Glass Transition Temperatures and Thermal Conductivities of Polybutadiene Crosslinked with Randomly Distributed Sulfur Chains Using Molecular Dynamic Simulation.

The thermal conductivities and glass transition temperatures of polybutadiene crosslinked with randomly distributed sulfur chains having different lengths from mono-sulfur (S1) to octa-sulfur (S8) were investigated. The thermal conductivities of the related models as a function of the heat flux autocorrelation function, applying an equilibrium molecular dynamic (EMD) simulation and the Green-Kubo method, were studied for a wide range of temperatures. The influence of the length of sulfur chains, degree of crosslinking, and molar mass of the crosslinker on the glass transition temperature and final values of thermal conductivities were studied. First, the degree of crosslinking is considered constant for the eight simulation models, from mono-sulfur (S1) to octa-sulfur (S8), while the molar mass of the sulfur is increases. The results show that the thermal conductivities of the crosslinked structure decrease with increasing temperature for each model. Moreover, by increasing the lengths of the sulfur chains and the molar weight of the crosslinker, thermal conductivity increases at a constant temperature. The MD simulation demonstrates that the glass transition temperature and density of the crosslinked structure enhance as the length of the sulfur chains and molar mass of the sulfur increase. Second, the molar weight of sulfur is considered constant in these eight models; therefore, the degree of crosslinking decreases with the increase in the lengths of the sulfur chains. The results show that the thermal conductivities of the crosslinked structure decrease with the increase in the temperature for each model. Moreover, by increasing the lengths of sulfur chains and thus decreasing the degree of crosslinking, the trend in changes in thermal conductivities are almost the same for all of these models, so thermal conductivity is constant for a specific temperature. In addition, the glass transition temperature and density of the crosslinked structure decrease.

Thermal Conductivities of Uniform and Random Sulfur Crosslinking in Polybutadiene by Molecular Dynamic Simulation.

Thermal conductivities of polybutadiene crosslinked with sulfur as a function of the heat flux autocorrelation function by using an equilibrium molecular dynamic (EMD) simulation were investigated. The Green-Kubo method was used to calculate thermal conductivities. All simulations were performed by applying the LAMMPS software (version 3 Mar 2020) package. The united-atom force field (OPLS-UA) from the Moltemplate software (version 2.20.3) was applied in the simulations. The influence of uniform and random distributions of sulfur in polybutadiene on the final value of thermal conductivities was studied by polymeric model structures with similar and variable degrees of crosslinking. The results showed that for identical degrees of crosslinking, the distribution of crosslinkers in the polymeric model structures significantly influenced the final value of thermal conductivity. Moreover, the influence of the crosslinking degree on the final value of thermal conductivity was studied by considering polymeric model structures with different degrees of crosslinking. The results demonstrate that by having a random distribution of sulfur, the thermal conductivity will be enhanced. However, by increasing the degree of crosslinking to the higher percentage in random crosslinked model structures, the value of thermal conductivity drops significantly due to possible higher crystallization of the model structures, which decrease the degree of freedom for phonon contributions.

New preparation methods for coated heat exchangers in adsorption refrigeration and heat pumps applications.

Adsorption refrigeration systems and heat pumps still possess a relatively reduced market share as compared to the traditional compression systems. Despite having the great advantage of being powered by cheap heat (instead of expensive electric work), the implementation of systems based on adsorption principles remains limited to few specific applications. The main drawback that needs to be solved is their reduced specific power due to the low thermal conductivity and low stability of the adsorbents. The current state of the art of commercial adsorption cooling systems rely on adsorbers based on coated finned heat exchangers to optimize the cooling power. It is a well known result, that the reduction of the thickness of the coating derives in a reduction of the mass transport impedance, and that the increment of the ratio surface to volume of conductive structures increases the power without reducing the efficiency. The metallic fibres used in this work can offer a ratio of specific surface in the range of 2500-50,000 m2/m3.Three methods of preparing very thin but stable salt-hydrate coatings on metallic surfaces, including metallic fibres, for the production of coated heat exchangers with high specific power, are presented for the first time. A surface treatment based on aluminium anodizing was chosen to create a stronger bond between coat and substrate. The microscopic structure of the resulting surface was analysed by Scan Electron Microscopy. To verify the presence of the desired species Attenuated Total Reflectance-Fourier Transformed Infrared and Energy dispersive X-ray spectroscopy were employed in the analysis. Their capacity to form hydrates was verified via simultaneous Thermogravimetric Analysis (TGA)/Differential Thermogravimetry (DTG). Over a mass difference of 0.07 g(water)/g(composite) was detected in the coating of MgSO4, which showed signs of dehydration at temperatures around 60 °C, and repeatability after rehydration. Also positive results were obtained with SrCl2 and ZnSO4 with mass differences around 0.02 g/g below 100 °C. Hydroxyethyl Cellulose was chosen as additive to increase the stability and adherence of the coatings. The adsorption properties of the product were evaluated with simultaneous TGA-DTG, while their adherence was characterized by means of a procedure based on the test described in ISO2409. Coatings of CaCl2 displayed a much improved consistency and adherence, while retaining its adsorption capacity, showing mass differences of around 0.1 g/g at temperatures below 100 °C. Also MgSO4 retains the capacity of forming hydrates, showing a mass difference of more than 0.04 g/g below 100 °C. Finally, coated metallic fibres were investigated. Results show that the effective heat conductivity of a fibre structure coated with Al2(SO4)3 can be up to 4.7 times higher as compared to a block of pure Al2(SO4)3 . The coverage of the pursued coatings was visually investigated and the internal structure was evaluated by microscopic imaging of cross-sections. Coatings of around 50 µm of Al2(SO4)3 were generated, but in general the process requires optimization to achieve a more uniform distribution.

