Graphene bimetallic-like cantilevers: probing graphene/substrate interactions

The remarkable mechanical properties of graphene, the thinnest, lightest, and strongest material in existence, are desirable in applications ranging from composite materials to sensors and actuators. Here, we demonstrate that these mechanical properties are strongly affected by the interaction with the substrate onto which graphene is deposited. By measuring the temperature-dependent deflection of graphene/substrate "bimetallic" cantilevers we determine strain, thermal expansion coefficient, and the adhesion force acting on graphene films attached to a substrate. Graphene deposited on silicon nitride (SiN(x)) is under much larger strain, ε(g) ～ 1.5 × 10(-2), compared to graphene on gold (Au), ε(g) < 10(-3). The thermal expansion coefficient α(g) of graphene attached to SiN(x) is found to be negative, in the range from (- 5... - 1) × 10(-6)K(-1) and smaller in magnitude than α(g) of suspended graphene. We also estimate the interfacial shear strength of the graphene/SiN(x) interface to be ～1 GPa at room temperature.     

Negative thermal expansion coefficient of graphene measured by Raman spectroscopy

The thermal expansion coefficient (TEC) of single-layer graphene is estimated with temperature-dependent Raman spectroscopy in the temperature range between 200 and 400 K. It is found to be strongly dependent on temperature but remains negative in the whole temperature range with a room temperature value of (-8.0 ± 0.7) × 10(-6) K(-1). The strain caused by the TEC mismatch between graphene and the substrate plays a crucial role in determining the physical properties of graphene, and hence its effect must be accounted for in the interpretation of experimental data taken at cryogenic or elevated temperatures.     

Micro/nanoscale spatial resolution temperature probing for the interfacial thermal characterization of epitaxial graphene on 4H-SiC

Limited internal phonon coupling and transfer within graphene in the out-of-plane direction significantly affects graphene-substrate interfacial phonon coupling and scattering, and leads to unique interfacial thermal transport phenomena. Through the simultaneous characterization of graphene and SiC Raman peaks, it is possible, for the first time, to distinguish the temperature of a graphene layer and its adjacent 4H-SiC substrate. The thermal probing resolution reaches the nanometer scale with the graphene (≈1.12 nm) and is on the micrometer scale (≈12 μm) within SiC next to the interface. A very high thermal resistance at the interface of 5.30 (-0.46) (+0.46) x 10(-5) Km2 W(-1) is observed by using a Raman frequency method under surface Joule heating. This value is much higher than those from molecular dynamics predictions of 7.01(-1.05) (+1.05) x 10(-1) and 8.47(-0.75) (+0.75) x 10(-10) Km2 w(-1) for surface heat fluxes of 3 × 10(9) and 1 × 10(9) and 1 x 10(10) W m(-2) , respectively. This analysis shows that the measured anomalous thermal contact resistance stems from the thermal expansion mismatch between graphene and SiC under Joule heating. This mismatch leads to interface delamination/separation and significantly enhances local phonon scattering. An independent laser-heating experiment conducted under the same conditions yielded a higher interfacial thermal resistance of 1.01(-0.59) (+1.23) x 10(-4) Km2 W(-1). Furthermore, the peak width method of Raman thermometry is also employed to evaluate the interfacial thermal resistance. The results are 3.52 × 10(-5) and 8.57 × 10(-5) K m2 W(-1) for Joule-heating and laser-heating experiments, respectively, confirming the anomalous thermal resistance between graphene and SiC. The difference in the results from the frequency and peak-width methods is caused by the thermal stress generated in the heating processes.     

