Project description:Amorphous chalcogenide alloys are key materials for data storage and energy scavenging applications due to their large non-linearities in optical and electrical properties as well as low vibrational thermal conductivities. Here, we report on a mechanism to suppress the thermal transport in a representative amorphous chalcogenide system, silicon telluride (SiTe), by nearly an order of magnitude via systematically tailoring the cross-linking network among the atoms. As such, we experimentally demonstrate that in fully dense amorphous SiTe the thermal conductivity can be reduced to as low as 0.10 ± 0.01 W m-1 K-1 for high tellurium content with a density nearly twice that of amorphous silicon. Using ab-initio simulations integrated with lattice dynamics, we attribute the ultralow thermal conductivity of SiTe to the suppressed contribution of extended modes of vibration, namely propagons and diffusons. This leads to a large shift in the mobility edge - a factor of five - towards lower frequency and localization of nearly 42% of the modes. This localization is the result of reductions in coordination number and a transition from over-constrained to under-constrained atomic network.
Project description:In this study, the thermal, chemical and structural stability of 1H,1H,2H,2H-perfluorodecyl acrylate polymers (p-PFDA) synthetized by initiated chemical vapor deposition (iCVD) were investigated. PFDA polymers are known for their interesting crystalline aggregation into a lamellar structure that induces super-hydrophobicity and oleophobicity. Nevertheless, when considering applications which involve chemical, mechanical and thermal stresses, it is important to know the limits under which the crystalline aggregation and the resulting polymer properties are stable. For this, chemical, morphological and structural properties upon multiple heating/cooling cycles were investigated both for linear PFDA polymers and for differently strong cross-linked alterations thereof. Heat treatment leaves the chemical composition of the linear PFDA polymers largely unchanged, while a more ordered crystalline structure with smoother morphology is observed. At the same time, the hydrophobicity and the integrity of the polymer deteriorate upon heating. The integrity and hydrophobicity of cross-linked p-PFDA films was preserved likely because of the lack of internal strain due to the coexistence of both crystalline and amorphous phases. The possibility to finely tune the degree of cross-linking can therefore expand the application portfolio in which PFDA polymers can be utilized.
Project description:The value measured in the amorphous structure with the same chemical composition is often considered as a lower bound for the thermal conductivity of any material: the heat carriers are strongly scattered by disorder, and their lifetimes reach the minimum time scale of thermal vibrations. An appropriate design at the nano-scale, however, may allow one to reduce the thermal conductivity even below the amorphous limit. In the present contribution, using molecular-dynamics simulation and the Green-Kubo formulation, we study systematically the thermal conductivity of layered phononic materials (superlattices), by tuning different parameters that can characterize such structures. We have discovered that the key to reach a lower-than-amorphous thermal conductivity is to block almost completely the propagation of the heat carriers, the superlattice phonons. We demonstrate that a large mass difference in the two intercalated layers, or weakened interactions across the interface between layers result in materials with very low thermal conductivity, below the values of the corresponding amorphous counterparts.
Project description:High thermal conductivity is critical for many applications of polymers (for example, packaging of light-emitting diodes), in which heat must be dissipated efficiently to maintain the functionality and reliability of a system. Whereas uniaxially extended chain morphology has been shown to significantly enhance thermal conductivity in individual polymer chains and fibers, bulk polymers with coiled and entangled chains have low thermal conductivities (0.1 to 0.4 W m-1 K-1). We demonstrate that systematic ionization of a weak anionic polyelectrolyte, polyacrylic acid (PAA), resulting in extended and stiffened polymer chains with superior packing, can significantly enhance its thermal conductivity. Cross-plane thermal conductivity in spin-cast amorphous films steadily grows with PAA degree of ionization, reaching up to ~1.2 W m-1 K-1, which is on par with that of glass and about six times higher than that of most amorphous polymers, suggesting a new unexplored molecular engineering strategy to achieve high thermal conductivities in amorphous bulk polymers.
Project description:Thermal conductivity of two-dimensional (2D) materials is of interest for energy storage, nanoelectronics and optoelectronics. Here, we report that the thermal conductivity of molybdenum disulfide can be modified by electrochemical intercalation. We observe distinct behaviour for thin films with vertically aligned basal planes and natural bulk crystals with basal planes aligned parallel to the surface. The thermal conductivity is measured as a function of the degree of lithiation, using time-domain thermoreflectance. The change of thermal conductivity correlates with the lithiation-induced structural and compositional disorder. We further show that the ratio of the in-plane to through-plane thermal conductivity of bulk crystal is enhanced by the disorder. These results suggest that stacking disorder and mixture of phases is an effective mechanism to modify the anisotropic thermal conductivity of 2D materials.
