Imperial College London


Faculty of EngineeringDepartment of Mechanical Engineering




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Mrs Chrissy Stevens +44 (0)20 7594 7064




673City and Guilds BuildingSouth Kensington Campus





Publication Type

467 results found

Ueda M, Wainwright B, Spikes H, Kadiric Aet al., 2022, The effect of friction on micropitting, Wear, Vol: 488-489, Pages: 1-13, ISSN: 0043-1648

Micropitting is a type of surface fatigue damage that occurs in rolling-sliding contacts operating under thin oil film conditions. It is caused by stress fluctuations, brought about by surface asperity interactions, which lead to initiation and propagation of numerous surface fatigue cracks and subsequent loss of material. Despite its increasing importance to gear and bearing reliability, the mechanisms of micropitting are poorly understood. This is particularly the case concerning the effects of friction on micropitting which are difficult to study under controlled conditions. This is because it is difficult to isolate the friction effects from other influential factors, in particular from the build-up of any anti-wear tribofilm and its subsequent effect on the running-in of counterface roughness that is known to strongly affect micropitting through its influence on severity of asperity stresses. This paper presents new data on the impact of friction on micropitting obtained using a new test methodology. Micropitting tests were conducted using a ball-on-disc MTM rig with the additional functionality to continuously monitor the growth of tribofilm during the test. Friction was varied by using custom-made oils containing different concentrations of MoDTC. Crucially, the effect of friction was isolated from the effect of counterface roughness running-in by introducing the MoDTC blend only after the running-in period was completed with a ZDDP solution alone. This approach eliminates the influence of MoDTC on ZDDP anti-wear tribofilm growth in early stages and hence ensures the same running-in takes place in each test. This gives similar asperity pressure history, regardless of the amount of MoDTC present.Resultsshow that friction has a very significant impact on micropitting; for example, the extent of micropitting was reduced by a factor of 10 when friction coefficient was reduced from about 0.1 to 0.04. Lower friction results in fewer surface cracks which grow at a s

Journal article

Ueda M, Spikes H, Kadiric A, 2022, Influence of black oxide coating on micropitting and ZDDP tribofilm formation, Tribology Transactions, Vol: 65, Pages: 1-21, ISSN: 1040-2004

Micropitting is a type of surface fatigue damage that occurs in rolling-sliding contacts operating under thin oil film conditions. Application of black oxide (BO) coating to steel rubbing surfaces has been suggested as a potential approach to alleviate micropitting. This paper confirms that BO coatings can prevent micropitting and identifies the predominant mechanism by which this occurs.Micropitting tests were carried out using ZDDP solutions in a ball on disc tribometer. Micropitting was preferentially generated on the smooth balls and this was completely prevented by applying a BO coating to the rougher discs, regardless of whether the balls were coated or not. In contrast, when the rough discs were not BO-coated, micropitting was consistently generated on both BO-coated and uncoated balls. BO coating has about one quarter the hardness of the steel used and was found to be very rapidly removed from the surface asperity peaks at the onset of rubbing, despite the presence of ZDDP. This resulted in an almost immediate and very large reduction of the surface roughness of the discs and this prevented high asperity stresses that would normally initiate and propagate the surface fatigue cracks leading to micropitting. Parallel measurement showed that BO did not suppress tribofilm growth, so the ZDDP was able to protect against adhesive wear while not promoting micropitting. The insights presented here can help with the design of components and lubricants that are effective in controlling both sliding wear and micropitting.

