CORROSION INHIBITION OF MILD STEEL BY COUMARATE-BASED IONIC LIQUIDS AND COATINGS.

The use of ionic liquids (ILs) as corrosion inhibitors gained attention due to their attractive properties such as high inhibition efficiency and ability to absorb onto metal surfaces. In this work, six  ILs, based on the coumarate anion combined with different nitrogen cations (triethylammonium, pyrrolidinium and imidazolium with short and long alkyl chain attached to the nitrogen atom) have been synthesized and evaluated as inhibitors for steel. The anticorrosion properties of these ILs in solution were investigated electrochemically and the metal surface was analyzed by SEM. Moreover, the IL prepared from the coumarate anion and N-dimethyl-N-tetradecyl ammonium ([DTA]Cou) was incorporated into an UV-coating formulation as an additive and by designing a similar ionic monomer which covalently links to the formulation. Impedance spectroscopy during 11 days of exposure to a solution of NaCl 0,01M, confirmed the high performance of the inhibitor in both solution and when incorporated into a coating. The synthesized ILs present efficiencies in solution exceeding 70%, in particular the ILs [DTA]Cou and tetradecyl imidazolium coumarate ([C14Im]Cou) showed efficiencies of 88% and 91% respectively. The obtained inhibitors showed interesting anticorrosion behaviors and demonstrated how different cations and an increase in the chain length affect the inhibition properties.

Lignin-Derivative Ionic Liquids as Corrosion Inhibitors.

Corrosion is a significant problem that negatively affects a wide range of structures and buildings, resulting in their premature failure, which causes safety hazards and significant economic loss. For this reason, various approaches have been developed to prevent or minimize the effects of corrosion, including corrosion inhibitors. Recently, biobased inhibitors have gained a certain interest thanks to their unique properties, eco-friendliness, and availability. Among all the green precursors, lignin is of particular interest, being a natural polymer that can be obtained from different sources including agricultural residues. Corrosion inhibitors based on ionic liquids (ILs) also present interesting advantages, such as low volatility and high tunability. If combined, it may be possible to obtain new lignin-based ILs that present interesting corrosion inhibitor properties. In this work, the inhibition properties of new biobased lignin ILs and the influence of anions and cations on the corrosion of mild steel in an aqueous solution of 0.01 M NaCl were investigated by Potentiostatic Electrochemical Impedance Spectroscopy (PEIS) and Cyclic Potentiodynamic Polarization (CPP). Moreover, the surface was characterized using SEM, EDS, and optical profilometry. The IL choline syringate showed promising performance, reducing the corrosion current after 24 h immersion in 0.01 M sodium chloride, from 1.66 µA/cm2 for the control to 0.066 µA/cm2 with 10 mM of the IL present. In addition to its performance as a corrosion inhibitor, both components of this IL also meet or exceed the current additional desired properties of such compounds, being readily available, and well tolerated in organisms and the environment.

Effect of cetrimonium carrier micelles on bacterial membranes and extracellular DNA, an in silico study.

Microorganisms do not live as dispersed single cells but rather they form aggregates with extracellular polymeric substances at interfaces. Biofilms are considered efficient life forms because they shield bacteria from biocides and collect dilute nutrients. This is a big concern in industry since the microorganisms can colonize a wide range of surfaces, accelerating material deterioration, colonizing medical devices, contaminating ultrapure drinking water, increasing energy costs and creating focus of infection. Conventional biocides that target a specific component of the bacteria are not effective in the presence of biofilms. Efficient biofilm inhibitors are based on a multitarget approach interacting with the bacteria and the biofilm matrix. Their rationale design requires a thorough understanding of inhibitory mechanisms that are still largely lacking today. Herein we uncover via molecular modelling the inhibition mechanism of cetrimonium 4-OH cinnamate (CTA-4OHcinn). Simulations show that CTA-4OH micelles can disrupt symmetric and asymmetric bilayers, representative of inner and outer bacterial membranes, following three stages: adsorption, assimilation, and defect formation. The main driving force for micellar attack is electrostatic interactions. In addition to disrupting the bilayers, the micelles work as carriers facilitating the trapping of 4OH cinnamate anions within the bilayer upper leaflet and overcoming electrostatic repulsion. The micelles also interact with extracellular DNA (e-DNA), which is one of the main components of biofilms. It is observed that CTA-4OHcinn forms spherical micelles on the DNA backbone; which hinders their ability to pack. This is demonstrated by modelling the DNA along the hbb histone-like protein, showing that in the presence of CTA-4OHcinn, DNA does not pack properly around hbb. The abilities of CTA-4OHcinn to cause cell death through membrane disruption and to disperse a mature, multi-species biofilm are also confirmed experimentally.

