Teng Zhang

Thermal Transport in Graphene Oxide – From Ballistic Extreme to Amorphous Limit

Graphene oxide is being used in energy, optical, electronic and sensor devices due to its unique properties. However, unlike its counterpart – graphene – the thermal transport properties of graphene oxide remain unknown. In this work, we use large-scale molecular dynamics simulations with reactive potentials to systematically study the role of oxygen adatoms on the thermal transport in graphene oxide. For pristine graphene, highly ballistic thermal transport is observed. As the oxygen coverage increases, the thermal conductivity is significantly reduced. An oxygen coverage of 5% can reduce the graphene thermal conductivity by ~90% and a coverage of 20% lower it to ~8.8u2005W/mK. This value is even lower than the calculated amorphous limit (~11.6u2005W/mK for graphene), which is usually regarded as the minimal possible thermal conductivity of a solid. Analyses show that the large reduction in thermal conductivity is due to the significantly enhanced phonon scattering induced by the oxygen defects which introduce dramatic structural deformations. These results provide important insight to the thermal transport physics in graphene oxide and offer valuable information for the design of graphene oxide-based materials and devices.

Functionalized Graphene Enables Highly Efficient Solar Thermal Steam Generation

The ability to efficiently utilize solar thermal energy to enable liquid-to-vapor phase transition has great technological implications for a wide variety of applications, such as water treatment and chemical fractionation. Here, we demonstrate that functionalizing graphene using hydrophilic groups can greatly enhance the solar thermal steam generation efficiency. Our results show that specially functionalized graphene can improve the overall solar-to-vapor efficiency from 38% to 48% at one sun conditions compared to chemically reduced graphene oxide. Our experiments show that such an improvement is a surface effect mainly attributed to the more hydrophilic feature of functionalized graphene, which influences the water meniscus profile at the vapor-liquid interface due to capillary effect. This will lead to thinner water films close to the three-phase contact line, where the water surface temperature is higher since the resistance of thinner water film is smaller, leading to more efficient evaporation. This strategy of functionalizing graphene to make it more hydrophilic can be potentially integrated with the existing macroscopic heat isolation strategies to further improve the overall solar-to-vapor conversion efficiency.

High-Contrast, Reversible Thermal Conductivity Regulation Utilizing the Phase Transition of Polyethylene Nanofibers

Reversible thermal conductivity regulation at the nanoscale is of great interest to a wide range of applications such as thermal management, phononics, sensors, and energy devices. Through a series of large-scale molecular dynamics simulations, we demonstrate a thermal conductivity regulation utilizing the phase transition of polyethylene nanofibers, enabling a thermal conductivity tuning factor of as high as 12, exceeding all previously reported values. The thermal conductivity change roots from the segmental rotations along the polymer chains, which introduce along-chain morphology disorder that significantly interrupts phonon transport along the molecular chains. This phase transition, which can be regulated by temperature, strain, or their combinations, is found to be fully reversible in the polyethylene nanofibers and can happen at a narrow temperature window. The phase change temperature can be further tuned by engineering the diameters of the nanofibers, making such a thermal conductivity regulation scheme adaptable to different application needs. The findings can stimulate significant research interest in nanoscale heat transfer control.

Molecular Bridge Enables Anomalous Enhancement in Thermal Transport across Hard‐Soft Material Interfaces

Conventional wisdom tells us that interfacial thermal transport is more efficient when the interface adhesion energy is enhanced. In this study, it is demonstrated that molecular bridges consisting of small molecules chemically absorbed on solid surfaces can enhance the thermal transport across hard-soft material interfaces by as much as 7-fold despite a significant decrease in the interface adhesion energy. This work provides an unconventional strategy to improve thermal transport across material interfaces.

Hydrogenation of Penta-Graphene Leads to Unexpected Large Improvement in Thermal Conductivity

Penta-graphene (PG) has been identified as a novel two-dimensional (2D) material with an intrinsic bandgap, which makes it especially promising for electronics applications. In this work, we use first-principles lattice dynamics and iterative solution of the phonon Boltzmann transport equation (BTE) to determine the thermal conductivity of PG and its more stable derivative, hydrogenated penta-graphene (HPG). As a comparison, we also studied the effect of hydrogenation on graphene thermal conductivity. In contrast to hydrogenation of graphene, which leads to a dramatic decrease in thermal conductivity, HPG shows a notable increase in thermal conductivity, which is much higher than that of PG. Considering the necessity of using the same thickness when comparing thermal conductivity values of different 2D materials, hydrogenation leads to a 63% reduction in thermal conductivity for graphene, while it results in a 76% increase for PG. The high thermal conductivity of HPG makes it more thermally conductive than most other semiconducting 2D materials, such as the transition metal chalcogenides. Our detailed analyses show that the primary reason for the counterintuitive hydrogenation-induced thermal conductivity enhancement is the weaker bond anharmonicity in HPG than PG. This leads to weaker phonon scattering after hydrogenation, despite the increase in the phonon scattering phase space. The high thermal conductivity of HPG may inspire intensive research around HPG and other derivatives of PG as potential materials for future nanoelectronic devices. The fundamental physics understood from this study may open up a new strategy to engineer thermal transport properties of other 2D materials by controlling bond anharmonicity via functionalization.