Journal article

Zhang J, Campen S, Wong J, Spikes Het al., 2022, Oxidational wear in lubricated contacts – or is it?, Tribology International, Vol: 165, Pages: 1-9, ISSN: 0301-679X

This study examines the influence of inert gas atmosphere on the wear behaviour of rubbing steel-on-steel contacts lubricated by two hydrocarbon base fluids, isooctane and hexadecane. It is found that for both fluids, wear and mean friction in nitrogen and argon atmospheres are considerably lower than in dry air. As the oxygen content in nitrogen is increased, mean friction and wear both increase, to level out above about 10% oxygen (an O2 partial pressure of 10 kPa). Raman analysis of rubbed surfaces shows the presence of a carbon film on surfaces rubbed in inert gas and at low O2 levels. This film is not observed at high O2 levels.These findings indicate that the prevailing model of oxidational wear in lubricated contacts, that states that wear is greater in air than in inert gas because of corrosion by oxygen, is largely incorrect. Instead, the deleterious effect of oxygen on lubricated wear is primarily due to it preventing the formation of a lubricious, carbon-based boundary film that is generated from hydrocarbon base fluids on rubbing steel surfaces in inert gas conditions.The ability of organic fuels and lubricants to form carbon-based films on rubbing steel surfaces in inert atmospheres may provide a mechanism for reducing friction and wear of fuel- and oil-lubricated machine components. The study also provides a platform from which to design lubricant formulations for use in inert atmospheres.

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

Pagkalis K, Spikes H, Jelita Rydel J, Ingram M, Kadiric Aet al., 2021, The influence of steel composition on the formation and effectiveness of anti-wear films in tribological contacts, Tribology Letters, Vol: 69, Pages: 1-20, ISSN: 1023-8883

The effectiveness of antiwear additives in laboratory tests is commonly evaluated using specimens made of AISI 52100 through-hardened bearing steel. However, many lubricated machine components are made of steels with significantly different material compositions, which raises an important practical question of whether the performance of antiwear additives with these other steel types is different from that established with AISI 52100. To help answer this question, this paper investigates the influence of steel composition on the formation and effectiveness of antiwear films. Four steels that are commonly used in tribological applications, namely AISI 52100 through-hardened bearing steel, 16MnCr5 case-carburised gear steel, M2 high speed steel and 440C stainless steel are tested in rolling-sliding, ball-on-disc contacts lubricated with three custom-made oils, one containing ZDDP and two containing different types of ashless antiwear additives. The relative effectiveness of their boundary films was assessed by measuring their thickness and associated wear and friction over 12 h of rubbing at two specimen roughness levels. For ZDDP it was found that the formation of antiwear film was not significantly influenced by steel composition or specimen surface roughness. A similar tribofilm thickness, final tribofilm roughness and friction was observed with all four steels. No measurable wear was observed. By contrast, for the ashless antiwear additives the thickness and effectiveness of their tribofilms was strongly influenced by steel composition, particularly at higher roughness levels. The exact trends in film thickness vs steel relationship depended on the specific chemistry of the ashless additive (ester-based or acid-based) but in general, relative to AISI 52100 steel, M2 steel promoted ashless tribofilm formation whilst 440C retarded ashless tribofilm formation. This behaviour is attributed to the presence of different alloying elements and the ability of the additives

Journal article

Ueda M, Kadiric A, Spikes H, 2021, Wear of hydrogenated DLC in MoDTC-containing oils, Wear, Vol: 474-475, Pages: 1-10, ISSN: 0043-1648

This paper describes a study of the effect on MoDTC-promoted a-C:H DLC wear of adding various surface-active additives used in engine lubricants, including ZDDP, an ashless EP additive, Ca detergents, dispersants, an OFM and a PAMA, to an MoDTC solution. Tribofilms formed on wear tracks on steel were analysed using SLIM, TEM, STEM-EDX, Raman spectroscopy and XPS. Relevant mechanisms by which these additives reduce the impact of MoDTC on DLC wear have also been suggested. DLC wear in PAO+Mo can be reduced by the presence of other surface-active additives in three ways. Firstly, asperity contact between DLC and steel can be mitigated by forming thick antiwear tribofilms. Secondly, other additives can increase the ratio of MoS2:MoO3, reducing the amount of wear-enhancing MoO3 in the tribofilm. Thirdly, the amount of MoDTC tribofilm including MoO3 can be reduced by the competitive adsorption of other surface-active additives. This study has practical implications for ways in which DLC surfaces can be protected by lubricant formulation.

