Water-Mediated Epoxy/Surface Adhesion: Understanding the Interphase Region.

Epoxy resins coatings are commonly found in corrosion protection coatings but the presence of water can affect their adhesion to the substrate, often weakening the adhesion of the coating to the solid, reducing its efficiency. Nevertheless, small amounts of water can enhance the epoxy/substrate interactions. In this work, the interphase region of an epoxy precursor and metal oxide substrates is investigated using molecular simulations and it is found that water accumulates between the epoxy layer and the solid substrate. At high water concentrations (9 wt %) the interaction between the epoxy precursor and the solid surface is weakened regardless of the nature of the solid, but at low water concentrations the nature of the solid surface becomes important. For hematite, the presence of water decreases the strength of adhesion but for goethite the presence of a small amount of water (3 wt %) enhances the adhesion to the surface resulting in a densification at the interface.

Molecular origins of Epoxy-Amine/Iron oxide interphase formation.

HYPOTHESIS: Interphase properties in composites, adhesives and protective coatings can be predicted on the basis of interfacial interactions between polymeric precursor molecules and the inorganic surface during network formation. The strength of molecular interactions is expected to determine local segmental mobility (polymer glass transition temperature, Tg) and cure degree. EXPERIMENTS: Conventional analysis techniques and atomic force microscopy coupled with infrared (AFM-IR) are applied to nanocomposite specimens to precisely characterise the epoxy-amine/iron oxide interphase, whilst molecular dynamics simulations are applied to identify the molecular interactions underpinning its formation. FINDINGS: Attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and high-resolution AFM-IR mapping confirm the presence of nanoscale under-cured interphase regions. Interfacial segregation of the molecular triethylenetetraamine (TETA) cross-linker results in an excess of epoxy functionality near synthetic hematite, (Fe2O3) magnetite (Fe3O4) and goethite (Fe(O)OH) particle surfaces. This occurs independently of the variable surface binding energies, as a result of entropic segregation during the cure. Thermal analysis and molecular dynamics simulations demonstrate that restricted segmental motion is imparted by strong interfacial binding between surface Fe sites in goethite, where the position of surface hydroxyl protons enables synergistic hydrogen bonding and electrostatic binding to Fe atoms at specific sites. This provides a strong driving force for molecular orientation resulting in significantly raised Tg values for the goethite composite samples.

The development of a comprehensive toolbox based on multi-level, high-throughput screening of MOFs for CO/N2 separations.

The separation of CO/N2 mixtures is a challenging problem in the petrochemical sector due to the very similar physical properties of these two molecules, such as size, molecular weight and boiling point. To solve this and other challenging gas separations, one requires a holistic approach. The complexity of a screening exercise for adsorption-based separations arises from the multitude of existing porous materials, including metal-organic frameworks. Besides, the multivariate nature of the performance criteria that needs to be considered when designing an optimal adsorbent and a separation process - i.e. an optimal material requires fulfillment of several criteria simultaneously - makes the screening challenging. To address this, we have developed a multi-scale approach combining high-throughput molecular simulation screening, data mining and advanced visualization, as well as process system modelling, backed up by experimental validation. We have applied our recent advances in the engineering of porous materials' morphology to develop advanced monolithic structures. These conformed, shaped monoliths can be used readily in industrial applications, bringing a valuable strategy for the development of advanced materials. This toolbox is flexible enough to be applied to multiple adsorption-based gas separation applications.

Adsorption of Epoxy Oligomers on Iron Oxide Surfaces: The Importance of Surface Treatment and the Role of Entropy.

Epoxy-based coatings are widely used in a range of industries as protective coatings. The performance of the final solid-polymer system is dependent on the physicochemical properties of the interface and the interaction between the polymer and the solid substrate. In this study, we perform atomistic molecular dynamics simulations to investigate the binding of a common component in epoxy resins, diglycidyl ether of bisphenol A (DGEBA), on two iron oxide surfaces, hematite (0001) and magnetite (100), and investigate the effect of surface hydroxylation on the binding energy. We show that adsorption of DGEBA on hematite is more favorable than on magnetite and that the adsorbed molecules are highly localized on the pristine hematite surface but mobile on highly hydroxylated hematite surfaces and magnetite surfaces irregardless of surface hydroxylation fraction. A high degree of hydroxylation significantly reduces the binding energy of DGEBA on hematite but not on magnetite. The free-energy calculations confirm the trends observed upon hydroxylation, but the magnitude of the potential of mean force is lower than the binding energy due to the entropic contributions. Therefore, it can be suggested that DGEBA will adsorb more strongly on a surface containing a higher content of hematite than magnetite and that the presence of hydroxyl groups will weaken this adsorption. The presence of hydroxyl groups increases mobility of the chains, which can affect the coating rigidity.

