Imperial College London

Dr James P. Ewen

Faculty of EngineeringDepartment of Mechanical Engineering

RAEng Research Fellow



j.ewen Website




462City and Guilds BuildingSouth Kensington Campus





Publication Type

41 results found

S Bhamra J, P Ewen J, Ayestarán Latorre C, A R Bomidi J, W Bird M, Dini Det al., 2023, Atomic-scale insights into the tribochemical wear of diamond on quartz surfaces, Applied Surface Science, Vol: 639, Pages: 1-13, ISSN: 0169-4332

A detailed understanding of diamond wear is crucial due to its use in high-performance cutting tools. Despite being a much harder material, diamond shows appreciable wear when cutting silicon dioxides due to a tribochemical mechanism. Here, we use nonequilibrium molecular dynamics simulations with a reactive force field to investigate the wear of single-crystal diamond tips sliding on α-quartz surfaces. Atom-by-atom attrition of carbon atoms is initiated by the formation of C-O interfacial bonds, followed by C-C cleavage, and either diffusion into the substrate or further oxidation to form CO2 molecules. Water molecules dissociate to form hydroxyl groups, which passivates the surfaces and reduces interfacial bonding and wear. At low loads, the initial wear rate increases exponentially with temperature and normal stress, consistent with stress-augmented thermally activated wear models. At higher loads, the initial wear rate becomes less sensitive to the normal stress, eventually plateauing towards a constant value. This behaviour can be described using the multibond wear model. After long sliding distances, wear also occurs through cluster detachment via tail fracture. Here, wear becomes approximately proportional to the sliding distance and normal load, consistent with the Archard model. The normalised wear rates from the simulations are within the experimentally-measured range.

Journal article

Ntioudis S, Ewen JP, Dini D, Turner CHet al., 2023, A hybrid off-lattice kinetic Monte Carlo/molecular dynamics method for amorphous thin film growth, Computational Materials Science, Vol: 229, ISSN: 0927-0256

The ability to understand and model the growth of amorphous thin films on solid surfaces is essential to a wide range of industrial applications, from the deposition of wear-resistant coatings to the production of solar cells. Here, a three-dimensional (3D) hybrid off-lattice kinetic Monte Carlo/molecular dynamics (kMC/MD) algorithm is developed to study the growth of thin amorphous films on solid substrates with atomistic resolution over timescales of tens of seconds. We use this method to study the growth of polyphosphate films from tricresyl phosphate (TCP) molecules on an iron substrate. Molecular adsorption/desorption, bond breaking/formation processes, and diffusion of iron ions through the film are simulated in the kMC stage and the film is relaxed during the MD stage. The kMC/MD method is approximately eleven orders of magnitude faster than equivalent reactive force field (ReaxFF) MD simulations. The simulated film growth rate and topology agree well with experimental results and the chemical structure of the film is consistent with previous molecular dynamics simulations of iron polyphosphates. The newly-developed hybrid kMC/MD methodology can be adapted to yield important insights into thin film growth for several other potential applications.

Journal article

Weiand E, Rodriguez-Ropero F, Roiter Y, Koenig P, Angioletti-Uberti S, Dini D, Ewen Jet al., 2023, Effects of surfactant adsorption on the wettability and friction of biomimetic surfaces, Physical Chemistry Chemical Physics, Vol: 25, Pages: 21916-21934, ISSN: 1463-9076

The properties of solid–liquid interfaces can be markedly altered by surfactant adsorption. Here, we use molecular dynamics (MD) simulations to study the adsorption of ionic surfactants at the interface between water and heterogeneous solid surfaces with randomly arranged hydrophilic and hydrophobic regions, which mimic the surface properties of human hair. We use the coarse-grained MARTINI model to describe both the hair surfaces and surfactant solutions. We consider negatively-charged virgin and bleached hair surface models with different grafting densities of neutral octadecyl and anionic sulfonate groups. The adsorption of cationic cetrimonium bromide (CTAB) and anionic sodium dodecyl sulfate (SDS) surfactants from water are studied above the critical micelle concentration. The simulated adsorption isotherms suggest that cationic surfactants adsorb to the surfaces via a two-stage process, initially forming monolayers and then bilayers at high concentrations, which is consistent with previous experiments. Anionic surfactants weakly adsorb via hydrophobic interactions, forming only monolayers on both virgin and medium bleached hair surfaces. We also conduct non-equilibrium molecular dynamics simulations, which show that applying cationic surfactant solutions to bleached hair successfully restores the low friction seen with virgin hair. Friction is controlled by the combined surface coverage of the grafted lipids and the adsorbed CTAB molecules. Treated surfaces containing monolayers and bilayers both show similar friction, since the latter are easily removed by compression and shear. Further wetting MD simulations show that bleached hair treated with CTAB increases the hydrophobicity to similar levels seen for virgin hair. Treated surfaces containing CTAB monolayers with the tailgroups pointing predominantly away from the surface are more hydrophobic than bilayers due to the electrostatic interactions between water molecules and the exposed cationic headgrou