绿-黄可逆电热致变色织物的制备及其性能

石墨烯因其优异的导电性、优越的柔韧性和环境稳定性, 在可穿戴电子纺织品领域发挥了重要作用。本工作通过丝网印刷技术分别将自制的石墨烯浆料和复合热致变色油墨印在聚酯织物的正反面, 构筑了一种石墨烯基绿-黄可逆电热致变色织物。采用SEM、XRD以及FTIR等分析了织物的结构性质和变色原理, 采用红外热成像仪及全色差色度仪研究了织物的热学以及变色性能。结果表明：石墨烯电热致变色织物厚度约为250 μm, 在12 V电压下逐渐加热超过45 ℃, 焦耳热主要通过热传导至变色层, 结晶紫内酯的闭开环实现绿-黄可逆变色, 其变色响应时间约为15 s, 褪色响应时间约为27 s。石墨烯电热致变色织物经历30°~180°的弯曲角度后, 电压-电流曲线保持稳定。经200次加热/冷却循环后, 性能未发生明显衰退。本研究成功制备了颜色在绿-黄之间变化、响应迅速、循环性能良好的可逆电热致变色织物：石墨烯膜‖聚酯织物‖热致变色膜, 在军事伪装和可穿戴显示领域有一定的应用前景。     

Research of thermal response simulation and mold structure optimization for rapid heat cycle molding processes, respectively, with steam heating and electric heating

The dynamic mold temperature control system is the key of rapid heat cycle molding (RHCM) technology because it significantly affects the stability of the process, productivity and the quality of the final polymer part. For this reason, the approaches and techniques for dynamic mold temperature control were discussed in this study and two different dynamic mold temperature control methods, respectively, with steam heating and electric heating were found to be very feasible in mass production. The methods and principles of mold design for the two RHCM technologies were also discussed and then several different kinds of mold structures were designed. By constructing the corresponding thermal response analytical models for these RHCM molds, the temperature responses of the molding systems in the heating and cooling process of RHCM were simulated and studied. The effects of the mold design parameters such as the insulation layer between mold plate and mold inert, and mold material, on thermal response efficiency and temperature uniformity of the two RHCM processes were analyzed based on the simulation results. The results show that the insulation layer can increase the upper limit temperature of RHCM with steam heating and improve the heating speed of RHCM with electric heating. It can also greatly decrease the energy consumption of the two RHCM processes. The heating efficiency of RHCM with steam heating can be effectively improved by increasing the thermal conductivity of the cavity/core material, while the situation is diametrically opposite for RHCM with electric heating. Therefore, we acquired an optimized mold design principle and method for RHCM with steam heating and electric heating, respectively. Finally, a new electric heating mold with a cooling plate was proposed to enhance the cooling efficiency. The thermal response of this new electric heating mold was also simulated. The simulation results show that the cooling plate can significantly improve the cooling and heating efficiency.     

石墨烯/聚砜酰胺复合薄膜的结构与性能

采用旋涂法将石墨烯和聚砜酰胺（PSA）制成不同石墨烯质量分数的石墨烯/PSA复合薄膜,利用光学显微镜、傅里叶变换红外光谱、表面电阻测试、热失重分析和紫外光谱表征和分析石墨烯/PSA复合薄膜的化学组成、大分子结构、热性能、导电性能、力学性能和抗紫外性能。结果表明:少量的石墨烯可均匀分散于PSA基体中,其加入基本没有改变PSA的化学结构;石墨烯二维纳米材料可作为异相成核剂,有助于提高复合薄膜的结晶度,其加入使复合薄膜的力学性能和热性能也有所提高;当石墨烯质量分数为0.1%时,石墨烯/PSA复合薄膜的表面比电阻由纯PSA薄膜的3.10×1012 Ω迅速降至1.40×106 Ω,随着石墨烯质量分数的增大,石墨烯/PSA复合薄膜的导电性能随之提高。石墨烯对加强复合薄膜对紫外光的吸收和散射、提高其抗紫外线性能有重要作用。      

Graphene-multilayer graphene nanocomposites as highly efficient thermal interface materials

We found that the optimized mixture of graphene and multilayer graphene, produced by the high-yield inexpensive liquid-phase-exfoliation technique, can lead to an extremely strong enhancement of the cross-plane thermal conductivity K of the composite. The "laser flash" measurements revealed a record-high enhancement of K by 2300% in the graphene-based polymer at the filler loading fraction f = 10 vol %. It was determined that the relatively high concentration of the single-layer and bilayer graphene flakes (~10-15%) present simultaneously with the thicker multilayers of large lateral size (~1 μm) were essential for the observed unusual K enhancement. The thermal conductivity of the commercial thermal grease was increased from an initial value of ~5.8 W/mK to K = 14 W/mK at the small loading f = 2%, which preserved all mechanical properties of the hybrid. Our modeling results suggest that graphene-multilayer graphene nanocomposite used as the thermal interface material outperforms those with carbon nanotubes or metal nanoparticles owing to graphene's aspect ratio and lower Kapitza resistance at the graphene-matrix interface.     

