺的重要组成部分,更是一个充满未知奇迹的探索领域。其独特的物理性质使得它在电子热控方面备受瞩目。文中剖析了热控应用中至关重要的典型液态金属的物理参数和性能,深入挖掘了液态金属在电子热控中的应用场景,介绍了它作为热界面材料、相变储能材料和循环工质的现状和研究进展,并进一步阐述了液态金属在电子热控应用中面临的主要技术挑战,提出了应对这些技术挑战的技术途径,指出了液态金属未来的研究方向。

聚酰亚胺辅助制备高定向石墨烯基全炭泡沫及其在导热聚合物复合材料中的应用

石墨烯及其衍生物具有高纵横比的二维层状结构,在加工过程中通常倾向于水平排列。因此,石墨烯基复合热界面材料虽然具有较高的面内热导率,但其表现出的低面外热导率难以满足实际应用需求。本文通过定向冷冻策略制备了竖直排列的聚酰亚胺/石墨纳米片(PG)导热骨架以提高聚合物复合材料的面外热导率,其中石墨纳米片(GNs)为高导热石墨烯薄膜的粉体边角料。在该过程中,采用水溶性聚酰胺盐溶液直接分散疏水的GNs,热亚胺化后获得的聚酰亚胺在辅助GNs定向排列的同时经石墨化处理转变为人造石墨。同时,GNs的引入提高了PG骨架的有序度和密度,进一步提高了聚二甲基硅氧烷(PDMS)基复合材料的强度和导热性能。结果表明,所制备的PDMS/PG复合材料(PG:21.1%)的面外热导率达14.56 W·m^(−1)·K^(−1),是纯PDMS的81倍。这种简便的聚酰亚胺辅助二维疏水填料定向排列的方法为各向异性热界面材料的规模制备提供了思路,同时实现了石墨烯薄膜边角料的再利用。

Rational design of graphene structures for preparing high-performance thermal interface materials: A mini review

With the explosive development in integration of electronic components and the increasing complexity of packaging systems,semiconductor chips own extremely high operation temperatures given by the horrible heat accumulation attributed to the drastically increasing power density. Therefore, highly efficient heat dissipation with the help of rationally designed thermal interface materials(TIMs) is the key to maintaining the device performance and lifespan. Graphene exhibits an ultrahigh intrinsic thermal conductivity, which has attracted a large amount of academic interest due to its significant potential for developing high-performance TIMs. In this tutorial review, we summarize the recent advances in graphene-based TIMs, especially emphasizing the determinate effects of graphene structure and alignment in enhancing the heat transfer capacity of corresponding samples,with detailed discussion in the superiorities and limitations of various graphene skeletons. In addition, we also provide prospects for the challenges and opportunities in the future development of graphene-based TIMs.