Journal article

Ueda M, Kadiric A, Spikes H, 2021, Influence of steel surface composition on ZDDP tribofilm growth using Ion implantation, Tribology Letters, Vol: 69, ISSN: 1023-8883

This paper examines the influence of steel surface composition on antiwear tribofilm formation by ion-implanting typical steel alloying elements, Ni, Mo, Cr, V and W, into AISI 52100 bearing steel surfaces. Such implantation changes the chemical composition of the steel surface but has relatively little effect on its mechanical properties or topography. The behaviour of zinc dialkyldithiophosphate (ZDDP) antiwear additive was studied. The study employs a ball on disc tribometer with ability to monitor tribofilm development and a range of analytical tools including STEM-EDX, XPS and FIB-TEM to analyse the formed tribofilms. It was found that Ni implantation promotes ZDDP tribofilm formation while Mo and Cr implantation deters tribofilm growth. V and W implantation do not significantly change tribofilm formation. Results on the influence of ZDDP concentration on tribofilm formation rate with different implanted metals suggest that one important mechanism by which steel composition influences tribofilm formation may be by controlling the extent of ZDDP adsorption. This study shows the importance of steel surface composition on ZDDP response and also demonstrates a powerful way to study and potentially improve the tribological performance of machine components via a combination of lubricant formulation and surface modification.

Journal article

Zhang J, Ueda M, Campen S, Spikes Het al., 2021, Boundary friction of ZDDP tribofilms, Tribology Letters, Vol: 69, Pages: 1-17, ISSN: 1023-8883

The frictional properties of ZDDP tribofilms at low entrainment speeds in boundary lubrication conditions have been studied in both rolling/sliding and pure sliding contacts. It has been found that the boundary friction coefficients of these tribofilms depend on the alkyl structure of the ZDDPs. For primary ZDDPs, those with linear alkyl chains give lower friction those with branched alkyl chain ZDDPs, and a cyclohexylmethyl-based ZDDP gives markedly higher friction than non-cyclic ones. Depending on alkyl structure, boundary friction coefficient in rolling-sliding conditions can range from 0.09 to 0.14. These differences persist over long duration tests lasting up to 120 h. For secondary ZDDPs, boundary friction appears to depend less strongly on alkyl structure and in rolling-sliding conditions stabilises at ca 0.115 for the three ZDDPs studied. Experiments in which the ZDDP-containing lubricant is changed after tribofilm formation by a different ZDDP solution or a base oil indicate that the characteristic friction of the initial ZDDP tribofilm is lost almost as soon as rubbing commences in the new lubricant. The boundary friction rapidly stabilises at the characteristic boundary friction of the replacement ZDDP, or in the case of base oil, a value of ca 0.115 which is believed to represent the shear strength of the bare polyphosphate surface. The single exception is when a solution containing a cyclohexylethyl-based ZDDP is replaced by base oil, where the boundary friction coefficient remains at the high value characteristic of this ZDDP despite the fact that rubbing in base oil removes about 20 nm of the tribofilm. XPS analysis of the residual tribofilm reveals that this originates from presence of a considerable proportion of C-O bonds at the exposed tribofilm surface, indicating that not all of the alkoxy groups are lost from the polyphosphate during tribofilm formation. Very slow speed rubbing tests at low temperature show that the ZDDP solutions give boundar

Journal article

Kontou A, Taylor RI, Spikes HA, 2021, Effects of dispersant and ZDDP additives on fretting wear, Tribology Letters, Vol: 69, Pages: 1-13, ISSN: 1023-8883

This paper examines the effect of dispersant and anti-wear additives on fretting wear in lubricated bearing steel contacts. Reciprocating sliding ball-on-flat fretting tests with a stroke length of 50 μm have been carried out on steel-to-steel contacts in both dry and lubricated conditions. Wear and friction coefficient have been measured, and surface characterisation has been carried out using optical techniques to investigate fretting wear. The presence of base oil reduces fretting wear markedly compared to dry conditions, but fretting damage is still observed at low reciprocation frequencies. As frequency is increased, there is a transition from oxidative to adhesive/scuffing damage. The anti-wear additive ZDDP is effective in forming a tribofilm on the surfaces and reducing visible oxidation and wear. A succinimide dispersant also reduces the accumulation of solid debris but does not alleviate wear damage. The combination of both ZDDP anti-wear additive and dispersant in base oil appears to provide significant protection against fretting wear.