Tris(dialkylamino)cyclopropenium dialkylphosphate ionic liquids as lubricants.

Six new tris(dialkylamino)cyclopropenium dialkylphosphate ionic liquids (ILs), [C3(NR2)3]BEHP (NR2 = NEt2, NBuMe, NPr2, NBu2, NHex2, NDec2; BEHP = bis(2-ethylhexyl)phosphate), were prepared and characterised as potential lubricants. Thermophysical and thermochemical properties of these ILs were investigated, namely: viscosity, density, conductivity, miscibility, thermal stability and phase transitions. Miscibility studies indicated that [C3(NEt2)3]BEHP would not be suitable due to its water solubility and hexane immiscibility. [C3(NDec2)3]BEHP was not investigated as a lubricant due to its low purity (the chloride salt of this cation is also hexane miscible). Of the other four, [C3(NHex2)3]BEHP was found to exhibit significantly less wear for pin-on-disk test conditions than the standard phosphonium [P6,6,6,14]BEHP IL. The amount of wear was found to generally decrease with increasing molecular weight.

RE(III) 3-Furoate Complexes: Synthesis, Structure, and Corrosion Inhibiting Properties.

In this study, two types of Rare Earth (RE) 3-furoate complexes were synthesized by metathesis reactions between RE chlorides or nitrates and preformed sodium 3-furoate. Two different structural motifs were identified as Type 1RE and Type 2RE. The Type 1RE monometallic complexes form 2D polymeric networks with the composition [RE(3fur)3(H2O)2]n (1RE = 1La, 1Ce, 1Pr, 1Nd, 1Gd, 1Dy, 1Ho, 1Y; 3furH = 3-furoic acid) while Type 2RE bimetallic complexes form 3D polymeric systems [NaRE(3fur)4]n (2RE = 2Ho, 2Y, 2Er, 2Yb, 2Lu). The stoichiometric mole ratio used (RE: Na(3fur) = 1:3 or 1:4) in the metathesis reaction determines whether 1RE or 2RE (RE = Ho or Y) is formed, but 2RE (RE = Er, Yb, Lu) were obtained regardless of the ratio. The corrosion inhibition behaviour of the compounds has been examined using immersion studies and electrochemical measurements on AS1020 mild steel surfaces by a 0.01 M NaCl medium. Immersion test results revealed that [Y(3fur)3(H2O)2]n has the highest corrosion inhibition capability with 90% resistance after 168 h of immersion. Potentiodynamic polarisation (PP) measurements also indicate the dominant behaviour of the 1Y compound, and the PP curves show that these rare earth carboxylate compounds act predominantly as anodic inhibitors.

Extracellular DNA: A Critical Aspect of Marine Biofilms.