Single-step formation of a graphene-metal hybrid transparent and electrically conductive film

We report here a rapid (10 s of heating) graphene growth method that can be carried out on any desired substrate, including an insulator, thus negating the need for the transfer from the metal substrate. This technique is based on metal-induced crystallization of amorphous carbon (a-C) to graphene, and involves an ultra-thin metal layer that is less than 10 nm in thickness. Rapid annealing of a bilayer of a-C and metal deposited on the surface leads to the formation of graphene film, and to subsequent breaking-up of the thin metal layer underneath the film, thus resulting in the formation of a graphene–metal hybrid film which is both transparent and electrically conducting. Based on Raman studies, we have also systematically compared ultra-thin metal-induced crystallization behavior with a case of conventional thick metal. Based on the present investigation, it was observed that the dominant growth mechanism in ultra-thin metal-induced crystallization is nucleation controlled.     

Enhanced Peltier Effect in Wrinkled Graphene Constriction by Nano‐Bubble Engineering

Inspired by the promising applications in thermopower generation from waste heat and active on‐chip cooling, the thermoelectric and electrothermal properties of graphene have been extensively pursued by seeking ingeniously designed structures with thermoelectric conversion capability. The graphene wrinkle is a ubiquitous structure formed inevitably during the synthesis of large‐scale graphene films but the corresponding properties for thermoelectric and electrothermal applications are rarely investigated. Here, the electrothermal Peltier effect from the graphene wrinkle fabricated on a germanium substrate is reported. Peltier cooling and heating across the wrinkle are visualized unambiguously with polarities consistent with p‐type doping and in accordance with the wrinkle spatial distribution. By direct patterning of the nano‐bubble structure, the current density across the wrinkle can be boosted by current crowding to enhance the Peltier effect. The observed Peltier effect can be attributed to the nonequilibrium charge transport by interlayer tunneling across the van der Waals barrier of the graphene wrinkle. The graphene wrinkle in combination with nano‐bubble engineering constitutes an innovative and agile platform to design graphene and other more general two‐dimensional (2D) thermoelectrics and opens the possibility for realizing active on‐chip cooling for 2D nanoelectronics with van der Waals junctions.     

Enhancement of Heat Dissipation in Ultraviolet Light‐Emitting Diodes by a Vertically Oriented Graphene Nanowall Buffer Layer

For III‐nitride‐based devices, such as high‐brightness light‐emitting diodes (LEDs), the poor heat dissipation of the sapphire substrate is deleterious to the energy efficiency and restricts many of their applications. Herein, the role of vertically oriented graphene (VG) nanowalls as a buffer layer for improving the heat dissipation in AlN films on sapphire substrates is studied. It is found that VG nanowalls can effectively enhance the heat dissipation between an AlN film and a sapphire substrate in the longitudinal direction because of their unique vertical structure and good thermal conductivity. Thus, an LED fabricated on a VG‐sapphire substrate shows a 37% improved light output power under a high injection current (350 mA) with an effective 3.8% temperature reduction. Moreover, the introduction of VG nanowalls does not degrade the quality of the AlN film, but instead promotes AlN nucleation and significantly reduces the epilayer strain that is generated during the cooling process. These findings suggest that the VG nanowalls can be a good buffer layer candidate in III‐nitride semiconductor devices, especially for improving the heat dissipation in high‐brightness LEDs.     