Prediction of Thermal Conductivities of Rubbers by MD Simulations-New Insights.

In this article, two main approaches to the prediction of thermal conductivities by molecular dynamics (MD) simulations are discussed, namely non-equilibrium molecular dynamics simulations (NEMD) and the application of the Green-Kubo formula, i.e., EMD. NEMD methods are more affected by size effects than EMD methods. The thermal conductivities of silicone rubbers in special were found as a function of the degree of crosslinking. Moreover, the thermal conductivities of thermoplastic polyurethane as function of the mass fraction of soft segments were obtained by those MD simulations. All results are in good agreement with data from the experimental literature. After the analysis of normalized heat flux autocorrelation functions, it has been revealed that heat in the polymers is mainly transferred by low-frequency phonons. Simulation details as well as advantages and disadvantages of the single methods are discussed in the article.

Thermo-Electro-Mechanical Simulation of Electro-Active Composites.

In this contribution, a computational thermo-electro-mechanical framework is considered, to simulate coupling between the mechanical, electrical and thermal fields, in nonhomogeneous electro-active materials. A thermo-electro-mechanical material model and a mixed Q1P0 finite element framework are described and used for the simulations. Finite element simulations of the response of heterogeneous structures consisting of a soft matrix and a stiff incluison are considered. The behavior of the composite material is studied for varying initial temperatures, different volume fractions and various aspect ratios of the inclusion. For some of the examples, the response of the structure beyond a limit point of electro-mechanical instability is traced. Regarding the soft matrix of the composite, thermal properties of silicone rubber at normal conditions have been obtained by molecular dynamics (MD) simulations. The material parameters obtained by MD simulations are used within the finite element simulations.

Thermal Conductivity of Polybutadiene Rubber from Molecular Dynamics Simulations and Measurements by the Heat Flow Meter Method.

Thermal conductivities of polybutadiene rubbers crosslinked by 2.4 and 2.8 phr of sulfur have been found to be functions of temperature via molecular dynamics (MD) simulations using the Green-Kubo method. From an analysis of the heat flux autocorrelation functions, it has been revealed that the dominant means of heat transport in rubbers is governed by deformations of polymeric chains. Thermal conductivities of rubber samples vulcanized by 2.4 and 2.8 phr of sulfur have been measured by the heat flow meter method between 0 ∘C and 60 ∘C at atmospheric pressure. The temperature dependencies of the thermal conductivities of rubbers and their glass transition temperatures derived from MD simulations are in good agreement with the literature and experimental data. Details are discussed in the paper.

Thermal Conductivities of Crosslinked Polyisoprene and Polybutadiene from Molecular Dynamics Simulations.

For the first time, the thermal conductivities of vulcanized polybutadiene and polyisoprene have been investigated according to their degree of crosslinking. The C-C and C-S-S-C crosslink bridges, which can be obtained via vulcanization processes using peroxides and sulfur, respectively, are considered. The temperature dependence of the thermal conductivity of soft rubber derived from molecular dynamics (MD) simulations is in very good agreement with the experimental results. The contributions of bonded and non-bonded interactions in the MD simulations and their influence on the thermal conductivities of polyisoprene and polybutadiene are presented. The details are discussed in this paper.

Estimating a Stoichiometric Solid's Gibbs Free Energy Model by Means of a Constrained Evolutionary Strategy.

