Position of Carbonyl Group Affects Tribological Performance of Ester Friction Modifiers.

The tribological properties of lubricants can be effectively improved by the introduction of amphiphilic molecules, whose performance is largely affected by their polar head groups. In this work, the tribological performance in steel-steel contacts of two isomers, glycerol monostearate (GMS) and stearyl glycerate (SG), a glyceride and a glycerate, were investigated as organic friction modifiers (OFM) in hexadecane. SG exhibits a much lower friction coefficient and wear than GMS despite their similar structures. The same applies when comparing the performance of oleyl glycerate (OG) and its isomer, glycerol monooleate (GMO). Surface chemical analysis shows that SG forms a polar, carbon-based, tribofilm of around tens of nanometers thick, while GMS does not. This tribofilm shows low friction and robustness under nanotribology test, which may contribute to its superior performance at the macro-scale. The reason for this tribofilm formation can be due to the stronger adsorption of SG on the steel surface than that of GMS. The tribofilm formation can be stress-activated since lower friction and higher tribofilm coverage can be obtained under high load. This work offers insights into the lubrication mechanism of a novel OFM and provides strategies for OFM design.

Probing the Nanoscale Heterogeneous Mixing in a High-Performance Polymer Blend.

The blend of polyetheretherketone (PEEK) and polybenzimidazole (PBI) produces a high-performance blend (PPB) that is a potential replacement material in several industries due to its high temperature stability and desirable tribological properties. Understanding the nanoscale structure and interface of the two domains of the blend is critical for elucidating the origin of these desirable properties. Whilst achieving the physical characterisation of the domain structures is relatively uncomplicated, the elucidation of structures at the interface presents a significant experimental challenge. In this work, we combine atomic force microscopy (AFM) with an IR laser (AFM-IR) and thermal cantilever probes (nanoTA) to gain insights into the chemical heterogeneity and extent of mixing within the blend structure for the first time. The AFM-IR and nanoTA measurements show that domains in the blend are compositionally different from those of the pure PEEK and PBI polymers, with significant variations observed in a transition region several microns wide in proximity to domain boundary. This strongly points to physical mixing of the two components on a molecular scale at the interface. The versatility intrinsic to the combined methodology employed in this work provides nano- and microscale chemical information that can be used to understand the link between properties of different length scales across a wide range of materials.

Temperature dependence of molybdenum dialkyl dithiocarbamate (MoDTC) tribofilms via time-resolved Raman spectroscopy.

Molybdenum dialkyl dithiocarbamate (MoDTC) is a friction reducing additive commonly used in lubricants. MoDTC works by forming a low-friction molybdenum disulphide (MoS2) film (tribofilm) on rubbed surfaces. MoDTC-induced MoS2 tribofilms have been studied extensively ex-situ; however, there is no consensus on the chemical mechanism of its formation process. By combining Raman spectroscopy with a tribometer, effects of temperature and shear stress on MoS2 tribofilm formation in steel-steel contacts were examined. Time-resolved Raman spectra of the tribofilm were acquired, together with the instantaneous friction coefficient. The tribofilm is constantly being formed and removed mechanically during rubbing. Increasing shear stress promotes MoS2 formation. The nature of the tribofilm is temperature-dependent, with high-temperature tribofilms giving a higher friction than lower temperature films. Below a critical temperature Tc, a small amount of MoS2 gives significant friction reduction. Above Tc, a patchy film with more MoS2, together with a substantial amount of amorphous carbon attributed to base oil degradation, forms. The composition of this tribofilm evolves during rubbing and a temporal correlation is found between carbon signal intensity and friction. Our results highlight the mechanochemical nature of tribofilm formation process and the role of oil degradation in the effectiveness of friction modifier MoDTC.

Mechanochemistry of Zinc Dialkyldithiophosphate on Steel Surfaces under Elastohydrodynamic Lubrication Conditions.

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 polymerization.

Adsorption of Organic Friction Modifier Additives.

Organic friction modifier additives (OFMs) are surfactant molecules added to engine oils to reduce friction in the boundary lubrication regime. They are thought to work by forming an absorbed layer, which provides low friction. This paper studied the relationship between the adsorption of OFMs and their friction and wear-reducing properties in a rubbing contact formed by a stationary glass ball and a rotating silicon disk under the boundary lubrication regime. The effect of molecular structure was investigated by using OFMs of various tail saturation and head group chemistry. OFMs tested were oleic acid, octadecylamine, oleylamine, and glycerol monooleate. The thickness of an OFM-adsorbed layer in hexadecane, examined in situ by spectroscopic ellipsometry and quartz crystal microbalance (QCM), depends on the molecular structure and the concentration of the OFM. As expected, the saturated, linear chain gives the thickest film. A critical OFM layer thickness of about 0.6 nm is necessary to achieve low initial and maximum friction. The thicker OFM layers are accompanied by narrower wear tracks, which are rougher than the wider, smoother wear tracks formed with thinner OFM layers. The interplay between the thickness of the OFM layer and wear track surface roughness results in all OFM layers having similar steady state friction. This shows that the apparent effect of OFM depends on the stage of the rubbing test: initially on friction, and then subsequently on surface damage. Despite OFMs and the base oil having similar refractive indices, ellipsometry was found to be a suitable technique for examining the adsorption of OFM additives from an oil-based solution and showed reasonable correlation with QCM results.