Journal article

Rahman MR, Shen L, Ewen JP, Collard B, Heyes DM, Dini D, Smith ERet al., 2023, Non-equilibrium molecular simulations of thin film rupture., J Chem Phys, Vol: 158

The retraction of thin films, as described by the Taylor-Culick (TC) theory, is subject to widespread debate, particularly for films at the nanoscale. We use non-equilibrium molecular dynamics simulations to explore the validity of the assumptions used in continuum models by tracking the evolution of holes in a film. By deriving a new mathematical form for the surface shape and considering a locally varying surface tension at the front of the retracting film, we reconcile the original theory with our simulation to recover a corrected TC speed valid at the nanoscale.

Journal article

Weiand E, Ewen JP, Roiter Y, Koenig PH, Page SH, Rodriguez-Ropero F, Angioletti-Uberti S, Dini Det al., 2023, Nanoscale friction of biomimetic hair surfaces, Nanoscale, Vol: 15, Pages: 7086-7104, ISSN: 2040-3364

We investigate the nanoscale friction between biomimetic hair surfaces using chemical colloidal probe atomic force microscopy experiments and nonequilibrium molecular dynamics simulations. In the experiments, friction is measured between water-lubricated silica surfaces functionalised with monolayers formed from either octadecyl or sulfonate groups, which are representative of the surfaces of virgin and ultimately bleached hair, respectively. In the simulations, friction is monitored between coarse-grained model hair surfaces with different levels of chemical damage, where a specified amount of grafted octadecyl groups are randomly replaced with sulfonate groups. The sliding velocity dependence of friction in the simulations can be described using an extended stress-augmented thermally activation model. As the damage level increases in the simulations, the friction coefficient generally increases, but its sliding velocity-dependence decreases. At low sliding velocities, which are closer to those encountered experimentally and physiologically, we observe a monotonic increase of the friction coefficient with damage ratio, which is consistent with our new experiments using biomimetic surfaces and previous ones using real hair. This observation demonstrates that modified surface chemistry, rather than roughness changes or subsurface damage, control the increase in nanoscale friction of bleached or chemically damaged hair. We expect the methods and biomimetic surfaces proposed here to be useful to screen the tribological performance of hair care formulations both experimentally and computationally.

Journal article

Baláž M, Balema V, Blair RG, Boldyreva E, Bolm C, Braunschweig AB, Carpick RW, Craig SL, Emmerling F, Ewen JP, Fiore C, Friščić T, Grätz S, Halasz I, Hamzehpoor E, Ito H, Kim JG, Lampronti GI, Laurencin D, Mack J, Maini L, Mazzeo PP, Mohamed S, Nagapudi K, Niidu A, Vainauskas J, Zuffa Cet al., 2023, Shear processes and polymer mechanochemistry: general discussion., Faraday Discuss, Vol: 241, Pages: 466-484

Journal article

Abdelbar M, Ewen J, Dini D, Angioletti-Uberti Set al., 2023, Polymer brushes for friction control: Contributions of molecular simulations, Biointerphases, Vol: 18, ISSN: 1934-8630

When polymer chains are grafted to solid surfaces at sufficiently high density, they form brushes that can modify the surface properties. In particular, polymer brushes are increasingly being used to reduce friction in water-lubricated systems close to the very low levels found in natural systems, such as synovial joints. New types of polymer brush are continually being developed to improve with lower friction and adhesion, as well as higher load-bearing capacities. To complement experimental studies, molecular simulations are increasingly being used to help to understand how polymer brushes reduce friction. In this paper, we review how molecular simulations of polymer brush friction have progressed from very simple coarse-grained models toward more detailed models that can capture the effects of brush topology and chemistry as well as electrostatic interactions for polyelectrolyte brushes. We pay particular attention to studies that have attempted to match experimental friction data of polymer brush bilayers to results obtained using molecular simulations. We also critically look at the remaining challenges and key limitations to overcome and propose future modifications that could potentially improve agreement with experimental studies, thus enabling molecular simulations to be used predictively to modify the brush structure for optimal friction reduction.

Journal article

Weiand E, Ewen JP, Roiter Y, Koenig PH, Page SH, Rodriguez-Ropero F, Angioletti-Uberti S, Dini Det al., 2022, Nanoscale Friction of Biomimetic Hair Surfaces