Multispecies biofilms represent a pervasive threat to marine-based industry, resulting in USD billions in annual losses through biofouling and microbiologically influenced corrosion (MIC). Biocides, the primary line of defence against marine biofilms, now face efficacy and toxicity challenges as chemical tolerance by microorganisms increases. A lack of fundamental understanding of species and EPS composition in marine biofilms remains a bottleneck for the development of effective, target-specific biocides with lower environmental impact. In the present study, marine biofilms are developed on steel with three bacterial isolates to evaluate the composition of the EPSs (extracellular polymeric substances) and population dynamics. Confocal laser scanning microscopy, scanning electron microscopy, and fluorimetry revealed that extracellular DNA (eDNA) was a critical structural component of the biofilms. Parallel population analysis indicated that all three strains were active members of the biofilm community. However, eDNA composition did not correlate with strain abundance or activity. The results of the EPS composition analysis and population analysis reveal that biofilms in marine conditions can be stable, well-defined communities, with enabling populations that shape the EPSs. Under marine conditions, eDNA is a critical EPS component of the biofilm and represents a promising target for the enhancement of biocide specificity against these populations.

Enhancing Biocide Efficacy: Targeting Extracellular DNA for Marine Biofilm Disruption.

Biofilm formation is a global health, safety and economic concern. The extracellular composition of deleterious multispecies biofilms remains uncanvassed, leading to an absence of targeted biofilm mitigation strategies. Besides economic incentives, drive also exists from industry and research to develop and apply environmentally sustainable chemical treatments (biocides); especially in engineered systems associated with the marine environment. Recently, extracellular DNA (eDNA) was implicated as a critical structural polymer in marine biofilms. Additionally, an environmentally sustainable, multi-functional biocide was also introduced to manage corrosion and biofilm formation. To anticipate biofilm tolerance acquisition to chemical treatments and reduce biocide application quantities, the present research investigated eDNA as a target for biofilm dispersal and potential enhancement of biocide function. Results indicate that mature biofilm viability can be reduced by two-fold using reduced concentrations of the biocide alone (1 mM instead of the recommended 10 mM). Importantly, through the incorporation of an eDNA degradation stage, biocide function could be enhanced by a further ~90% (one further log reduction in viability). Biofilm architecture analysis post-treatment revealed that endonuclease targeting of the matrix allowed greater biocide penetration, leading to the observed viability reduction. Biofilm matrix eDNA is a promising target for biofilm dispersal and antimicrobial enhancement in clinical and engineered systems.

Conditioning of metal surfaces enhances Shewanella chilikensis adhesion.

Microbiologically influenced corrosion and biofouling of steels depend on the adsorption of a conditioning film and subsequent attachment of bacteria. Extracellular deoxyribonucleic acid (eDNA) and amino acids are biologically critical nutrient sources and are ubiquitous in marine environments. However, little is known about their role as conditioning film molecules in early biofilm formation on metallic surfaces. The present study evaluated the capacity for eDNA and amino acids to form a conditioning film on carbon steel (CS), and subsequently, the influence of these conditioning films on bacterial attachment using a marine bacterial strain. Conditioning films of eDNA or amino acids were formed on CS through physical adsorption. Biochemical and microscopic analysis of eDNA conditioning, amino acid conditioning and control CS surfaces demonstrated that organic conditioning surfaces promoted bacterial attachment. The results highlight the importance of conditioning the surface in initial bacterial attachment to steel.

Efficiency of a Novel Multifunctional Corrosion Inhibitor Against Biofilms Developed on Carbon Steel.

In natural environments, populations of microorganisms rapidly colonise surfaces forming biofilms. These sessile communities comprise a variety of species which contribute to biofouling and microbiologically influenced corrosion (MIC), especially on metals. Species heterogeneity in natural systems confers higher tolerance to adverse conditions such as biocide treatment compared with single species laboratory simulations. Effective chemical treatments to combat recalcitrant biofilms are often dangerous to apply; both to operators and the environment, and face international embargoes. Today, there is a drive to exchange current toxic and environmentally hazardous biocides with less harmful compounds. One effective method of achieving this goal is to generate multi-functional compounds capable of tackling corrosion and biofilm formation simultaneously, thus reducing the number of compounds in dosing procedures. In a previous study, a novel corrosion inhibitor demonstrated biocidal effects against three marine isolates during the early stages of biofilm formation. The compound; CTA-4OHcinn, holds great promise as a multi-functional inhibitor, however its effect on complex, multi-species biofilms remains unknown. Here we evaluate CTA-4OHcinn biocidal capacity against multi-species biofilms developed from oilfield samples. Mature biofilms were developed and treated with 10 mM CTA-4OHcinn for 4 h. The effects of the compound were assessed using mean probable number (MPN), adenosine triphosphate (ATP) quantification, scanning electron microscopy (SEM) and confocal laser scanning microscopy (CLSM). Results demonstrate that CTA-4OHcinn significantly reduces the viability of mature biofilms, supporting previous demonstrations on the secondary function of CTA-4OHcinn as a biocide. CLSM results further indicate that CTA-4OHcinn targets the cell membrane resulting in lysis. This finding complements the established corrosion inhibition function of CTA-4OHcinn, indicating the compound is a true multi-functional organic corrosion inhibitor.