High-throughput molecular simulations reveal the origin of ion free energy barriers in graphene oxide membranes.

Graphene oxide (GO) membranes are highly touted as materials for contemporary separation challenges including desalination, yet understanding of the interplay between their structure and salt rejection is limited. K+ ion permeation through hydrated GO membranes was investigated by combining structurally realistic molecular models and high-throughput molecular dynamics simulations. We show that it is essential to consider the complex GO microstructure to quantitatively reproduce experimentally-derived free energy barriers to K+ permeation for membranes with various interlayer distances less than 1.3 nm. This finding confirms the non-uniformity of GO nanopores and the necessity of the high-throughput approach for this class of material. The large barriers arise due to significant dehydration of K+ inside the membrane, which can have as few as 3 coordinated water molecules, compared to 7 in bulk solution. Thus, even if the membranes have an average pore size larger than the ion's hydrated diameter, the significant presence of pores whose size is smaller than the hydrated diameter creates bottlenecks for the permeation process.

Solvent-induced morphological transitions in methacrylate-based block-copolymer aggregates.

Poly(ethylene oxide)-b-poly(butylmethacrylate) (PEO-b-PBMA) copolymers have recently been identified as excellent building blocks for the synthesis of hierarchical nanoporous materials. Nevertheless, while experiments have unveiled their potential to form bicontinuous phases and vesicles, a general picture of their phase and aggregation behavior is still missing. By performing Molecular Dynamics simulations, we here apply our recent coarse-grained model of PEO-b-PBMA to investigate its self-assembly in water and tetrahydrofuran (THF) and unveil the occurrence of a wide spectrum of mesophases. In particular, we find that the morphological phase diagram of this ternary system incorporates bicontinuous and lamellar phases at high copolymer concentrations, and finite-size aggregates, such as dispersed sheets or disk-like aggregates, spherical vesicles and rod-like vesicles, at low copolymer concentrations. The morphology of these mesophases can be controlled by tuning the THF/water relative content, which has a striking effect on the kinetics of self-assembly as well as on the resulting equilibrium structures. Our results disclose the fascinating potential of PEO-b-PBMA copolymers for the templated synthesis of nanostructured materials and offer a guideline to fine-tune their properties by accurately selecting the THF/water ratio.

Initial Studies Directed toward the Rational Design of Aqueous Graphene Dispersants.

This study presents preliminary experimental data suggesting that sodium 4-(pyrene-1-yl)butane-1-sulfonate (PBSA), 5, an analogue of sodium pyrene-1-sulfonate (PSA), 1, enhances the stability of aqueous reduced graphene oxide (RGO) graphene dispersions. We find that RGO and exfoliated graphene dispersions prepared in the presence of 5 are approximately double the concentration of those made with commercially available PSA, 1. Quantum mechanical and molecular dynamics simulations provide key insights into the behavior of these molecules on the graphene surface. The seemingly obvious introduction of a polar sulfonate head group linked via an appropriate alkyl spacer to the aromatic core results in both more efficient binding of 5 to the graphene surface and more efficient solvation of the polar head group by bulk solvent (water). Overall, this improves the stabilization of the graphene flakes by disfavoring dissociation of the stabilizer from the graphene surface and inhibiting reaggregation by electrostatic and steric repulsion. These insights are currently the subject of further investigations in an attempt to develop a rational approach to the design of more effective dispersing agents for rGO and graphene in aqueous solution.

In Silico Design and Characterization of Graphene Oxide Membranes with Variable Water Content and Flake Oxygen Content.