<jats:title>Abstract</jats:title><jats:p>We investigate the nanoscale friction between biomimetic hair surfaces using chemical colloidal probe atomic force microscopy experiments and nonequilibrium molecular dynamics simulations. In the experiments, friction is measured between water-lubricated silica surfaces functionalised with monolayers of either octadecyl or sulfonate groups, which are representative of the surfaces of virgin and ultimately bleached hair, respectively. In the simulations, friction is monitored between coarse-grained model hair surfaces with different levels of chemical damage, where different fractions of grafted lipid molecules are randomly replaced with sulfonate groups. The sliding velocity dependence of friction can be described using an extended stress-augmented thermally activation model. As the damage level increases, the friction generally increases, but its sliding velocity-dependence decreases. At low sliding speeds, which are closer to those encountered physiologically and experimentally, we observe a monotonic increase of friction with the damage ratio, which is consistent with our new experiments using biomimetic surfaces and previous ones using real hair. This observation demonstrates that modified surface chemistry, rather than roughness changes or subsurface damage, control the increase in nanoscale friction of damaged hair. We expect the experimental and computational model surfaces proposed here to be useful to screen the tribological performance of hair care formulations.</jats:p>

Journal article

Zhang J, Ewen J, Spikes H, 2022, Substituent effects on the mechanochemical response of zinc dialkyldithiophosphate, Molecular Systems Design & Engineering, Vol: 7, Pages: 1045-1055, ISSN: 2058-9689

Mechanochemistry is known to play a key role in the function of some lubricant additives, such as the tribofilm growth of zinc dialkyldithiophosphate (ZDDP). This raises the intriguing possibility of tailoring the mechanochemical response of additives by modifying their alkyl substituents. Here, we study the tribofilm formation rate of ZDDPs containing several different alkyl groups on steel surfaces from a high-friction base oil. We use macroscale tribometer experiments under full-film elastohydrodynamic lubrication conditions to enable careful control of the temperature and stress during tribofilm growth. We show how the chain length and the presence of branches or bulky cycloaliphatic groups can lead to large differences in the temperature- and stress-dependencies of the tribofilm formation rate, which can be explained through variations in packing density, steric hindrance, and stress transmission efficiency. Our rate data are successfully fitted using the Bell model; a simple modification of the Arrhenius equation that is commonly employed to model the kinetics of mechanochemical processes. Using this model, we observe large differences in the activation energy, pre-exponential factor, and activation volume for the various ZDDPs. Our findings show how structure–performance relationships can be identified for lubricant additives, which may be useful to optimise their molecular structure.

Journal article

Ewen J, Maffioli L, Smith E, Daivis P, Dini D, Todd Bet al., 2022, Slip and stress from low strain-rate nonequilibrium molecular dynamics: The transient-time correlation function technique, The Journal of Chemical Physics, Vol: 156, Pages: 1-11, ISSN: 0021-9606

We derive the transient-time correlation function (TTCF) expression for the computation of phase variables of inhomogenous confined atomistic fluids undergoing boundary-driven planar shear (Couette) flow at constant pressure. Using nonequilibrium molecular dynamics simulations, we then apply the TTCF formalism to the computation of the shear stress and the slip velocity for atomistic fluids at realistic low shear rates, in systems under constant pressure and constant volume. We show that, compared to direct averaging of multiple trajectories, the TTCF method dramatically improves the accuracy of the results at low shear rates and that it is suitable to investigate the tribology and rheology of atomistically detailed confined fluids at realistic flow rates.

Journal article

Rahman M, Shen L, Ewen J, Dini D, Smith Eet al., 2022, The intrinsic fragility of the liquid-vapor interface: a stress network perspective, Langmuir: the ACS journal of surfaces and colloids, Vol: 38, Pages: 4669-4679, ISSN: 0743-7463

The evolution of the liquid-vapour interface of a Lennard-Jones fluid is examined with molecular dynamics simulations using the intrinsic sampling method. Results suggest, in agreement with capillary wave theory, clear damping of the density profiles as the temperature is increased. We identify a linear variation of the space-filling nature (fractal dimension) of the stress-clusters at the intrinsic surface with increasing surface tension, or equivalently, with decreasing temperature. A percolation analysis of these stress networks indicates that the stress field is more disjointed at higher temperatures. This leads to more fragile interfaces that result in a reduction in surface tension at higher temperature.

Journal article

Weiand E, Ewen J, Koenig P, Roiter Y, Page S, Angioletti-Uberti S, Dini Det al., 2022, Coarse-grained molecular models of the surface of hair, Soft Matter, Vol: 2022, ISSN: 1744-683X

We present a coarse-grained molecular model of the surface of human hair, which consists of a supported lipid monolayer, in the MARTINI framework. Using coarse-grained molecular dynamics (MD) simulations, we identify a lipid grafting distance that yields a monolayer thickness consistent with both atomistic MD simulations and experimental measurements of the hair surface. Coarse-grained models for fully-functionalised, partially damaged, and fully damaged hair surfaces are created by randomly replacing neutral thioesters with anionic sulfonate groups. This mimics the progressive removal of fatty acids from the hair surface by bleaching and leads to chemically heterogeneous surfaces. Using molecular dynamics (MD) simulations, we study the island structures formed by the lipid monolayers at different degrees of damage in vacuum and in the presence of polar (water) and non-polar (n-hexadecane) solvents. We also use MD simulations to compare the wetting behaviour of water and n-hexadecane droplets on the model surfaces through contact angle measurements, which are compared to experiments using virgin and bleached hair. The model surfaces capture the experimentally-observed transition of the hair surface from hydrophobic (and oleophilic) to hydrophilic (and oleophobic) as the level of bleaching damage increases. By selecting surfaces with specific damage ratios, we obtain contact angles from the MD simulations that are in good agreement with experiments for both solvents on virgin and bleached human hairs. To negate the possible effects of microscale curvature and roughness of real hairs on wetting, we also conduct additional experiments using biomimetic surfaces that are co-functionalised with fatty acids and sulfonate groups. In both the MD simulations and experiments, the cosine of the water contact angle increases linearly with the sulfonate group surface coverage with a similar slope. We expect that the proposed systems will be useful for future molecular dynamics si