Modelling cetrimonium micelles as 4-OH cinnamate carriers targeting a hydrated iron oxide surface.

HYPOTHESIS: Molecular interactions between 4-OH-cinnamate and cetrimonium in solution result in improved adsorption of the cinnamate on mild steel, developing a protective mechanism against the diffusion of corrosive chloride to the oxide surface. Fundamental understanding of this mechanism should allow new design routes for the development of eco-friendly corrosion inhibitors. EXPERIMENTS: Via classic molecular dynamics, simulations were carried out for cetrimonium and 4-OH-cinnamate in aqueous solutions at different ionic strengths and the results were validated with experimental SAXS data. Self-aggregation of cetrimonium 4-OH-cinnamate on a hydrated hematite surface was then simulated and results were compared with cryo-TEM imaging for the same compound. Finally, the effect of the adsorbed aggregates on chloride diffusion to the oxide surface was modelled. FINDINGS: Simulations showed the encapsulation of 4-OH-cinnamate into cetrimonium micelles, consistent with experiments. The newly formed micelles adsorb onto a hydrated iron oxide surface by forming hydrogen bonds between their carboxylate outer-shell groups and the surface hydroxyls. As the adsorbate concentrations increase, there is a morphological transition from spherical to wormlike adsorbed aggregates. The wormlike structure can block chloride ions, demonstrating a synergistic inhibitory mechanism between both cetrimonium and 4-OH-cinnamate. Encapsulation and delivery of active compounds to certain targets, such as carcinogenic tumors, have been well studied in biochemistry research, we demonstrate that the same mechanism can be applied to the design of efficient corrosion inhibitors, optimizing their delivery to the metal surface.

Evaluation of a novel, multi-functional inhibitor compound for prevention of biofilm formation on carbon steel in marine environments.

Chemical biocides remain the most effective mitigation strategy against microbiologically influenced corrosion (MIC), one of the costliest and most pervasive forms of corrosion in industry. However, toxicity and environmental concerns associated with these compounds are encouraging the development of more environmentally friendly MIC inhibitors. In this study, we evaluated the antimicrobial effect of a novel, multi-functional organic corrosion inhibitor (OCI) compound, cetrimonium trans-4-hydroxy-cinnamate (CTA-4OHcinn). Attachment of three bacterial strains, Shewanella chilikensis, Pseudomonas balearica and Klebsiella pneumoniae was evaluated on wet-ground (120 grit finish) and pre-oxidised carbon steel surfaces (AISI 1030), in the presence and absence of the new OCI compound. Our study revealed that all strains preferentially attached to pre-oxidised surfaces as indicated by confocal laser scanning microscopy, scanning electron microscopy and standard colony forming unit (CFU) quantification assays. The inhibitor compound at 10 mM demonstrated 100% reduction in S. chilikensis attachment independent of initial surface condition, while the other two strains were reduced by at least 99.7% of the original viable cell number. Our results demonstrate that CTA-4OHcinn is biocidal active and has promise as a multifunctional, environmentally sound MIC inhibitor for industrial applications.