Graphene oxide (GO) membranes offer exceptional promise for certain aqueous separation challenges, such as desalination. Central to unlocking this promise and optimizing performance for a given separation is the establishment of a detailed molecular-level understanding of how the membrane's composition affects its structural and transport properties. This understanding is currently lacking, in part due to the fact that, until recently, molecular models with a realistic distribution of oxygen functionalities and interlayer flake structure were unavailable. To understand the effect of composition on the properties of GO membranes, models with water contents and oxygen contents, varying between 0% and 40% by weight, were prepared in this work using classical molecular dynamics simulations. The change in membrane interlayer distance distribution, water connectivity, and water diffusivity with water and oxygen content was quantified. Interlayer distance distribution analysis showed that the swelling of GO membranes could be controlled by separately tuning both the flake oxygen content and the membrane water content. Water-molecule cluster analysis showed that a continuous and fully connected network of water nanopores is not formed until the water content reaches ∼20%. The diffusivity of water in the membrane was also found to strongly depend on both the water and the oxygen content. These insights help understand the structure and transport properties of GO membranes with sub-nanometer interlayer distances and could be exploited to enhance the performance of GO membranes for aqueous separation applications. More broadly, the high-throughput in silico approach adopted could be applied to other nanomaterials with intrinsic non-stoichiometry and structural heterogeneity.

Competitive Adsorption of a Multifunctional Amine and Phenol Surfactant with Ethanol on Hematite from Nonaqueous Solution.

Surfactants, which contain phenol and amine groups, are commonly used in industries to protect metallic surfaces, and their efficiency depends strongly on factors such as pressure and temperature, solvent properties, and the presence of other surfactants in the system. In this work, we present a molecular simulation study of the competitive adsorption between a multifunctional phenol and amine surfactant model and ethanol at the oil/solid interface formed between iso-octane and a model hematite (α-Fe2O3) slab. We show that the surfactant strongly adsorbs at the iso-octane/hematite interface in the absence of ethanol at moderate temperatures. As the concentration of ethanol is increased, the ethanol molecules compete effectively for the adsorption sites on the iron oxide surface. This competition drives the surfactant molecules to remain in the bulk solution, while ethanol forms ordered and strongly coordinated layers at the oil/solid interface, despite the well-known complete miscibility of ethanol in iso-octane in bulk under standard conditions. Potential of mean force calculations show that the free energy of adsorption of the surfactant is approximately two times larger than that for a single ethanol molecule, but the simulations also reveal that a single surfactant chain needs to displace up to five ethanol molecules to adsorb onto the surface. The end result is more favorable ethanol adsorption which agrees with the experimental analysis of similar oil/iron oxide systems also reported in this work.

Design Rules for Graphene and Carbon Nanotube Solvents and Dispersants.

The constantly widening industrial applications of carbon-based nanomaterials puts into sharp perspective the lack of true solvents in which the materials spontaneously exfoliate to individual molecules. This work shows that the different geometry of graphene compared to that of carbon nanotubes can change the potency of a molecule to act as a solvent or dispersant. Through analysis of the structure/function relationships, we derive a number of design rules that will aid the identification of the best solvent or dispersant candidates.

Liquid Adsorption of Organic Compounds on Hematite α-Fe2O3 Using ReaxFF.

ReaxFF-based molecular dynamics simulations are used in this work to study the effect of the polarity of adsorbed molecules in the liquid phase on the structure and polarization of hematite (α-Fe2O3). We compared the adsorption of organic molecules with different polarities on a rigid hematite surface and on a flexible and polarizable surface. We show that the displacements of surface atoms and surface polarization in a flexible hematite model are proportional to the adsorbed molecule's polarity. The increase in electrostatic interactions resulting from charge transfer in the outermost solid atoms in a flexible hematite model results in better-defined adsorbed layers that are less ordered than those obtained assuming a rigid solid. These results suggest that care must be taken when parametrizing empirical transferable force fields because the calculated charges on a solid slab in vacuum may not be representative of a real system, especially when the solid is in contact with a polar liquid.

Adsorption and Diffusion of C1 to C4 Alkanes in Dual-Porosity Zeolites by Molecular Simulations.