Project description:The long-term stability of pharmaceutical formulations of poorly-soluble drugs in polymers determines their bioavailability and therapeutic applicability. However, these formulations do not only often tend to crystallize during storage, but also tend to undergo unwanted amorphous-amorphous phase separations (APS). Whereas the crystallization behavior of APIs in polymers has been measured and modeled during the last years, the APS phenomenon is still poorly understood. In this study, the crystallization behavior, APS, and glass-transition temperatures formulations of ibuprofen and felodipine in polymeric PLGA excipients exhibiting different ratios of lactic acid and glycolic acid monomers in the PLGA chain were investigated by means of hot-stage microscopy and DSC. APS and recrystallization was observed in ibuprofen/PLGA formulations, while only recrystallization occurred in felodipine/PLGA formulations. Based on a successful modeling of the crystallization behavior using the Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT), the occurrence of APS was predicted in agreement with experimental findings.
Project description:Electrically insulating polymers are indispensable for electronic and energy applications, but their poor thermal conduction has increasingly become a bottleneck for high-performance devices. Highly drawn low-dimensional polymeric fibers and thin films can exhibit metallic conductivity. Extending this to bulk materials required by real world applications is prohibitive due to the additional interfacial thermal conduction barriers. It is demonstrated that highly aligned ultrahigh molecular weight polyethylene microfibers can be incorporated into a silicone matrix to yield a fully organic bulk polymer composite with a continuous vertical phonon pathway. This leads to a perpendicular thermal conductivity of 38.27 W m-1 K-1 , at par with metals and two orders of magnitude higher than other bulk organic polymers. Taking further advantage of the mechanical flexibility of the microfibers, the processing method offers the freedom to tailor heat transfer pathways in a macroscopic 3D space. The material/process opens up opportunities for efficient thermal management in high-performance devices.
Project description:High-thermal-conductivity polymers are very sought after for applications in various thermal management systems. Although improving crystallinity is a common way for increasing the thermal conductivity (k) of polymers, it has very limited capacity when the crystallinity is already high. In this work, by heat-stretching a highly crystalline microfiber, a significant k enhancement is observed. More interestingly, it coincides with a reduction in crystallinity. The sample is a Spectra S-900 ultrahigh-molecular-weight polyethylene (UHMW-PE) microfiber of 92% crystallinity and high degree of orientation. The optimum stretching condition is 131.5 °C, with a strain rate of 0.0129 s-1 to a low strain ratio (∼6.6) followed by air quenching. The k enhancement is from 21 to 51 W/(m·K), the highest value for UHMW-PE microfibers reported to date. X-ray diffraction study finds that the crystallinity reduces to 83% after stretching, whereas the crystallite size and crystallite orientation are not changed. Cryogenic thermal characterization shows a reduced level of phonon-defect scattering near 30 K. Polarization Raman spectroscopy finds enhanced alignment of amorphous chains, which could be the main reason for the k enhancement. A possible relocation of amorphous phase is also discussed and indirectly supported by a bending test.
Project description:Thermal conductivity is important for almost all applications involving heat transfer. The theory and modeling of crystalline materials is in some sense a solved problem, where one can now calculate their thermal conductivity from first principles using expressions based on the phonon gas model (PGM). However, modeling of amorphous materials still has many open questions, because the PGM itself becomes questionable when one cannot rigorously define the phonon velocities. In this report, we used our recently developed Green-Kubo modal analysis (GKMA) method to study amorphous silicon dioxide (a-SiO2). The predicted thermal conductivities exhibit excellent agreement with experiments and anharmonic effects are included in the thermal conductivity calculation for all the modes in a-SiO2 for the first time. Previously, localized modes (locons) have been thought to have a negligible contribution to thermal conductivity, due to their highly localized nature. However, in a-SiO2 our results indicate that locons contribute more than 10% to the total thermal conductivity from 400?K to 800?K and they are largely responsible for the increase in thermal conductivity of a-SiO2 above room temperature. This is an effect that cannot be explained by previous methods and therefore offers new insight into the nature of phonon transport in amorphous/glassy materials.
Project description:Traditional polymers are both electrically and thermally insulating. The development of electrically conductive polymers has led to novel applications such as flexible displays, solar cells, and wearable biosensors. As in the case of electrically conductive polymers, the development of polymers with high thermal conductivity would open up a range of applications in next-generation electronic, optoelectronic, and energy devices. Current research has so far been limited to engineering polymers either by strong intramolecular interactions, which enable efficient phonon transport along the polymer chains, or by strong intermolecular interactions, which enable efficient phonon transport between the polymer chains. However, it has not been possible until now to engineer both interactions simultaneously. We report the first realization of high thermal conductivity in the thin film of a conjugated polymer, poly(3-hexylthiophene), via bottom-up oxidative chemical vapor deposition (oCVD), taking advantage of both strong C=C covalent bonding along the extended polymer chain and strong ?-? stacking noncovalent interactions between chains. We confirm the presence of both types of interactions by systematic structural characterization, achieving a near-room temperature thermal conductivity of 2.2 W/m·K, which is 10 times higher than that of conventional polymers. With the solvent-free oCVD technique, it is now possible to grow polymer films conformally on a variety of substrates as lightweight, flexible heat conductors that are also electrically insulating and resistant to corrosion.