Effect of Aging on the Removal of Asphaltene Deposits with Aromatic Solvent.

Surface deposition of destabilized colloidal particles of asphaltenes poses a serious and costly problem during petroleum production. Remediation of asphaltene-fouled well bore and surface facilities is often undertaken by flowing aromatic solvent to remove deposited films. However, little is known about the properties of deposited asphaltene films during their removal by solvent rinsing. Here, we carry out quartz crystal microbalance with dissipation monitoring (QCM-D) experiments to investigate surface deposition of destabilized colloidal particles of asphaltenes and their subsequent removal by solvent rinsing. It is shown that the properties of deposited films during solvent removal depend on the history of the deposit. Newly formed deposit films are removed immediately without significant change in their mechanical properties during removal. However, deposits that remain on the surface for an extended time in a poor solvent (a low asphaltene solubility solvent), "aged deposits", are more difficult to remove and exhibit increased dissipation during the removal period, indicating that they swell and are softer. Liquid-cell atomic force microscopy (AFM) confirms that aged deposits swell when the quality of the solvent is subsequently improved by exchanging for a high asphaltene solubility solvent. Deposit swelling is accompanied by a change in film morphology, from particulate to continuous. Stubborn deposits of aged asphaltene films, which remain after solvent rinsing, may be partly removed by flowing dissolved asphaltenes in good solvent. Hence, reinjection of asphaltenes during remediation can aid deposit removal.

Cargo Release from Polymeric Vesicles under Shear.

In this paper we study the release of cargo from polymeric nano-carriers under shear. Vesicles formed by two star block polymers- A 12 B 6 C 2 ( A B C ) and A 12 B 6 A 2 ( A B A )-and one linear block copolymer- A 14 B 6 ( A B ), are investigated using dissipative particle dynamics (DPD) simulations. A - and C -blocks are solvophobic and B -block is solvophilic. The three polymers form vesicles of different structures. The vesicles are subjected to shear both in bulk and between solvophobic walls. In bulk shear, the mechanisms of cargo release are similar for all vesicles, with cargo travelling through vesicle membrane with no preferential release location. When sheared between walls, high cargo release rate is only observed with A B C vesicle after it touches the wall. For A B C vesicle, the critical condition for high cargo release rate is the formation of wall-polymersome interface after which the effect of shear rate in promoting cargo release is secondary. High release rate is achieved by the formation of solvophilic pathway allowing cargo to travel from the vesicle cavity to the vesicle exterior. The results in this paper show that well controlled target cargo release using polymersomes can be achieved with polymers of suitable design and can potentially be very useful for engineering applications. As an example, polymersomes can be used as carriers for surface active friction reducing additives which are only released at rubbing surfaces where the additives are needed most.

Structure of Amphiphilic Terpolymer Raspberry Vesicles.

Terpolymer raspberry vesicles contain domains of different chemical affinities. They are potential candidates as multi-compartment cargo carriers. Their efficacy depends on their stability and load capacity. Using a model star terpolymer system in an aqueous solution, a dissipative particle dynamic (DPD) simulation is employed to investigate how equilibrium aggregate structures are affected by polymer concentration and pairwise interaction energy in a solution. It is shown that a critical mass of polymer is necessary for vesicle formation. The free energy of the equilibrium aggregates are calculated and the results show that the transition from micelles to vesicles is governed by the interactions between the longest solvophobic block and the solvent. In addition, the ability of vesicles to encapsulate solvent is assessed. It is found that reducing the interaction energy favours solvent encapsulation, although solvent molecules can permeate through the vesicle's shell when repulsive interactions among monomers are low. Thus, one can optimize the loading capacity and the release rate of the vesicles by turning pairwise interaction energies of the polymer and the solvent. The ability to predict and control these aspects of the vesicles is an essential step towards designing vesicles for specific purposes.

Flow measurements of a polyphenyl ether oil in an elastohydrodynamic contact.

A novel methodology, based on the use of phosphorescence imaging, is applied to determine the local through-thickness velocity profile of lubricant in an elastohydrodynamic contact. The technique has spatial and temporal resolutions of 40 µm and 340 µs respectively and thus allows lubricant rheology to be investigated at conditions close to service conditions. The capability of the newly-developed method is verified by examining the flow of 5P4E polyphenyl ether, a lubricant base fluid used in very high temperature applications and is well-known for its high viscosity-pressure coefficient. Experimental results highlight the effect of the contact pressure on the velocity profile of this fluid in lubricated contacts. At low pressures, the velocity profile of 5P4E is close to linear, characteristic of Couette flow. As the local pressure increases, its velocity profile progressively deviates from a Couette profile and shear banding is evident at high pressure.