Ultrathin,Washable, and Large‐Area Graphene Papers for Personal Thermal Management

Freestanding, flexible/foldable, and wearable bifuctional ultrathin graphene paper for heating and cooling is fabricated as an active material in personal thermal management (PTM). The promising electrical conductivity grants the superior Joule heating for extra warmth of 42 °C using a low supply voltage around 3.2 V. Besides, based on its high out‐of‐plane thermal conductivity, the graphene paper provides passive cooling via thermal transmission from the human body to the environment within 7 s. The cooling effect of graphene paper is superior compared with that of the normal cotton fiber, and this advantage will become more prominent with the increased thickness difference. The present bifunctional graphene paper possesses high durability against bending cycles over 500 times and wash time over 1500 min, suggesting its great potential in wearable PTM.     

Synthesis of large area, homogeneous, single layer graphene films by annealing amorphous carbon on Co and Ni

The synthesis of large area, homogenous, single layer graphene on cobalt (Co) and nickel (Ni) is reported. The process involves vacuum annealing of sputtered amorphous carbon (a-C) deposited on Co/sapphire or Ni/sapphire substrates. The improved crystallinity of the metal film, assisted by the sapphire substrate, proves to be the key to the quality of as-grown graphene film. The crystallinity of the Co and Ni metal films was improved by sputtering the metal at elevated temperature as was verified by X-ray diffraction (XRD). After sputtering of a-C and annealing, large area, single layer graphene that occupies almost the entire area of the substrate was produced. With this method, 100 mm²-area single layer graphene can be synthesized and is limited only by the substrate and vacuum chamber size. The homogeneity of the graphene film is not dependent on the cooling rate, in contrast to syntheses using polycrystalline metal films and conventional chemical vapor deposition (CVD) growth. Our facile method of producing single layer graphene on Co and Ni metal films should lead to large scale graphene-based applications.     

基于激光选区熔化成形Ni-Cu合金模板的Ni-Cu-石墨烯复合材料的制备

采用优化的SLM成形参数,用激光选区熔化(SLM)增材制造技术制备了三维Ni-Cu合金.使用三维Ni-Cu合金基底材料用化学气相沉积法(CVD)制备Ni-Cu合金/石墨烯复合材料,研究了 CVD法生长反应温度对石墨烯结构的影响并分析其原因.结果表明,石墨烯层的厚度随着反应温度的提高而减小.与未生长石墨烯的样品相比,在1...     

Probing mechanical properties of graphene with Raman spectroscopy

The use of Raman scattering techniques to study the mechanical properties of graphene films is reviewed here. The determination of Grüneisen parameters of suspended graphene sheets under uni- and bi-axial strain is discussed, and the values are compared to theoretical predictions. The effects of the graphene−substrate interaction on strain and to the temperature evolution of the graphene Raman spectra are discussed. Finally, the relation between mechanical and thermal properties is presented along with the characterization of thermal properties of graphene with Raman spectroscopy.     

Facile preparation of graphene nanoribbon filled silicone rubber nanocomposite with improved thermal and mechanical properties

In the present study, graphene nanoribbon was prepared through unzipping the multi walled carbon nanotubes, and its reinforcing effect as a filler to the silicone rubber was further investigated. The results showed that carbon nanotubes could be unzipped to graphene nanoribbon using strong oxidants like potassium permanganate and sulfuric acid. The prepared graphene nanoribbon could homogeneously disperse within silicone rubber matrix using a simple solution mixing approach. It was also found from the thermogravimetric analysis curves that the thermal stability of the graphene nanoribbon filled silicone rubber nanocomposites improved compared to the pristine silicone rubber. Besides, with the incorporation of the nanofiller, the mechanical properties of the resulting nanocomposites were significantly enhanced, in which both the tensile stress and Young’s modulus increased by 67% and 93% respectively when the mass content of the graphene nanoribbon was 2.0 wt%. Thus it could be expected that graphene nanoribbon had large potentials to be applied as the reinforcing filler to fabricate polymers with increased the thermal and mechanical properties.     