Journal article

Garcia Gonzalez C, Ueda M, Spikes H, Wong Jet al., 2021, Temperature dependence of Molybdenum dialkyl dithiocarbamate (MoDTC) tribofilms via time-resolved Raman spectroscopy, Scientific Reports, Vol: 11, Pages: 3621-3621, ISSN: 2045-2322

Molybdenum dialkyl dithiocarbamate (MoDTC) is a friction reducing additive commonly used in lubricants. MoDTC works by forming a low-friction molybdenum disulphide (MoS<sub>2</sub>) film (tribofilm) on rubbed surfaces. MoDTC-induced MoS<sub>2</sub> 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 MoS<sub>2</sub> 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 MoS<sub>2</sub> 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 T<sub>c</sub>, a small amount of MoS<sub>2</sub> gives significant friction reduction. Above T<sub>c,</sub> a patchy film with more MoS<sub>2</sub>, 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.

Journal article

Zhang J, Ueda M, Campen S, Spikes Het al., 2021, Boundary friction of ZDDP tribofilms (vol 69, 8, 2021), Tribology Letters, Vol: 69, Pages: 1-1, ISSN: 1023-8883

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

Ueda M, Kadiric A, Spikes H, 2020, ZDDP tribofilm formation on non-ferrous surfaces, Tribology Online, Vol: 15, Pages: 318-331, ISSN: 1881-218X

The current trend for using lower viscosity lubricants with the aim of improving fuel economy of mechanical systems means that machine components are required to operate for longer periods in thin oil film, boundary and mixed lubrication conditions, where the risk of surface damage is increased. In addition, non-ferrous materials are increasingly being introduced in machine components to reduce wear and increase efficiency. Thus, understanding of the ZDDP antiwear tribofilm formation on both ferrous and non-ferrous surfaces is increasingly important in order to formulate lubricants that give desired antiwear performance with both types of materials. In this paper the effect of ferrous and non-ferrous rubbing materials, namely, steel, Si3N4, WC, SiC and a-C:H DLC coating, on ZDDP tribofilm formation was investigated. Among non-ferrous materials, it was found that ZDDP tribofilms were formed on Si3N4 and WC in the boundary lubrication regime, but almost no tribofilms were formed on SiC and a-C:H DLC. In addition, although tribofilms formed on some non-ferrous surfaces, they were easily removed under boundary lubrication by direct asperity contact because of their weak adhesion to the substrate. This tribofilm removal makes quantification of ZDDP tribofilm formation rate on non-ferrous surfaces under boundary lubrication conditions difficult. By contrast, under high shear stress EHL conditions, thick tribofilms formed without film removal with the tribofilm thickness being the greatest for steel, followed by Si3N4 and then WC, with no tribofilm formation observed on SiC and DLC. QCM results suggest that ZDDP tribofilm formation might be considerably affected by the extent to which ZDDP adsorbs on the substrate surface. The chemical properties of tribofilms are discussed and a possible mechanism by which ZDDP forms tribofilm on non-ferrous surfaces is suggested. This study has practical implications for ways in which non-ferrous surfaces can be protected from wear via l

Journal article

Luiz JF, Spikes H, 2020, Tribofilm formation, friction and wear-reducing properties of some phosphorus-containing antiwear additives, Tribology Letters, Vol: 68, Pages: 1-24, ISSN: 1023-8883