Modeling of thermodynamic properties, like heat capacities for stoichiometric solids, includes the treatment of different sources of data which may be inconsistent and diverse. In this work, an approach based on the covariance matrix adaptation evolution strategy (CMA-ES) is proposed and described as an alternative method for data treatment and fitting with the support of data source dependent weight factors and physical constraints. This is applied to a Gibb's Free Energy stoichiometric model for different magnesium sulfate hydrates by means of the NASA9 polynomial. Its behavior is proved by: (i) The comparison of the model to other standard methods for different heat capacity data, yielding a more plausible curve at high temperature ranges; (ii) the comparison of the fitted heat capacity values of MgSO4·7H2O against DSC measurements, resulting in a mean relative error of a 0.7% and a normalized root mean square deviation of 1.1%; and (iii) comparing the Van't Hoff and proposed Stoichiometric model vapor-solid equilibrium curves to different literature data for MgSO4·7H2O, MgSO4·6H2O, and MgSO4·1H2O, resulting in similar equilibrium values, especially for MgSO4·7H2O and MgSO4·6H2O. The results show good agreement with the employed data and confirm this method as a viable alternative for fitting complex physically constrained data sets, while being a potential approach for automatic data fitting of substance data.

New Experimental Installation to Determine Adsorptive Properties of Magnesium Sulphate.

Adsorption processes are of great interest in catalysis, material separation, and thermal management. In recent decades, adsorbents have been further investigated because of their applications in adsorption refrigeration, heat pumps, and thermal energy storage. Thus, there is an increasing need to determine the macroscopic properties of the adsorbent, specifically their adsorption/desorption capacity and speed, because these two factors determine the power and size of the corresponding adsorber. Many designs have been proposed, but there is still not a generally adopted technology for the analysis of those properties. In this paper, a novel instrument is described, which is capable of determining the macrokinetic properties of an adsorbent composite, with better control and higher accuracy than gravimetric, volumetric, or barometric installations, and lower price and complexity than spectroscopic installations. The design of the installation is detailed, highlighting the main challenges and critical factors. The two working modes of the installation are described, and one example is provided and analyzed for each of them.

Thermal Conductivity of Polyisoprene and Polybutadiene from Molecular Dynamics Simulations and Transient Measurements.

The thermal conductivities of untreated polyisoprene and polybutadiene were calculated by molecular dynamics (MD) simulations using a Green-Kubo approach between -10 °C and 50 °C at atmospheric pressure. For comparison, the thermal conductivities of untreated polyisoprene with a molecular weight of 54,000 g/mol and untreated polybutadiene with a molecular weight of 45,000 g/mol were measured by the transient hot wire method in similar conditions. The simulation results of both polymers are in good agreement with the experimental data. We observed that the MD simulations slightly overestimate the thermal conductivity due to the chosen force field description. Details are discussed in the paper.

A Benchmark Open-Source Implementation of COSMO-SAC.

The COSMO-SAC modeling approach has found wide application in science as well as in a range of industries due to its good predictive capabilities. While other models for liquid phases, as for example UNIFAC, are in general more accurate than COSMO-SAC, these models typically contain many adjustable parameters and can be limited in their applicability. In contrast, the COSMO-SAC model only contains a few universal parameters and subdivides the molecular surface area into charged segments that interact with each other. In recent years, additional improvements to the construction of the sigma profiles and evaluation of activity coefficients have been made. In this work, we present a comprehensive description of how to postprocess the results of a COSMO calculation through to the evaluation of thermodynamic properties. We also assembled a large database of COSMO files, consisting of 2261 compounds, freely available to academic and noncommercial users. We especially focus on the documentation of the implementation and provide the optimized source code in C++, wrappers in Python, and sample sigma profiles calculated from each approach, as well as tests and validation results. The misunderstandings in the literature relating to COSMO-SAC are described and corrected. The computational efficiency of the implementation is demonstrated.

Numerical simulation of an atmospheric pressure RF-driven plasma needle and heat transfer to adjacent human skin using COMSOL.

Plasma medicine is an emerging field where plasma physics is used for therapeutical applications. Temperature is an important factor to take into account with respect to the applications of plasma to biological systems. During the treatment, the tissue temperature could increase to critical values. In this work, a model is presented, which is capable of predicting the skin temperature during a treatment with a radio frequency driven plasma needle. The main gas was helium. To achieve this, a discharge model was coupled to a heat transfer and fluid flow model. The results provide maximum application times for different power depositions in order to avoid reaching critical skin temperatures.

Selective modification of the acid-base properties of ceria by supported Au.

Au supported on CeO(2) prepared by deposition-precipitation with urea leads to a basic catalyst. Au acts in two ways as surface modifier. First, Au selectively interacts with Ce(4+) cations by either blocking access to or reducing Ce(4+) to Ce(3+). Second, the resulting Au atoms (presumably as Au(+) ions) act as soft, weak Lewis acid sites stabilizing carbanion intermediates and enhancing hydride abstraction in the dehydrogenation of alcohols. In consequence, the thus-synthesized basic catalyst catalyzes the dehydrogenation of propan-2-ol to acetone with high efficiency and without notable deactivation. Additionally, the dehydration pathway of propan-2-ol is eliminated, as Au also quantitatively blocks access to strongly acidic Ce(4+) ions or reduces them to Ce(3+).