Morphology-influenced thermal conductivity of polyethylene single chains and crystalline fibers

In this paper, the thermal conductivities of polyethylene (PE) single chains and aligned crystalline fibers are calculated using molecular dynamics simulations with the condensed-phase optimized molecular potentials for atomistic simulation studies potential. The segment disorder along the PE chains is found to play an important role in thermal transport in both single PE chains and crystalline PE fibers. In a crystalline PE, thermal conductivity decreases as temperature increases since thermal expansion creates space for chain segment rotation. A critical temperature around 400u2009K is identified where thermal conductivity decreases by about 90%. The results show that chain morphology is critical to the thermal transport in PE structures.

Role of Chain Morphology and Stiffness in Thermal Conductivity of Amorphous Polymers

Designing thermally conductive polymer is of scientific interest and practical importance for applications like thermal interface materials, electronics packing, and plastic heat exchangers. In this work, we study the fundamental relationship between the molecular morphology and thermal conductivity in bulk amorphous polymers. We use polyethylene as a model system and performed systematic parametric study in molecular dynamics simulations. We find that the thermal conductivity is a strong function of the radius of gyration of the molecular chains, which is further correlated to persistence length, an intrinsic property of the molecule that characterizes molecular stiffness. Larger persistence length can lead to more extended chain morphology and thus higher thermal conductivity. Further thermal conductivity decomposition analysis shows that thermal transport through covalent bonds dominates the effective thermal conductivity over other contributions from nonbonded interactions (van der Waals) and translation of molecules disregarding the morphology. As a result, the more extended chains due to larger persistence length provide longer spatial paths for heat to transfer efficiently and thus lead to higher thermal conductivity. In addition, rigid rod-like polymers with very large persistence length tend to spontaneously crystallize and form orientated chains, leading to a thermal conductivity increase by more than 1 order of magnitude. Our results will provide important insights into the design of thermally conductive amorphous polymers.

Giant Thermal Rectification from Polyethylene Nanofiber Thermal Diodes.

The realization of phononic computing is held hostage by the lack of high-performance thermal devices. Here, it is shown through theoretical analysis and molecular dynamics simulations that unprecedented thermal rectification factors (as large as 1.20) can be achieved utilizing the phase-dependent thermal conductivity of polyethylene nanofibers. More importantly, such high thermal rectifications only need very small temperature differences (<20 °C) across the device, which is a significant advantage over other thermal diodes which need temperature biases on the order of the operating temperature. Taking this into consideration, it is shown that the dimensionless temperature-scaled rectification factors of the polymer nanofiber diodes range from 12 to 25-much larger than those of other thermal diodes (<8). The polymer nanofiber thermal diode consists of a crystalline portion whose thermal conductivity is highly phase-sensitive and a cross-linked portion which has a stable phase. Nanoscale size effect can be utilized to tune the phase transition temperature of the crystalline portion, enabling thermal diodes capable of operating at different temperatures. This work will be instrumental to the design of high performance, inexpensive, and easily processible thermal devices, based on which thermal circuits can be built to ultimately enable phononic computing.

Nanostructures Significantly Enhance Thermal Transport across Solid Interfaces

The efficiency of thermal transport across solid interfaces presents large challenges for modern technologies such as thermal management of electronics. In this paper, we report the first demonstration of significant enhancement of thermal transport across solid interfaces by introducing interfacial nanostructures. Analogous to fins that have been used for macroscopic heat transfer enhancement in heat exchangers, the nanopillar arrays patterned at the interface help interfacial thermal transport by the enlarged effective contact area. Such a benefit depends on the geometry of nanopillar arrays (e.g., pillar height and spacing), and a thermal boundary conductance enhancement by as much as ∼88% has been measured using the time-domain thermoreflectance technique. Theoretical analysis combined with low-temperature experiments further indicates that phonons with low frequency are less influenced by the interfacial nanostructures due to their large transmissivity, but the benefit of the nanostructure is fully developed at room temperature where higher frequency phonons dominate interfacial thermal transport. The findings from this work can potentially be generalized to benefit real applications such as the thermal management of electronics.

Chain conformation-dependent thermal conductivity of amorphous polymer blends: the impact of inter- and intra-chain interactions

Polymers with high thermal conductivities are of great interest for both scientific research and industrial applications. In this study, model amorphous polymer blends are studied using molecular dynamics simulations. We have examined the effects of inter- and intra-chain interactions on the molecular-level conformations of the blends, which in turn impact their thermal conductivity. It is found that the thermal conductivity of polymer blends is strongly related to the molecular conformation, especially the spatial extent of the molecular chains indicated by their radius of gyration. Tuning the intra-chain van der Waals (vdW) interaction leads to different molecular structures of the minor component in the binary blend, but the thermal conductivity is not changed. However, increasing the inter-chain vdW interactions between the major and the minor components will increase the thermal conductivity of the blend, which is due to the conformation change in the major component that leads to enhanced thermal transport along the chain backbone through the intra-chain bonding interactions. The fundamental structure-property relationship from this study may provide useful guidance for designing and synthesizing polymer blends with desirable thermal conductivity.