The film-forming, friction and wear properties of a range of model and commercial ashless P and P/S antiwear additives have been studied. A method has been developed for removing the tribofilms formed by such additives in order to effectively quantify mild wear. In general the P/S additives studied formed thinner tribofilms but gave lower wear than the S-free P ones. In extended wear tests, three P/S additives gave wear as low, or lower, than a primary zinc dialkyldithiophosphate (ZDDP). For almost all lubricants tested the wear rate measured in short tests was considerably higher than that in long tests due to the greater contribution of running-in wear in the former. This highlights the importance of basing antiwear additive choice on reasonably long tests, where running-in becomes only a small component of the wear measured. It has been found that for both P and P/S ashless additives the addition of oil-soluble metal compounds based on Ti and Ca boosts tribofilm formation and can lead to very thick films, comparable to those formed by ZDDP. However, this thick film formation tends to be accompanied by an increase in mixed friction and also does not appear to reduce wear but may even increase it.

Journal article

Spikes HA, 2020, Triboelectrochemistry: influence of applied electrical potentials on friction and wear of lubricated contacts, Tribology Letters, Vol: 68, Pages: 1-27, ISSN: 1023-8883

Research on the effects of applied electrical potential on friction and wear, a topic sometimes termed “Triboelectrochemistry”, has been reviewed. Historically, most such research has focussed on aqueous lubricants, whose relatively high electrical conductivities enable use of three-electrode electrochemical kinetic techniques, in which the electrode potential at a single electrode | fluid interface is controlled relative to a suitable reference electrode. This has led to identification of several different mechanisms by which applied electrode potentials can influence friction and wear. Of these, the most practically important are: (i) promotion of adsorption/desorption of polar additives on tribological surfaces by controlling the latters’ surface charges; (ii) stimulation or suppression of redox reactions involving either oxygen or lubricant additives at tribological surfaces. In recent years, there has been growing interest in the effects of applied electrical potentials on rubbing contacts lubricated by non-aqueous lubricants, such as ester- and hydrocarbon-based oils. Two different approaches have been used to study this. In one, a DC potential difference in the mV to V range is applied directly across a thin film, lubricated contact to form a pair of electrode | fluid interfaces. This has been found to promote some additive reactions and to influence friction and wear. However, little systematic exploration has been reported of the underlying processes and generally the electrode potentials at the interfaces have not been well defined. The second approach is to increase the conductivity of non-aqueous lubricants by adding secondary electrolytes and/or using micro/nanoscale electrodes, to enable the use of three-electrode electrochemical methods at single metal | fluid interfaces, with reference and counter electrodes. A recent development has been the introduction of ionic liquids as both base fluids and lubricant additives. These have relat

Journal article

Southby M, Morgan N, Kontou A, Spikes Het al., 2020, Lubricating composition, EP3615641A1


Kim HM, Spikes H, 2020, Correlation of elastohydrodynamic friction with molecular structure of highly refined hydrocarbon base oils, Tribology Letters, Vol: 68, Pages: 1-14, ISSN: 1023-8883

The molecular compositions of a range of low viscosity hydrocarbon base oils spanning API Groups II to IV have been quantified using 13C NMR and correlated with base oil elastohydrodynamic (EHD) friction. A strong correlation has been found between the proportions of paraffin, linear and branched carbons and EHD friction, with a high proportion of linear and paraffinic carbon atoms contributing to low-EHD friction but branched carbons contributing to high-EHD friction. Correlation equations have been developed to predict EHD friction based on base oil composition. At very high temperature and low pressure, this correlation breaks down as the lubricant in the contact does not reach sufficiently high shear stress for shear thinning to occur. For Group IV polyalphaolefin, the correlation must be extended to account for the very high proportion of linear carbons originating from linear alkene oligomerization. The correlations developed in this study can be used to guide the design of low-EHD friction base oils.