Electrochemical and Surface Characterization Study on the Corrosion Inhibition of Mild Steel 1030 by the Cationic Surfactant Cetrimonium Trans-4-hydroxy-cinnamate.

Effective corrosion inhibition of mild steel 1030 at 0.01 M NaCl concentration was achieved by the use of the nontoxic surfactant salt cetrimonium trans-4-hydroxy-cinnamate (CTA-4OHcinn). Polarization analysis on the steel samples immersed for 24 h in the control and CTA-4OHcinn-containing solutions shows the development of a passivation potential that is more obvious at higher inhibitor concentrations along with a maximum inhibition efficiency of 97.8%. Electrochemical impedance spectroscopy (EIS) pinpoints the effect of the inhibitor on the corroding regions of the metal surface, showing an increase in the local electric resistance and conversely a decrease in the local capacitance, which indicates that the charge transfer in the corroding regions is being hindered by a deposition process. This is consistent with scanning electron microscopy (SEM) images, showing the presence of a porous oxide matrix that fills localized corrosion sites on the metal surface after 24 h of immersion in a 0.01 M NaCl + 10 mM inhibitor solution. Additionally, SEM analysis also shows the formation of an organic film surrounding the defects that is able to shield chloride attack. As a result of diffusion of chloride from the defects below the protective film, filiform corrosion can be seen. Time-resolved impedance analysis over the first 120 min of immersion in the control and inhibitor solution shows that significant inhibitor protection does not take place immediately and there is a lag phase in the first 50 min of immersion, suggesting that early localized corrosion drives further adsorption of inhibitor micelles on the metal surface. This is in agreement with X-ray photoelectron spectroscopy (XPS) analysis, which indicates a complete surface coverage over the first 2 h of immersion in a concentrated inhibitor solution. XPS also shows the heterogeneity of the film, where some parts are poorly covered, revealing the underlying surface containing iron.

A novel approach to improve the oil miscibility and incorporate multifunctionality in ionic liquids as lubricant additives.

Recently ionic liquids (ILs) have shown promising tribological properties as additives in base oils; however their lack of miscibility is a problem, with very few ILs being compatible with lubricant oil formulation (non-polar base oils). This work shows the use of a surfactant which can increase the range of available ILs that are stable when added to these base oils. In this study a range of tetraalkylphosphonium based ILs were successfully blended with a PIBSA surfactant and these blends were all shown to be miscible in a non-polar base oil. Without the PIBSA a number of the ILs were immiscible in the base oil. The tribological properties of IL additives that are miscible in the non-polar base oils were compared with and without the surfactant present and showed that the presence of the PIBSA did not affect the IL additives performance. Additionally, two ILs that are immiscible without the surfactant showed the greatest reduction in friction and wear. SEM analysis showed an increase in the amount of phosphorus on the wear surface when the surfactant was present, suggesting that the PIBSA enhances tribo-film formation. NMR, FTIR, DLS and TEM investigations into the interactions between the PIBSA and the ILs showed that the improved stability in the base oil may be due to intermolecular interactions such as hydrophobic, van der Waals, dipole-dipole or ion-dipole that reduce the size distribution of the previously immiscible ILs. The presence of the ILs was also shown to improve the resistance to corrosion. Prior to this study the ILs available for use as lubricant additives was severely limited and compromised, mostly based upon their miscibility. Here the use of PIBSA to increase the range of ILs available as lubricant additives has vastly improved the promise that they represent in this area.

Design of Polymeric Corrosion Inhibitors Based on Ionic Coumarate Groups.

