Polymerization and Structure of Opposing Polymer Brushes Studied by Computer Simulations

A model of the polymerization process during the formation of a pair of polymer brushes was designed and investigated. The obtained system consisted of two impenetrable parallel surfaces with the same number of chains grafted on both surfaces. Coarse-grained chains embedded in nodes of a face-centered cubic lattice with excluded volume interactions were obtained by a ‘grafted from’ procedure. The structure of synthesized macromolecular systems was also studied. Monte Carlo simulations using the dynamic lattice liquid model were employed using dedicated parallel machine ARUZ in a large size and time scale. The parameters of the polymerization process were found to be crucial for the proper structure of the brush. It was found that for high grafting densities, chains were increasingly compressed, and there is surprisingly little interpenetration of chains from opposite surfaces. It was predicted and confirmed that in a polydisperse sample, the longer chains have unique configurations consisting of a stretched stem and a coiled crown.

Study on Annular Pressure Buildup in Offshore Heavy Oil Thermal Recovery Wells Considering Dissolved Gas Contained in Annuli

In the offshore industry, especially heavy oil thermal recovery wells, due to the great temperature difference between the low-temperature seawater and high-temperature heavy oil, it is easy to cause the temperature increase of annular fluid in the operation process which will result in the annular pressure buildup phenomenon (APB). The increase of annulus pressure may lead to the failure of the casing and wellbore integrity, which will seriously affect the normal production and lead to great economic loss. In order to study the formation of APB and provide a basis for the field operation design, a radial full-size physical experiment of APB was carried out in this work and an annular pressure prediction model in the presence of dissolved gas was proposed based on the experimental results. The verification and comparison analyses of the full-liquid model and the dissolved gas model were conducted with the experimental data. Furthermore, the sensitivity analysis of the influence of the dissolved gas volume fraction and casing deformation on APB was carried out. The results show that the prediction results calculated by the dissolved gas model are in good agreement with the experimental data and the prediction accuracy is higher than that of the full-liquid model. When the annular dissolved gas volume fraction is less than 0.1%, the full-liquid model can be used to simplify and approximate calculations. Ignoring casing deformation will produce prediction error in each annulus, which means this simplification should be used with extreme caution. This work provides a valuable experimental reference for the study of APB, as well as a novel model for APB prediction in the field.

A Thermodynamic model for the subsolidus evolution and melting of peridotite

We present a structural update to the thermodynamic model for calculating peridotite phase relations and melt compositions at 0.01 to 60 kbar and from 600 °C to the peridotite liquidus in the system K2O–Na2O–CaO–FeO–MgO–Al2O3–SiO2–TiO2–Fe2O3–Cr2O3 (KNCFMASTOCr), based on the model of Holland et al., 2018 [Melting of Peridotites through to Granites: A Simple Thermodynamic Model in the System KNCFMASHTOCr. Journal of Petrology 59, 881–900]. The new model is better able to predict the phase relations and melting of ultramafic rocks, in particular the abundance of orthopyroxene in the residue and the concentration of silica in the melt. In addition, improvements in modelling Cr-spinels mean that the model is now able to reproduce Cr-content of garnet and spinel above and below the solidus without modification to the knorringite free energy. Model calculations indicate that, for peridotite composition KR4003, the spinel to garnet transition intersects the solidus at 22.1–24.8 kbar and orthopyroxene disappears from the solidus at 29.1 kbar. Below the solidus, the model is able to reproduce the abundances and compositions of phases in experimental studies and natural samples spanning a range of compositions, allowing it to be used for investigating subsolidus equilibration during mantle cooling and pressurisation/decompression. The liquid model provides a good fit to experimental data and is able to replicate the position of the solidus and the composition of both melt and residue at and above the solidus for a range of peridotite compositions. The model may therefore be used to investigate fractional mantle melting and basalt generation in modern geodynamic regimes, and also to explore equilibrium mantle melting in the early Earth. The model can also be used to explore liquid and residue compositions for melting of non-pyrolitic mantle, for which there is a paucity of experimental data. We demonstrate the scope of the model using two case studies investigating the subsolidus evolution and melting of a silica-rich cratonic peridotite from the Kaapvaal craton.

A tied Fermi liquid to Luttinger liquid model for nonlinear transport in conducting polymers

Organic conjugated polymers demonstrate great potential in transistors, solar cells and light-emitting diodes, whose performances are fundamentally governed by charge transport. However, the morphology–property relationships and the underpinning charge transport mechanisms remain unclear. Particularly, whether the nonlinear charge transport in conducting polymers is appropriately formulated within non-Fermi liquids is not clear. In this work, via varying crystalline degrees of samples, we carry out systematic investigations on the charge transport nonlinearity in conducting polymers. Possible charge carriers’ dimensionality is discussed when varying the molecular chain’s crystalline orders. A heterogeneous-resistive-network (HRN) model is proposed based on the tied-link between Fermi liquids (FL) and Luttinger liquids (LL), related to the high-ordered crystalline zones and weak-coupled amorphous regions, respectively. The HRN model is supported by precise electrical and microstructural characterizations, together with theoretic evaluations, which well describes the nonlinear transport behaviors and provides new insights into the microstructure-correlated charge transport in organic solids.