Journal article

Zhang J, Spikes H, 2020, Measurement of EHD friction at very high contact pressures, Tribology Letters, Vol: 68, Pages: 1-12, ISSN: 1023-8883

EHD friction curves have been measured up to very high pressure (pmean = 5 GPa, pmax = 7.5 GPa) using a newly developed, rolling-sliding, ball on disc machine, the ETM. Six base fluids have been studied, spanning the API base oil categories Group I to Group V. At high pressures, thermal effects become substantial even at quite modest slide-roll ratios, and these must be considered when analysing friction measurements in terms of the underlying rheological properties of the oils. By comparing measurements from steel/steel and WC/WC ball and disc combinations with very different thermal conductivities, the use of thermal correction to derive isothermal friction curves has been validated. At relatively low pressures (mean pressure = 1 GPa), there are substantial differences between the EHD friction properties of the various API Group base oils, but as pressure is raised these diminish and the EHD friction coefficients of all the Groups approach a similar maximum value at a given temperature. EHD friction continues to be quite strongly temperature dependent even at very high pressure. As pressure is increased, EHD friction curves become progressively steeper, so that friction coefficients at very low slide-roll ratios (1 to 2% SRR) become several times greater at high than at low pressure. This has important practical implications for the efficiency of rolling element bearings at high pressures since these components normally operate in this SRR range. There is no evidence of any of the base oils reaching a limiting shear stress over the whole pressure and temperature range studied. Instead, shear stress continues to increase with log(strain rate) in accord with the Eyring-activated flow model up to very high pressures.

Journal article

Fry B, Moody G, Spikes HA, Wong JSSet al., 2020, Adsorption of organic friction modifier additives, Langmuir, Vol: 36, Pages: 1147-1155, ISSN: 0743-7463

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. OFM 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, 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 friction. This shows that the apparent effect of OFM depends on the stage of 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.

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

Fry B, Moody G, Spikes H, Wong Jet al., 2019, Effect of surface cleaning on performance of organic friction modifiers, Tribology Transactions, Vol: 63, Pages: 305-313, ISSN: 1040-2004

The performance of surface active additives, such as friction modifiers, depends on their interactions with surfaces. Their effectiveness thus hinges upon the surface conditions. In this work, the effect of cleaning methods of test substrates on the friction reduction capabilities of different organic friction modifier (OFM) additives was investigated. 52100 steel discs and balls were the test specimens. They were cleaned in five different ways. The cleaned surfaces were characterised by using ellipsometry and atomic force microscopy. The tribological performance of stearic acid (STA), octadecylamine (ODA) and octadecanol (ODO) on these surfaces were then tested. As-received steel surfaces were covered with contaminants which may impede the formation of OFM surface layer. Cleaning these surfaces with solvents cannot completely removed these contaminants, with residue layers remain. Cleaning with oxygen or argon plasma results in cleaner surfaces as compared to those cleaned by solvents only. The impact of the choice of cleaning methods on friction depends on the strength of the interaction between the OFM and the steel surface, which determines the ability of an OFM to displace surface contaminations. Cleaner surfaces result in lower initial friction for STA and ODA. Steady state friction is also affected, but to a smaller extent. It may be because most containments remained in the wear track are mechanically removed during rubbing.

Journal article

Ueda M, Kadiric A, Spikes H, 2019, On the crystallinity and durability of ZDDP tribofilm, Tribology Letters, Vol: 67, Pages: 1-13, ISSN: 1023-8883

The current trend for using lower-viscosity lubricants with the aim of improving fuel economy of mechanical systems means that machine components are required to operate for longer periods in thin oil film, mixed lubrication conditions, where the risk of surface damage is increased. Consequently, the performance and durability of the tribofilms formed by antiwear additives, and in particular zinc dialkyldithiophosphate (ZDDP), the main antiwear oil additive used in engine oils, has become an increasingly important issue. In this paper, it is confirmed that ZDDP tribofilms are initially relatively easily removed by rubbing but that they become more durable during prolonged rubbing. FIB-TEM analyses at different stages of tribofilm formation show that during the early stages of rubbing only the tribofilm close to the steel substrate is nanocrystalline, while the outer region is amorphous and easily removed. However, after prolonged rubbing all regions of the tribofilm become nanocrystalline and able to withstand rubbing in base oil without being removed. XPS analysis shows that after extended rubbing the outermost polyphosphate structures change from longer-chain structures such as metaphosphate and polyphosphate to shorter-chain structures including orthophosphate. This depolymerization of ZDDP tribofilm from long- to short-chain phosphate and consequent nanocrystallization are driven by heat and shear stress. EDX analysis shows that this conversion is promoted by diffusion of Fe cation into the bulk of the tribofilm. The finding that ZDDP tribofilms evolve during rubbing from a weaker amorphous structure to a more durable nanocrystalline one has important implications in terms of the behaviour of ZDDPs at low concentrations, on non-metallic surfaces and at very high contact pressures, as well as for the development of ZDDP tribofilm, friction and wear models.