Efficient, environmentally friendly organic corrosion inhibitors are being sought to alleviate the financial loss caused by corrosion degradation of mild steel materials. Here, we show the synthesis and characterization of monomeric ionic coumarate corrosion inhibitors and their integration into polymeric acrylic UV coatings. For this purpose, we investigated the effect of including the coumarate corrosion inhibitors into the acrylic UV coating by three different means. The corrosion inhibitors could be added as a standalone ionic liquid additive, or they can be ionically attached or covalently attached to the acrylic polymer network. To achieve this, two methacrylic monomers and one nonpolymerizable ionic coumarate compound were synthesized. The anticorrosion properties of the three coumarate compounds when added to a chloride aqueous solution were investigated by various techniques. Next, the three ionic coumarate compounds were integrated into an acrylic UV polymer composition. Here, the UV coating, which shows the best anticorrosion performance, was the one where the coumarate group is attached covalently or ionically to the polymer. The UV coating, which included the coumarate compound as a nonreactive additive, presented leaching problems from the coating, limiting its anticorrosion effect. The work herein shows that the development of polymeric corrosion inhibitors that combine the barrier properties of the polymer coating and the anticorrosive identity of the organic inhibitor is a powerful strategy to prevent corrosion.

Corrosion Inhibition of Mild Steel by Cetrimonium trans-4-Hydroxy Cinnamate: Entrapment and Delivery of the Anion Inhibitor through Speciation and Micellar Formation.

Chemical inhibitors are widely used to protect metallic alloys from corrosion in aqueous environments. This Letter investigates the possible synergistic behavior of a quaternary ammonium carboxylate compound toward the development of a new system taking advantage of the surface activity of a known antimicrobial surfactant molecule, hexadecyl trimethylammonium cation, combined with a known organic corrosion inhibitor, the trans-4-hydroxy-cinnamate anion. Short-term potentiodynamic polarization (PP) studies combined with immersion in aqueous chloride solutions demonstrated the high inhibition efficiency of the combination of ions, and NMR pfg-diffusion measurements revealed micellar formation that was concentration- and pH-dependent. The NMR data suggest that speciation changes occur in the solution that correlate with enhanced corrosion inhibition efficiency at higher pH and at concentrations above the CMC of the compound. This new contribution may provide a rational molecular design toward delivering corrosion inhibitors to a metal surface through controlled speciation in solution.

Leaching Behavior and Corrosion Inhibition of a Rare Earth Carboxylate Incorporated Epoxy Coating System.

While paint coatings act as important barriers to corrosion, defects can lead to localized, rapid metal loss. The addition of corrosion inhibitors that are capable of leaching from a coating to protect the metal surface at a defect can prevent this type of corrosion. This work investigates the release and corrosion protection capabilities of two rare earth (RE) carboxylate inhibitors from an epoxy coating as an initial step to understanding their leaching behavior and interaction with the coating system. Leaching experiments were performed via inductively coupled plasma mass spectroscopy (ICP-MS) analyses of the solutions in which free-standing coatings loaded with varying concentrations of inhibitor compounds had been immersed. Inhibitor release from the epoxy coating was observed to be dependent on initial inhibitor concentration, inhibitor chemistry, and solution pH conditions. The coating systems with greater initial inhibitor loadings showed higher leaching rates, particularly in acidic environments. Following immersion, the absence of characteristic inhibitor peaks in the FTIR spectra of the coatings also confirmed leaching had taken place. Cross-sectional views of the coatings after exposure to the pH 1 environment presented a chloride infusion zone at the coating/solution interface where the inhibitor had leached out. The RE active inhibition provided by the leached RE carboxylate inhibitors was verified by exposure of a coating defect to a chloride contaminated environment.

New dimensions in salt-solvent mixtures: a 4th evolution of ionic liquids.

In the field of ionic liquids (ILs) it has long been of fundamental interest to examine the transition from salt-in-solvent behaviour to pure liquid-salt behaviour, in terms of structures and properties. At the same time, a variety of applications have beneficially employed IL-solvent mixtures as media that offer an optimal set of properties. Their properties in many cases can be other than as expected on the basis of simple mixing concepts. Instead, they can reflect the distinct structural and interaction changes that occur as the mixture passes through the various stages from pure coulombic medium, to "plasticised" coulombic medium, into a meso-region where distinct molecular and ionic domains can co-exist. Such domains can persist to quite a high dilution into the salt-in-solvent regime and their presence manifests itself in a number of important synergistic interaction effects in diverse areas such as membrane transport and corrosion protection. Similarly, the use of ionic liquids in synthetic processes where there is a significant volume fraction of molecular species present can produce a variety of distinct and unexpected effects. The range of these salt-solvent mixtures is considerably broader than just those based on ionic liquids, since there is only minor value in the pure salt being a liquid at the outset. In other words, the extensive families of organic and metal salts become candidates for study and use. Our perspective then is of an evolution of ionic liquids into a broader field of fundamental phenomena and applications. This can draw on an even larger family of tuneable salts that exhibit an exciting combination of properties when mixed with molecular liquids.