石墨烯纳米流体研究进展

润滑与冷却是当前工业领域两个重要的议题。前者与机械装置、零部件的使用可靠性和寿命直接相关,对减少摩擦产生的能耗具有重大意义,而后者对于高功率密度器件的热管理至关重要。二者的结合在航空航天、汽车机械等领域广泛存在,而纳米流体是一种很好的承载二者的工作介质。本文针对石墨烯纳米流体这一热点,综述了石墨烯纳米流体的分散理论基础与方法,对影响石墨烯纳米流体悬浮稳定性因素进行了调研,归纳总结了纳米流体的导热机理、影响因素以及石墨烯纳米流体进展,分析了纳米流体未实现大面积应用的主要原因,同时对石墨烯作为添加剂应用于润滑领域的进展进行了评述。最终提出石墨烯纳米流体协同增强换热与减磨润滑的应用设计。在航天器等应用领域中,由于对石墨烯纳米流体的力热耦合综合性能缺乏广泛研究,以及航天器稳定性和长期运行可靠性等问题,未来的研究应以航天传热工质为基础,进行纳米粒子针对性设计,通过系统开展基于空间环境动态流动换热性能与回路寿命的研究,为未来实现纳米流体的航天器应用奠定理论基础和提供技术支撑。     

Intercalation of iridium atoms into a graphene layer on a metal

The intercalation of iridium atoms into a graphene (two-dimensional graphite) layer on a metal substrate (iridium (111) crystal face) has been studied. It is established that a thin film of iridium deposited at room temperature onto the graphene surface in a vacuum is completely destroyed on heating to 1000–1200 K and iridium atoms pass to an intercalated state between the graphene layer and the substrate. Vacuum deposition of iridium directly onto a heated sample of graphene/Ir(111) at 1000–1500 K leads to the accumulation of Ir atoms only in the intercalated state, while the outer surface of graphene remains free of the adsorbate.     

三维网状石墨烯/环氧树脂热界面复合材料的制备和热性能

三维网状石墨烯/环氧树脂热界面复合材料由于具有良好的热导性能和力学性能,而被广泛应用于微电子器件领域。但是通过化学剥离-还原法制备石墨烯,在填加石墨烯质量分数相同的条件下,石墨烯/环氧树脂热界面复合材料的热导率差别仍然很大。研究发现这主要是由于石墨烯表面官能团含量不同所导致的,因此很难建立统一的标准评估石墨烯作为导热填料的作用效果。为了避免表面官能团对石墨烯/环氧树脂复合物热导率的影响,本研究小组采用化学气相沉积法制备的三维网状石墨烯作为导热填料,对环氧树脂进行修饰,制备了一系列石墨烯/环氧树脂材料。通过研究三维网状石墨烯含量对石墨烯/环氧树脂材料热导率、力学性能及热导率在高温条件下稳定性的影响,有助于完善石墨烯修饰的环氧树脂热界面复合材料的研究,并建立石墨烯作为导热填料的评价体系。     

氧化石墨烯的制备及其对NH3的敏感特性研究

石墨烯独特的原子结构赋予其电学、热学、力学等方面的优异性能,在诸多领域具有广泛的应用。氧化石墨烯不仅具有石墨烯结构特点,而且具有大量的含氧官能团,增强了对气体的吸附能力,更适合应用于气敏传感器。通过改进的Hummer方法制备了片状多层氧化石墨烯,并对不同浓度的NH3进行敏感特性测试。结果表明氧化石墨烯对NH3具有良好的响应,在(1.5～3.5)×10-4范围内呈线性关系。     

PLASMA SPRAYED ZrO2 THICK THERMAL BARRIER COATINGS

ZrO₂ thermal barrier coatings have been plasma sprayed onto steel substrates with a FeCrAlY bond layer. During spraying the conditions have been varied by cooling the back side of the substrate in ice-water or heating it on a hot plate, and simultaneously cooling the sprayed surface with air at various pressures. The residual strain distributions have been measured in the as-sprayed couples using the incremental blind-hole method. The measurements show that residual strains can be controlled through temperature manipulation, and the method can be used to determine the optimum spraying conditions. The microstructure has been observed in a transmission electron microscope, and the effect of microstructural features on the microstrains are briefly discussed.