Journal article

Ayestaran Latorre C, Moore J, Remias J, Spikes H, Dini D, Ewen Jet al., 2021, Mechanochemistry of phosphate esters confined between sliding iron surfaces, Communications Chemistry, Vol: 4, Pages: 1-11, ISSN: 2399-3669

The molecular structure of lubricant additives controls not only their adsorption and dissociation behaviour at the nanoscale, but also their ability to reduce friction and wear at the macroscale. Here, we show using nonequilibrium molecular dynamics simulations with a reactive force field that tri(s-butyl)phosphate dissociates much faster than tri(n-butyl)phosphate when heated and compressed between sliding iron surfaces. For both molecules, dissociative chemisorption proceeds through cleavage of carbon−oxygen bonds. The dissociation rate increases exponentially with temperature and stress. When the rate−temperature−stress data are fitted with the Bell model, both molecules have similar activation energies and activation volumes and the higher reactivity of tri(s-butyl)phosphate is due to a larger pre-exponential factor. These observations are consistent with experiments using the antiwear additive zinc dialkyldithiophosphate. This study represents a crucial step towards the virtual screening of lubricant additives with different substituents to optimise tribological performance.

Journal article

Navarro Acero P, Mohr S, Bernabei M, Fernández C, Dominguez B, Ewen Jet al., 2021, Molecular simulations of surfactant adsorption on iron oxide from hydrocarbon solvents, Langmuir: the ACS journal of surfaces and colloids, Vol: 37, Pages: 14582-14596, ISSN: 0743-7463

The performance of organic friction modifiers (OFMs) depends on their ability to adsorb onto surfaces and form protective monolayers. Understanding the relationship between OFM concentration in the base oil and the resulting surface coverage is important for improving lubricant formulations. Here, we use molecular dynamics (MD) simulations to study the adsorption of three OFMs─stearic acid (SA), glycerol monoostearate (GMS), and glycerol monooleate (GMO)─onto a hematite surface from two hydrocarbon solvents─n-hexadecane and poly(α-olefin) (PAO). We calculate the potential of mean force of the adsorption process using the adaptive biasing force algorithm, and the adsorption strength increases in the order SA < GMS < GMO. We estimate the minimum area occupied by OFM molecules on the surface using annealing MD simulations and obtained a similar hard-disk area for GMS and GMO but a lower value for SA. Using the MD results, we determine the adsorption isotherms using the molecular thermodynamic theory (MTT), which agree well with one previous experimental data set for SA on hematite. For two other experimental data sets for SA, lateral interactions between surfactant molecules need to be accounted for within the MTT framework. SA forms monolayers with lower surface coverage than GMO and GMS at low concentrations but also has the highest plateau coverage. We validate the adsorption energies from the MD simulations using high-frequency reciprocating rig friction experiments with different concentrations of the OFMs in PAO. For OFMs with saturated tailgroups (SA and GMS), we obtain good agreement between the simulations and the experiments. The results deviate for OFMs containing Z-unsaturated tailgroups (GMO) due to the additional steric hindrance, which is not accounted for in the current simulation framework. This study demonstrates that MD simulations, alongside MTT, are an accurate and efficient tool to predict adsorption isotherms at solid–liquid int

Journal article

Bhamra J, Ewen J, Ayestaran Latorre C, Bomidi J, Bird M, Dasgupta N, van Duin A, Dini Det al., 2021, Interfacial bonding controls friction in diamond–rock contacts, The Journal of Physical Chemistry C: Energy Conversion and Storage, Optical and Electronic Devices, Interfaces, Nanomaterials, and Hard Matter, Vol: 125, Pages: 18395-18408, ISSN: 1932-7447