In-Situ-Activated N-Doped Mesoporous Carbon from a Protic Salt and Its Performance in Supercapacitors.

Protic salts have been recently recognized to be an excellent carbon source to obtain highly ordered N-doped carbon without the need of tedious and time-consuming preparation steps that are usually involved in traditional polymer-based precursors. Herein, we report a direct co-pyrolysis of an easily synthesized protic salt (benzimidazolium triflate) with calcium and sodium citrate at 850 °C to obtain N-doped mesoporous carbons from a single calcination procedure. It was found that sodium citrate plays a role in the final carbon porosity and acts as an in situ activator. This results in a large surface area as high as 1738 m2/g with a homogeneous pore size distribution and a moderate nitrogen doping level of 3.1%. X-ray photoelectron spectroscopy (XPS) measurements revealed that graphitic and pyridinic groups are the main nitrogen species present in the material, and their content depends on the amount of sodium citrate used during pyrolysis. Transmission electron microscopy (TEM) investigation showed that sodium citrate assists the formation of graphitic domains and many carbon nanosheets were observed. When applied as supercapacitor electrodes, a specific capacitance of 111 F/g in organic electrolyte was obtained and an excellent capacitance retention of 85.9% was observed at a current density of 10 A/g. At an operating voltage of 3.0 V, the device provided a maximum energy density of 35 W h/kg and a maximum power density of 12 kW/kg.

Addition of low concentrations of an ionic liquid to a base oil reduces friction over multiple length scales: a combined nano- and macrotribology investigation.

The efficacy of ionic liquids (ILs) as lubricant additives to a model base oil has been probed at the nanoscale and macroscale as a function of IL concentration using the same materials. Silica surfaces lubricated with mixtures of the IL trihexyl(tetradecyl)phosphonium bis(2,4,4-trimethylpentyl)phosphinate and hexadecane are probed using atomic force microscopy (AFM) (nanoscale) and ball-on-disc tribometer (macroscale). At both length scales the pure IL is a much more effective lubricant than hexadecane. At the nanoscale, 2.0 mol% IL (and above) in hexadecane lubricates the silica as well as the pure IL due to the formation of a robust IL boundary layer that separates the sliding surfaces. At the macroscale the lubrication is highly load dependent; at low loads all the mixtures lubricate as effectively as the pure IL, whereas at higher loads rather high concentrations are required to provide IL like lubrication. Wear is also pronounced at high loads, for all cases except the pure IL, and a tribofilm is formed. Together, the nano- and macroscales results reveal that the IL is an effective lubricant additive - it reduces friction - in both the boundary regime at the nanoscale and mixed regime at the macroscale.

Ionic Liquid Adsorption and Nanotribology at the Silica-Oil Interface: Hundred-Fold Dilution in Oil Lubricates as Effectively as the Pure Ionic Liquid.

The remarkable physical properties of ionic liquids (ILs) make them potentially excellent lubricants. One of the challenges for using ILs as lubricants is their high cost. In this article, atomic force microscopy (AFM) nanotribology measurements reveal that a 1 mol % solution of IL dissolved in an oil lubricates the silica surface as effectively as the pure IL. The adsorption isotherm shows that the IL surface excess need only be approximately half of the saturation value to prevent surface contact and effectively lubricate the sliding surfaces. Using ILs in this way makes them viable for large-scale applications.