We employ grand canonical Monte Carlo and molecular dynamics simulations to systematically study the adsorption and diffusion of C1 to C4 alkanes in hierarchical ZSM-5 zeolite with micropores (∼1 nm) and mesopores (>2 nm). The zeolite is characterized by a large surface area of active sites on the microporous scale with high permeability and access to the active sites, which arises from the enhanced transport at the mesoporous scale. We model this zeolite as a microporous Na+-exchanged alumino-sillicate zeolite ZSM-5/35 (Si/Al = 35) in which cylindrical mesopores with a diameter of 4 nm have been built by deleting atoms accordingly. We use the TraPPE and Vujic-Lyubartsev force fields along with the Lorentz-Berthelot combining rules to describe adsorbate-adsorbate and adsorbate-adsorbent interactions. The performance of the force fields is assessed by comparing against experimental single-component adsorption isotherms of methane and ethane in microporous ZSM-5/35, which we measured as part of this work. We compare the adsorption isotherms and diffusivities of the adsorbed alkanes in the dual-porosity zeolite with those in microporous ZSM-5/35 and discern the specific behavior at each porosity scale on the overall adsorption, self-diffusion, and transport behavior in zeolites with dual micro/mesoporosities.

Binding CO2 by a Cr8 Metallacrown.

The {Cr8 } metallacrown [CrF(O2 Ct Bu)2 ]8 , containing a F-lined internal cavity, shows high selectivity for CO2 over N2 . DFT calculations and absorption studies support the multiple binding of F-groups to the C-center of CO2 (C⋅⋅⋅F 3.190(9)-3.389(9) Å), as confirmed by single-crystal X-ray diffraction.

Assessment of MOF's Quality: Quantifying Defect Content in Crystalline Porous Materials.

A quantitative method for assessment of defects in metal-organic framework (MOF) is presented based on isotherms calculated using Grand Canonical Monte Carlo (GCMC) simulations. Defects in MOF structures generated during the synthesis and sample preparation can lead to large variations in experimentally measured adsorption isotherms but are difficult to quantify. We use as a case study CO2 adsorption on Cu3(BTC)2 MOF (BTC = benzene-1,3,5-tricarboxylic acid) to show that different samples reported in the literature have various proportions of principal pores blocked or side pores blocked, resulting in isotherms with different capacity and affinity toward CO2. The approach presented is easily generalized to other materials, showing that simulation results combined with experimentally measured gas adsorption isotherms can be used to quantitatively identify key defective features of the material.

Characterizing the structure of organic molecules of intrinsic microporosity by molecular simulations and X-ray scattering.

The design of a new class of materials, called organic molecules of intrinsic microporosity (OMIMs), incorporates awkward, concave shapes to prevent efficient packing of molecules, resulting in microporosity. This work presents predictive molecular simulations and experimental wide-angle X-ray scattering (WAXS) for a series of biphenyl-core OMIMs with varying end-group geometries. Development of the utilized simulation protocol was based on comparison of several simulation methods to WAXS patterns. In addition, examination of the simulated structures has facilitated the assignment of WAXS features to specific intra- and intermolecular distances, making this a useful tool for characterizing the packing behavior of this class of materials. Analysis of the simulations suggested that OMIMs had greater microporosity when the molecules were the most shape-persistent, which required rigid structures and bulky end groups. The simulation protocol presented here allows for predictive, presynthesis screening of OMIMs and similar complex molecules to enhance understanding of their structures and aid in future design efforts.

Dissolution of lamellar phases.

Dissolution of surfactant liquid crystals is an important process both at the manufacturing stage of surfactant based formulated products and during their use. Dissipative particle dynamics simulations were employed to study the production of surfactant-oil-water systems under both temperature and water quenches. Upon the dissolution of a high concentration lamellar phase surfactant, wormlike micelles are formed, which differ from the spherical micelles produced at the same concentration with a temperature quench. The surfactant molecules have a tendency to remain within their initially formed lamellar phase sheets and just rearrange into wormlike micelles. When a hydrophobic additive (oil) is added to the initial system, longer cylindrical micelles are formed, with the creation of some spherical micelles under dissolution. These micelles detach from the long cylinders as a result of their natural oscillations.

Adsorption of CO(2), CH(4), and N(2) on zeolitic imidazolate frameworks: experiments and simulations.