Understanding friction at diamond–rock interfaces is crucial to increase the energy efficiencyof drilling operations. Harder rocks usually are usually more difficult to drill; however, poorperformance is often observed for polycrystalline diamond compact (PDC) bits on soft calcitecontaining rocks, such as limestone. Using macroscale tribometer experiments with adiamond tip, we show that soft limestone rock (mostly calcite) gives much higher frictioncoefficients compared to hard granite (mostly quartz) in both humid air and aqueousenvironments. To uncover the physicochemical mechanisms that lead to higher kinetic frictionat the diamond–calcite interface, we employ nonequilibrium molecular dynamics simulations(NEMD) with newly developed Reactive Force Field (ReaxFF) parameters. In the NEMDsimulations, higher friction coefficients are observed for calcite than quartz when watermolecules are included at the diamond–rock interface. We show that the higher friction inwater-lubricated diamond–calcite than diamond–quartz interfaces is due to increasedinterfacial bonding in the former. For diamond–calcite, the interfacial bonds mostly formthrough chemisorbed water molecules trapped between the tip and the substrate, while mainlydirect tip-surface bonds form inside diamond–quartz contacts. For both rock types, the rate ofinterfacial bond formation increases exponentially with pressure, which is indicative of astress-augmented thermally activated process. The mean friction force is shown to be linearlydependant on the mean number of interfacial bonds during steady-state sliding. Theagreement between the friction behaviour observed in the NEMD simulations and tribometerexperiments suggests that interfacial bonding also controls diamond–rock friction at themacroscale. We anticipate that the improved fundamental understanding provided by thisstudy will assist in the development of bit materials and coatings to minimise friction byre

Journal article

Reddyhoff T, Ewen J, Deshpande P, Frogley M, Welch M, Montgomery Wet al., 2021, Macroscale superlubricity and polymorphism of long-chain n-alcohols, ACS Applied Materials and Interfaces, Vol: 13, Pages: 9239-9251, ISSN: 1944-8244

Simple n-alcohols, such as 1-dodecanol, show anomalous film-forming and friction behaviors under elastohydrodynamic lubrication (EHL) conditions, as found inside bearings and gears. Using tribometer, diamond anvil cell (DAC), and differential scanning calorimetry (DSC) experiments, we show that liquid 1-dodecanol undergoes a pressure-induced solidification when entrained into EHL contacts. Different solid polymorphs are formed inside the contact depending on the temperature and pressure conditions. Surprisingly, at a moderate temperature and pressure, 1-dodecanol forms a polymorph that exhibits robust macroscale superlubricity. The DAC and DSC experiments show that superlubricity is facilitated by the formation of lamellar, hydrogen-bonded structures of hexagonally close-packed molecules, which promote interlayer sliding. This novel superlubricity mechanism is similar to that proposed for the two-dimensional materials commonly employed as solid lubricants, but it also enables the practical advantages of liquid lubricants to be maintained. When the pressure is increased, 1-dodecanol undergoes a polymorphic transformation into a phase that gives a higher friction. The DAC and DSC experiments indicate that the high-friction polymorph is an orthorhombic crystal. The polymorphic transformation pressure coincides with the onset of a dimple formation in the EHL films, revealing that the anomalous film shapes are caused by the formation of rigid orthorhombic crystals inside the contact. This is the first demonstration of a macroscale superlubricity in an EHL contact lubricated by a nonaqueous liquid that arises from bulk effects rather than tribochemical transformations at the surfaces. Since the superlubricity observed here results from phase transformations, it is continuously self-replenishing and is insensitive to surface chemistry and topology. This discovery creates the possibility of implementing superlubricity in a wide range of machine components, which would resul

Journal article

Gao H, Ewen J, Hartkamp R, Mueser M, Dini Det al., 2021, Scale-dependent friction-coverage relations and non-local dissipation in surfactant monolayers, Langmuir: the ACS journal of surfaces and colloids, Vol: 37, Pages: 2406-2418, ISSN: 0743-7463

Surfactant molecules, known as organic friction modifiers (OFMs), are routinely added to lubricants to reduce friction and wear between sliding surfaces. In macroscale experiments, friction generally decreases as the coverage of OFM molecules on the sliding surfaces increases; however, recent nanoscale experiments with sharp atomic force microscopy (AFM) tips have shown increasing friction. To elucidate the origin of these opposite trends, we use nonequilibrium molecular dynamics (NEMD) simulations and study kinetic friction between OFM monolayers and an indenting nanoscale asperity. For this purpose, we investigate various coverages of stearamide OFMs on iron oxide surfaces and silica AFM tips with different radii of curvature. We show that the differences between the friction–coverage relations from macroscale and nanoscale experiments are due to molecular plowing in the latter. For our small tip radii, the friction coefficient and indentation depth both have a nonmonotonic dependence on OFM surface coverage, with maxima occurring at intermediate coverage. We rationalize the nonmonotonic relations through a competition of two effects (confinement and packing density) that varying the surface coverage has on the effective stiffness of the OFM monolayers. We also show that kinetic friction is not very sensitive to the sliding velocity in the range studied, indicating that it originates from instabilities. Indeed, we find that friction predominately originates from plowing of the monolayers by the leading edge of the tip, where gauche defects are created, while thermal dissipation is mostly localized in molecules toward the trailing edge of the tip, where the chains return to a more extended conformation.

