Determining Thermal Conductivity of Small Molecule Amorphous Drugs with Modulated Differential Scanning Calorimetry and Vacuum Molding Sample Preparation.
Ontology highlight
ABSTRACT:
SUBMITTER: Karl M
PROVIDER: S-EPMC6955963 | biostudies-literature |
REPOSITORIES: biostudies-literature
Similar Datasets
Project description:Recently, there has been a noticeable increase in the applications of composite mixtures containing molten salt and solid oxide for thermal energy conversion and storage systems. This highlights that thermal conductivity of the composites are central for the purpose of designing and devising processes. Measuring the thermal conductivity of molten samples at elevated temperatures remains challenging. In this study, the possibility to use heat flux differential scanning calorimetry (DSC) to measure the thermal conductivity of molten samples at elevated temperatures is reported for the first time. The thermal conductivity of composite mixtures containing eutectic (Li,Na)2CO3 with and without selected solid oxides at ~675 °C was determined by using the proposed DSC approach. This mixture is a candidate for high temperature waste heat conversion to electric energy. In the DSC measurement program, steps with repeated thermal cycles between 410 and 515 °C were included to limit the effect of the interface thermal contact resistance. The determined values 0.826 ± 0.001, and 0.077 ± 0.004 W m-1K-1 for the carbonate mixtures with and without solid MgO were found to match the reliable analysis at similar conditions.
| S-EPMC6539058 | biostudies-literature
Project description:The objective of this study was to characterise amorphous indapamide (IND) subjected to the physical ageing process by differential scanning calorimetry (DSC). The amorphous indapamide was annealed at different temperatures below the glass transition, i.e., 35, 40, 45, 65, 75 and 85 °C for different lengths of time, from 30 min up to a maximum of 32 h. DSC was used to characterise both the crystalline and the freshly prepared glass and to monitor the extent of relaxation at temperatures below the glass transition (Tg). No ageing occurred at 35, 40 and 45 °C at the measured lengths of times. Molecular relaxation time constants (τKWW) for samples aged at 65, 75 and 85 °C were determined by the Kohlrausch-Williams-Watts (KWW) equation. The fragility parameter m (a measure of the stability below the glass transition) was determined from the Tg dependence from the cooling and heating rates, and IND was found to be relatively stable ("moderately fragile") in the amorphous state. Temperature-modulated DSC was used to separate reversing and nonreversing processes for unaged amorphous IND. The enthalpy relaxation peak was clearly observed as a part of the nonreversing signal. Heat capacities data for unaged and physically aged IND were fitted to Cp baselines of solid and liquid states of IND, were integrated and enthalpy was presented as a function of temperature.
| S-EPMC7558952 | biostudies-literature
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.
| S-EPMC4571656 | biostudies-literature
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.
| S-EPMC5533546 | biostudies-other
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.
| S-EPMC6641735 | biostudies-literature
Project description:Thermal transport properties of amorphous polymers depend significantly on the chain morphology, and boundary chain folding is a common phenomenon in bulk or lamellar polymer materials. In this work, by using molecular dynamics simulations, we study thermal conductivity of lamellar amorphous polyethylene (LAPE) with varying chain length (L 0). For a short L 0 without boundary chain folding, thermal conductivity of LAPE is homogeneous along the chain length direction. In contrast, boundary chain folding takes place for large L 0, and the local thermal conductivity at the boundary is notably lower than that of the central region, indicating inhomogeneous thermal transport in LAPE. By analysing the chain morphology, we reveal that the boundary chain folding causes the reduction of both the orientation order parameter along the heat flow direction and the radius of gyration, leading to the reduced local thermal conductivity at the boundary. Further vibrational spectrum analysis reveals that the boundary chain folding shifts the vibrational spectrum to the lower frequency, and suppresses the transmission coefficient for both C-C vibration and C-H vibration. Our study suggests that the boundary chain folding is an important factor for polymers to achieve desirable thermal conductivity for plastic heat exchangers and electronic packaging applications.
| S-EPMC9073277 | biostudies-literature
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.
| S-EPMC5073306 | biostudies-literature
Project description:The thermal properties of the polymer, together with mechanical stability, have been one of the key engineering factors to be considered for various applications. Here, we engineered the thermal conductivity of the amorphous poly(acrylic acid) (PAA) polymer by vapor-phase infiltration (VPI), which has usually occurred during the atomic layer deposition process. We observed that the VPI causes metal infiltration (e.g., Al and Zn) into the amorphous PAA polymer, which noticeably increases the thermal conductivity of the PAA polymer. From spectroscopy analysis and density functional theory simulations, we found that the carboxyl groups (-COOH) in PAA are notably modified and the bonding states of carbon and oxygen are significantly altered by the infiltrated metal. The newly formed Al-mediated bonds likely provide continuous phonon propagation pathways, thereby enhancing the thermal conductance. We believe that VPI could be a simple and useful way to engineer the thermal properties of various polymeric materials.
| S-EPMC8567350 | biostudies-literature
Project description:Flufenamic acid (FFA) is a highly polymorphic drug molecule with nine crystal structures reported in the Cambridge Structural Database. This study explores the use of synchrotron X-ray powder diffraction combined with differential scanning calorimetry to study crystallization and polymorphic phase transitions upon heating FFA-polymer amorphous solid dispersions (ASDs). Ethyl cellulose (EC, 4 cp) and hydroxypropylmethylcellulose (HPMC) grades with different viscosities and substitution patterns were used to prepare dispersions with FFA at 5:1, 2:1, 1:1, and 1:5 w/w drug/polymer ratios by quench cooling. We employed a 6 cp HPMC 2910 material and two HPMC 2208 samples at 4000 and 100 000 cp. Hyphenated X-ray diffraction (XRD)-differential scanning calorimetry (DSC) studies show that the 6 and 100 000 cp HPMCs and 4 cp EC polymers can stabilize FFA form IV by inhibiting the transition to form I during heating. It appears that the polymers stabilize FFA in both amorphous and metastable forms via a combination of intermolecular interactions and viscosity effects. Increasing the polymer content of the ASD also inhibits polymorphic transitions, with drug/polymer ratios of 1:5 w/w resulting in FFA remaining amorphous during heating. The comparison of FFA ASDs prepared with different samples of HPMCs and ECs suggests that the chemical substitution of the polymer (HPMC 2208 has 19-24% methoxy groups and 4-12% hydroxypropyl groups, while HPMC 2910 has 28-30% methoxy groups and 7-12% hydroxypropyl groups) plays a more significant role in directing polymorphic transitions than the viscosity. A previously unreported polymorph of FFA was also noted during heating but its structure could not be determined.
| S-EPMC9097533 | biostudies-literature
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.
| S-EPMC8121845 | biostudies-literature