Experimental measurements and molecular simulations were conducted for two zeolitic imidazolate frameworks, ZIF-8 and ZIF-76. The transferability of the force field was tested by comparing molecular simulation results of gas adsorption with experimental data available in the literature for other ZIF materials (ZIF-69). Owing to the good agreement observed between simulation and experimental data, the simulation results can be used to identify preferential adsorption sites, which are located close to the organic linkers. Topological mapping of the potential-energy surfaces makes it possible to relate the preferential adsorption sites, Henry constant, and isosteric heats of adsorption at zero coverage to the nature of the host-guest interactions and the chemical nature of the organic linker. The role played by the topology of the solid and the organic linkers, instead of the metal sites, upon gas adsorption on zeolite-like metal-organic frameworks is discussed.

Monte carlo simulation of self-assembled ordered hybrid materials.

Lattice Monte Carlo simulations were performed to study the structure of hybrid organic-inorganic materials. Several cases were modeled where the composition corresponds to high surfactant concentration phases similar to that obtained from the synthesis of hybrid materials resulting from a phase separation. When using hybrid inorganic precursors, comparable to organosilicas, we observe that the organic segment is well mixed with the inorganic precursor and surfactant heads and no preferential location of the organic groups is observed. We show that the behavior of surfactant/hybrid precursor systems is analogous to those where co-surfactants or co-solvents are used, and that the lack of ordering in some cases can be explained by the change in solvent quality when using hybrid precursors. A comparison of structural characterization of the different phases using several tools, such as aggregate size distribution, density profiles, and pair radial distribution function is presented.

Adsorption of simple gases in MCM-41 materials: the role of surface roughness.

This paper reports the development and testing of atomistic models of silica MCM-41 pores. Model A is a regular cylindrical pore having a constant section. Model B has a surface disorder that reproduces the morphological features of a pore obtained from an on-lattice simulation that mimics the synthesis process of MCM-41 materials. Both models are generated using a similar procedure, which consists of carving the pore out of an atomistic silica block. The differences between the two models are analyzed in terms of small angle neutron scattering spectra as well as adsorption isotherms and isosteric heat curves for Ar at 87 K and Xe at 195 K. As expected for capillary condensation in regular nanopores, the Ar and Xe adsorption/desorption cycles for model A exhibit a large hysteresis loop having a symmetrical shape, i.e., with parallel adsorption and desorption branches. The features of the adsorption isotherms for model B strongly depart from those observed for model A. Both the Ar and Xe adsorption branches for model B correspond to a quasicontinuous pore filling that involves coexistence within the pore of liquid bridges and gas nanobubbles. As in the case of model A, the Ar adsorption isotherm for model B exhibits a significant hysteresis loop; however, the shape of the loop is asymmetrical with a desorption branch much steeper than the adsorption branch. In contrast, the adsorption/desorption cycle for Xe in model B is quasicontinuous and quasireversible. Comparison with adsorption and neutron scattering experiments suggests that model B is too rough at the molecular scale but reproduces reasonably the surface disorder of real MCM-41 at larger length scales. In contrast, model A is smooth at small length scales in agreement with experiments but seems to be too ordered at larger length scales.

Cosurfactant and cosolvent effects on surfactant self-assembly in supercritical carbon dioxide.

The impact of alcohol additives on the self-assembly of surfactants in supercritical carbon dioxide is investigated using lattice Monte Carlo simulations. We observe that all studied (model) alcohols reduce the critical micelle concentration. The reduction is stronger the longer the hydrocarbon chain of the alcohol, and the higher the alcohol concentration. Short-chain alcohols are found to concentrate in the surfactant layer of the aggregates, replacing surfactant molecules and leading to a strong decrease of the aggregation number and a large increase of the number of aggregates. On the other hand, only a small number of alcohol molecules with longer chain length are found in the aggregates, leading to a slight increase in the aggregation number. However, structural properties such as size and density profiles of aggregates at the same aggregation number are not influenced markedly. Consequently, short-chain alcohols act as cosurfactants, directly influencing the properties of the aggregates, while alcohols with longer hydrocarbon chains work as cosolvents, altering the properties of the solvent. However, the transition between both extremes is gradual.