Journal article

Ewen J, Spikes H, Dini D, 2021, Contributions of molecular dynamics simulations to elastohydrodynamic lubrication, Tribology Letters, Vol: 69, ISSN: 1023-8883

The prediction of friction under elastohydrodynamic lubrication (EHL) conditions remains one of the most important and controversial areas of tribology. This is mostly because the pressure and shear rate conditions inside EHL contacts are particularly severe, which complicates experimental design. Over the last decade, molecular dynamics (MD) simulation has played an increasingly significant role in our fundamental understanding of molecular behaviour under EHL conditions. In recent years, MD simulation has shown quantitative agreement with friction and viscosity results obtained experimentally, meaning that they can, either in isolation or through the use of multiscale coupling methods, begin to be used to test and inform macroscale models for EHL problems. This is particularly useful under conditions that are relevant inside machine components, but are difficult to obtain experimentally without uncontrollable shear heating.

Journal article

Ayestaran Latorre C, Ewen J, Dini D, Righi MCet al., 2021, Ab initio insights into the interaction mechanisms between boron, nitrogen and oxygen doped diamond surfaces and water molecules, Carbon, Vol: 171, Pages: 575-584, ISSN: 0008-6223

Diamond and diamond-like carbon coatings are used in many applications ranging from biomedicine to tribology. A wide range of dopants have been tested to modify the hydrophilicity of these surfaces, since this is central to their biocompatibility and tribological performance in aqueous environments. Despite the large number of experimental investigations, an atomistic understanding of the effects of different dopants on carbon film hydrophilicity is still lacking. In this study, we employ ab initio calculations to elucidate the effects of B, N, and O dopants in several mechanisms that could modify interactions with water molecules and thus hydrophilicity. These include the adsorption of intact water molecules on the surfaces, minimum energy pathways for water dissociation, and subsequent interactions of hydrogenated and hydroxylated surfaces with water molecules. We find that all of the dopants considered enhance hydrophilicity, but they do so through different means. Most notably, B dopants can spontaneously chemisorb intact water molecules and increase its interactions in H-bond networks.

Journal article

Kondratyuk N, Pisarev V, Ewen J, 2020, Probing the high-pressure viscosity of hydrocarbon mixtures using molecular dynamics simulations, Journal of Chemical Physics, Vol: 153, ISSN: 0021-9606

Computational predictions of the high-pressure viscosity of hydrocarbon mixtures could help to accelerate the development of fuels and lubricants with improved performance. In this study, we use molecular dynamics simulations to study the viscosity and density of methylcyclohexane, 1-methylnaphthalene, and their binary mixtures at 323 K and pressures of up to 500 MPa. The simulation results are in excellent agreement with previous experiments available up to 100 MPa for both pure compounds (200 MPa for 1-methylnaphthalene) and the binary mixtures. For 1-methylnaphthalene, the viscosity initially increases slower-than-exponential with pressure before it reaches an inflection point and then increases faster-than-exponential. The inflection point (300 MPa) occurs at a pressure slightly below the one at which 1-methylnaphthalene is expected to enter the supercooled phase (400 MPa). For methylcyclohexane, the increase in viscosity with pressure is slower-than-exponential over the entire pressure range studied. The binary mixtures show intermediate pressure–viscosity responses between the two pure cases. The applicability of equations commonly used to describe the pressure dependence of viscosity, as well as the viscosity of binary mixtures, is evaluated against the computational predictions.

Journal article

Tan Z, Ewen J, Galvan S, Forte A, De Momi E, Rodriguez y Baena F, Dini Det al., 2020, What does a brain feel like?, Journal of Chemical Education, Vol: 97, Pages: 4078-4083, ISSN: 0021-9584

We present a two-part hands-on science outreach demonstration utilizing composite hydrogels to produce realistic models of the human brain. The blends of poly(vinyl alcohol) and Phytagel closely match the mechanical properties of real brain tissue under conditions representative of surgical operations. The composite hydrogel is simple to prepare, biocompatible, and nontoxic, and the required materials are widely available and inexpensive. The first part of the demonstration gives participants the opportunity to feel how soft and deformable our brains are. The second part allows students to perform a mock brain surgery on a simulated tumor. The demonstration tools are suitable for public engagement activities as well as for various student training groups. The activities encompass concepts in polymer chemistry, materials science, and biology.

