A Critical Review of the Time-Dependent Performance of Polymeric Pipeline Coatings: Focus on Hydration of Epoxy-Based Coatings

The barrier performance of organic coatings is a direct function of mass transport and long-term stability of the polymeric structure. A predictive assessment of the protective coating cannot be conducted a priori of degradation effects on transport. Epoxy-based powder coatings are an attractive class of coatings for pipelines and other structures because application processing times are low and residual stresses between polymer layers are reduced. However, water ingress into the polymeric network of these coatings is of particular interest due to associated competitive sorption and plasticization effects. This review examines common analytical techniques for identifying parameters involved in transport in wet environments and underscores the gaps in the literature for the evaluation of the long-term performance of such coating systems. Studies have shown that the extent of polymer hydration has a major impact on gas and ion permeability/selectivity. Thus, transport analyses based only on micropore filling (i.e., adsorption) by water molecules are inadequate. Combinatorial entropy of the glassy epoxy and water vapor mixture not only affects the mechanism of membrane plasticization, but also changes the sorption kinetics of gas permeation and causes a partial gas immobility in the system. However, diffusivity, defined as the product of a kinetic mobility parameter and a concentration-dependent thermodynamic parameter, can eventually become favorable for gas transport at elevated temperatures, meaning that increasing gas pressure can decrease selectivity of the membrane for gas permeation. On the other hand, reverse osmosis membranes have shown that salt permeation is sensitive to, among other variables, water content in the polymer and a fundamental attribute in ionic diffusion is the effective size of hydrated ions. In addition, external electron sources—e.g., cathodic protection potentials for pipeline structures—can alter the kinetics of this transport as the tendency of ions to dissociate increases due to electrostatic forces. Focusing primarily on epoxy-based powder coatings, this review demonstrates that service parameters such as humidity, temperature, and concentration of aggressive species can dynamically develop different transport mechanisms, each at the expense of others. Although multilayered coating systems decrease moisture ingress and the consequences of environmental exposure, this survey shows that demands for extreme operating conditions can pose new challenges for coating materials and sparse data on transport properties would limit analysis of the remaining life of the system. This knowledge gap impedes the prediction of the likelihood of coating and, consequently, infrastructure failures.

Efficient Removal 17-Estradiol by Graphene-Like Magnetic Sawdust Biochar: Preparation Condition and Adsorption Mechanism

The occurrence of environmental endocrine disrupting chemicals (EDCs) in aquatic environments has caused extensive concern. Graphene-like magnetic sawdust biochar was synthesized using potassium ferrate (K2FeO4) to make activated sawdust biochar and applied for the removal of 17-estradiol (E2). The characterization showed that the surface morphology of five graphene-like magnetic sawdust biochars prepared with different preparation conditions were quite different. The specific surface area and pore structure increased with the increment of K2FeO4 addition. The results have shown that graphene-like magnetic sawdust biochar (1:1/900 °C) had the best removal on E2. The experimental results indicated that pseudo-first-order kinetic model and the Langmuir model could describe the adsorption process well, in which the equilibrium adsorption capacity (qe,1) of 1:1/900 °C were 59.18 mg·g−1 obtained from pseudo-first-order kinetic model and the maximum adsorption capacity (qmax) of 1:1/900 °C were 133.45 mg·g−1 obtained from Langmuir model at 298K. At the same time, lower temperatures, the presence of humic acid (HA), and the presence of NaCl could be regulated to change the adsorption reaction in order to remove E2. Adsorption capacity was decreased with the increase of solution pH because pH value not only changed the surface charge of graphene-like magnetic sawdust biochar, but also affected the E2 in the water. The possible adsorption mechanism for E2 adsorption on graphene-like magnetic sawdust biochar was multifaceted, involving chemical adsorption and physical absorption, such as H-bonding, π-π interactions, micropore filling effects, and electrostatic interaction. To sum up, graphene-like magnetic sawdust biochar was found to be a promising absorbent for E2 removal from water.

Molecular Investigation of CO2/CH4 Competitive Adsorption and Confinement in Realistic Shale Kerogen

The adsorption behavior and the mechanism of a CO2/CH4 mixture in shale organic matter play significant roles to predict the carbon dioxide sequestration with enhanced gas recovery (CS-EGR) in shale reservoirs. In the present work, the adsorption performance and the mechanism of a CO2/CH4 binary mixture in realistic shale kerogen were explored by employing grand canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulations. Specifically, the effects of shale organic type and maturity, temperature, pressure, and moisture content on pure CH4 and the competitive adsorption performance of a CO2/CH4 mixture were investigated. It was found that pressure and temperature have a significant influence on both the adsorption capacity and the selectivity of CO2/CH4. The simulated results also show that the adsorption capacities of CO2/CH4 increase with the maturity level of kerogen. Type II-D kerogen exhibits an obvious superiority in the adsorption capacity of CH4 and CO2 compared with other type II kerogen. In addition, the adsorption capacities of CO2 and CH4 are significantly suppressed in moist kerogen due to the strong adsorption strength of H2O molecules on the kerogen surface. Furthermore, to characterize realistic kerogen pore structure, a slit-like kerogen nanopore was constructed. It was observed that the kerogen nanopore plays an important role in determining the potential of CO2 subsurface sequestration in shale reservoirs. With the increase in nanopore size, a transition of the dominated gas adsorption mechanism from micropore filling to monolayer adsorption on the surface due to confinement effects was found. The results obtained in this study could be helpful to estimate original gas-in-place and evaluate carbon dioxide sequestration capacity in a shale matrix.

Evolution of wood cell wall nanopore size distribution in the hygroscopic range

Owing to technical difficulties, experimental assessment of wood cell wall pore size distribution (PSD) in the hygroscopic range still remains challenging. Here, a “trial-and-error” approach was proposed to calculate such distribution through bridging experimental and simulated sorption isotherms presented by the authors in the past. Two main assumptions were made in the calculations, namely, the generation of new and the swelling of existing cell wall pores during water sorption. The nanopore size distribution of dried cell wall derived from the experimental CO2 gas sorption isotherms was used as the initial boundary condition. Predicted pore size distributions were assessed to be fairly reasonable by comparing them at 95% relative humidity with the PSD of fully saturated cell walls derived from the solute exclusion method. The predicted distribution was relatively wide with several major peaks evolving in the hygroscopic range. The present work also showed that confounded by a wide PSD that includes mostly micropores, the shape of the experimental sorption isotherms was not reliable in assessing the sorption mechanism. The simulations suggested an alternative water sorption mechanism for wood, i.e. micropore filling of cell wall nanopores.