Journal article

Ewen JP, Ayestarán Latorre C, Gattinoni C, Khajeh A, Moore JD, Remias J, Martini A, Dini Det al., 2020, Substituent effects on the thermal decomposition of phosphate esters on ferrous surfaces, The Journal of Physical Chemistry C, Vol: 124, Pages: 9852-9865, ISSN: 1932-7447

Phosphate esters have a wide range of industrial applications, for example in tribology where they are used as vapour phase lubricants and antiwear additives. An atomic-level understanding of phosphate ester tribofilm formation mechanisms is required to improve their tribological performance. A process of particular interest is the thermal decomposition of phosphate esters on steel surfaces, since this initiates polyphosphate film formation. In this study, reactive force field (ReaxFF) molecular dynamics (MD) simulations are used to study the thermal decomposition of phosphate esters with different substituents on several ferrous surfaces. The ReaxFF parameterisation was validated for a representative system using density functional theory (DFT) calculations. During the MD simulations on Fe3O4(001) and α-Fe(110), chemisorption interactions between the phosphate esters and the surfaces occur even at room temperature, and the number of molecule-surface bonds increases as the temperature increases from 300 to 1000 K. Conversely, on hydroxylated, amorphous Fe3O4, most of the molecules are physisorbed and some desorption occurs at high temperature. Thermal decomposition rates were much higher on Fe3O4(001) and particularly α-Fe(110) compared to hydroxylated, amorphous Fe3O4. This suggests that water passivates ferrous surfaces and inhibits phosphate ester chemisorption, decomposition, and ultimately polyphosphate film formation. For the alkyl phosphates, thermal decomposition proceeds mainly through C-O and C-H cleavage on Fe3O4(001). Aryl phosphates show much higher thermal stability, and decomposition on Fe3O4(001) only occurs through P-O and C-H cleavage, which require very high temperature. The onset temperature for C-O cleavage on Fe3O4(001) increases as: tertiary alkyl < secondary alkyl < primary linear alkyl ≈ primary branched alkyl < aryl. This order is consistent with experimental observations for the thermal stability of antiwear addi

Journal article

Zhang J, Ewen JP, Ueda M, Wong JSS, Spikes HAet al., 2020, Mechanochemistry of zinc dialkyldithiophosphate on steel surfaces under elastohydrodynamic lubrication conditions, ACS Applied Materials & Interfaces, Vol: 12, Pages: 6662-6676, ISSN: 1944-8244

Zinc dialkyldithiophosphate (ZDDP) is added to engine lubricants to reduce wear and ensure reliable operation. ZDDP reacts under rubbing conditions to form protective zinc/iron phosphate tribofilms on steel surfaces. Recently, it has been demonstrated that this process can be promoted by applied stresses in lubricated contacts, as well as temperature, and is thus mechanochemical in origin. In this study, a tribology test rig capable of applying very high loads has been developed to generate ZDDP tribofilms under full-film elastohydrodynamic lubrication (EHL) conditions in steel/steel ball-on-disk contacts. This provides a well-defined temperature and stress environment with negligible direct asperity contact in which to study mechanochemical processes. ZDDPs with branched primary and secondary alkyl substituents have been studied in three base oils, two with high EHL friction and one with low EHL friction. In the high EHL friction base oils, the tribofilm growth rate increases exponentially with shear stress and temperature for both ZDDPs, as predicted by a stress augmented thermal activation model. Conversely, under otherwise identical conditions, negligible ZDDP tribofilm formation takes place in the low EHL friction base oil. This confirms that the ZDDP reaction is driven by macroscopic shear stress rather than hydrostatic pressure. The secondary ZDDP forms tribofilms considerably faster than the primary ZDDP under equivalent conditions, suggesting that the initial decomposition reaction is the rate determining step for tribofilm formation. The rate of tribofilm growth is independent of ZDDP concentration over the range studied, indicating that this process follows zero-order kinetics. Under full-film EHL conditions, ZDDP tribofilm formation is promoted by macroscopic shear stress applied through the base oil molecules, which induces asymmetric stress on adsorbed ZDDP molecules to promote their decomposition and initiate rapid phosphate polymerisation.

Journal article

Ewen J, Ramos Fernandez E, Smith E, Dini Det al., 2020, Nonequilibrium Molecular Dynamics Simulations of Tribological Systems, Modeling and Simulation of Tribological Problems in Technology, Editors: Paggi, Hills, Publisher: Springer Nature, Pages: 95-130, ISBN: 978-3-030-20376-4

Book chapter

Ayestarán Latorre C, Ewen JP, Gattinoni C, Dini Det al., 2019, Simulating surfactant-iron oxide interfaces: from density functional theory to molecular dynamics, The Journal of Physical Chemistry B, Vol: 123, Pages: 6870-6881, ISSN: 1520-6106

Understanding the behaviour of surfactant molecules on iron oxide surfaces is important for many industrial applications. Molecular dynamics (MD) simulations of such systems have been limited by the absence of a force-field (FF) which accurately describes the molecule-surface interactions. In this study, interaction energies from density functional theory (DFT) + U calculations with a van der Waals functional are used to parameterize a classical FF for MD simulations of amide surfactants on iron oxide surfaces. The Original FF, which was derived using mixing rules and surface Lennard-Jones (LJ) parameters developed for nonpolar molecules, were shown to significantly underestimate the adsorption energy and overestimate the equilibrium adsorption distance compared to DFT. Conversely, the Optimized FF showed excellent agreement with the interaction energies obtained from DFT calculations for a wide range of surface coverages and molecular conformations near to and adsorbed on α-Fe2O3(0001). This was facilitated through the use of a Morse potential for strong chemisorption interactions, modified LJ parameters for weaker physisorption interactions, and adjusted partial charges for the electrostatic interactions. The Original FF and Optimized FF were compared in classical nonequilibrium molecular dynamics (NEMD) simulations of amide molecules confined between iron oxide surfaces. When the Optimized FF was employed, the amide molecules were pulled closer to the surface and the orientation of the headgroups was more similar to that observed in the DFT calculations compared to the Original FF. The Optimized FF proposed here facilitates classical MD simulations of anhydrous amide-iron oxide interfaces in which the interactions are representative of accurate DFT calculations.

Journal article

Restrepo SE, van Eijk MCP, Ewen JP, 2019, Behaviour of n-alkanes confined between iron oxide surfaces at high pressure and shear rate: A nonequilibrium molecular dynamics study, Tribology International, Vol: 137, Pages: 420-432, ISSN: 0301-679X

The behaviour of n-alkanes confined and sheared between iron oxide surfaces has been studied using nonequilibrium molecular dynamics simulations. The molecular extension, orientation, film structure, flow, and friction have been investigated for a range of n-alkane chain lengths under conditions representative of the elastohydrodynamic lubrication regime. At high pressure, the molecules show strong layering and long-range order, suggesting solid-like films. Conversely, high shear rates result in less elongated, layered, and ordered molecules; indicating more liquid-like films. Although Couette flow is usually observed for short n-alkanes, the flow is often non-linear for long n-alkanes. The friction coefficient increases logarithmically with shear rate, but the slope decreases with increasing pressure such that it becomes insensitive to shear rate for long n-alkanes.

Journal article

Ewen J, Gao H, Mueser M, Dini Det al., 2019, Shear heating, flow, and friction of confined molecular fluids at high pressure, Physical Chemistry Chemical Physics, Vol: 21, Pages: 5813-5823, ISSN: 1463-9076

Understanding the molecular-scale behavior of fluids confined and sheared between solid surfaces is important for many applications, particularly tribology where this often governs the macroscopic frictional response. In this study, nonequilibrium molecular dynamics simulations are performed to investigate the effects of fluid and surface properties on the spatially resolved temperature and flow profiles, as well as friction. The severe pressure and shear rate conditions studied are representative of the elastohydrodynamic lubrication regime. In agreement with tribology experiments, flexible lubricant molecules give low friction, which increases linearly with logarithmic shear rate, while bulky traction fluids show higher friction, but a weaker shear rate dependence. Compared to lubricants, traction fluids show more significant shear heating and stronger shear localization. Models developed for macroscopic systems can be used to describe both the spatially resolved temperature profile shape and the mean film temperature rise. The thermal conductivity of the fluids increases with pressure and is significantly higher for lubricants compared to traction fluids, in agreement with experimental results. In a subset of simulations, the efficiency of the thermostat in one of the surfaces is reduced to represent surfaces with lower thermal conductivity. For these unsymmetrical systems, the flow and the temperature profiles become strongly asymmetric and some thermal slip can occur at the solid-fluid interface, despite the absence of velocity slip. The larger temperature rises and steeper velocity gradients in these cases lead to large reductions in friction, particularly at high pressure and shear rate.

Journal article

Ewen J, Heyes D, Dini D, 2018, Advances in nonequilibrium molecular dynamics simulations of lubricants and additives, Friction, Vol: 6, Pages: 349-386, ISSN: 2223-7704

Nonequilibrium molecular dynamics (NEMD) simulations have provided unique insights into the nanoscale behaviour of lubricants under shear. This review discusses the early history of NEMD and its progression from a tool to corroborate theories of the liquid state, to an instrument that can directly evaluate important fluid properties, towards a potential design tool in tribology. The key methodological advances which have allowed this evolution are also highlighted. This is followed by a summary of bulk and confined NEMD simulations of liquid lubricants and lubricant additives, as they have progressed from simple atomic fluids to ever more complex, realistic molecules. The future outlook of NEMD in tribology, including the inclusion of chemical reactivity for additives, and coupling to continuum methods for large systems, is also briefly discussed.

Journal article

Gattinoni C, Ewen JP, Dini D, 2018, Adsorption of Surfactants on alpha-Fe2O3(0001): A Density Functional Theory Study, JOURNAL OF PHYSICAL CHEMISTRY C, Vol: 122, Pages: 20817-20826, ISSN: 1932-7447

Journal article

Clark RH, Ewen JP, Heins RJ, Stevenson PAet al., 2018, Fuel composition, EP3337877A1


This data is extracted from the Web of Science and reproduced under a licence from Thomson Reuters. You may not copy or re-distribute this data in whole or in part without the written consent of the Science business of Thomson Reuters.

Request URL: Request URI: /respub/WEB-INF/jsp/search-html.jsp Query String: respub-action=search.html&id=01010307&limit=30&person=true