Journal article

Dawczyk J, Russo J, Spikes H, 2019, Ethoxylated amine friction modifiers and ZDDP, Tribology Letters, Vol: 67, ISSN: 1023-8883

The influence of a series of Ethomeens (ethoxylated alkylamine organic friction modifiers) on the durability and friction of tribofilms formed by a commercial blend of primary and secondary ZDDP in sliding/rolling contact has been studied. When pre-formed ZDDP tribofilms are rubbed in Ethomeen solution, boundary friction is reduced and some of the ZDDP film is removed. Ethomeens having just two ethoxy groups give lower boundary friction on ZDDP than those with 15 ethoxy groups, but result in much greater removal of the tribofilm itself. Based on XANES analysis, the film removed by both types of Ethomeen consists primarily of nanocrystalline orthophosphate. The level of boundary friction and its dependence on sliding speed, coupled with the dimensions of the molecules, suggests that the Ethomeens with two ethoxy groups may form quite closely packed vertical monolayers on ZDDP tribofilm surfaces, but that those with fifteen ethoxy groups cannot be close packed; yet they still reduce boundary friction significantly. The study shows that selection of an appropriate aminic friction modifier for use with ZDDP is a balance between its ability to reduce friction and its potentially harmful effect on a ZDDP tribofilm.

Journal article

Costa H, Spikes H, 2019, Interactions of ethanol with friction modifiers in model engine lubricants, Lubricants, Vol: 7, ISSN: 2075-4442

When employed as an engine fuel, ethanol can accumulate in the lubricant during use. Previous work has shown that ethanol contamination affects friction and elastohydrodynamic lubrication (EHL) film formation, and also the growth and stability of anti-wear tribofilms. The present work uses spacer-layer ultrathin interferometry and MTM tests to investigate how ethanol (both hydrated and anhydrous) interacts with friction modifiers in model lubricants. Small proportions (5 wt %) of ethanol were added to solutions of friction modifiers (one MoDTC and three organic friction modifiers) in a Group I base oil. For the three organic friction modifiers, the presence of ethanol promoted the formation of thick viscous boundary films so that very low friction coefficients were measured at low entrainment speeds. For the MoDTC additive, the presence of ethanol prevented the formation of a low friction film at low speeds at 70 °C, but this effect disappeared at 100 °C, probably due to ethanol evaporation.

Journal article

Ueda M, Spikes H, Kadiric A, 2019, In-situ observations of the effect of the ZDDP tribofilm growth on micropitting, Tribology International, Vol: 138, Pages: 342-352, ISSN: 0301-679X

The ongoing trend for using ever lower viscosities of lubricating oils, with the aim of improving the efficiency of mechanical systems, means that machine components are required to operate for longer periods under thin film, mixed lubrication conditions where the risk of surface damage is increased. For this reason, the role of zinc dialkyldithiophosphate (ZDDP) antiwear lubricant additive has become increasingly important in order to provide adequate surface protection. It is known that due to its exceptional effectiveness in reducing surface wear, ZDDP may promote micropitting by preventing adequate running-in of the contacting surfaces. However, the relationship between ZDDP tribofilm growth rate and the evolution of micropitting has not been directly demonstrated. To address this, we report the development of a novel technique using MTM-SLIM to obtain micropitting and observe ZDDP tribofilm growth in parallel throughout a test. This is then applied to investigate the effect of ZDDP concentration and type on micropitting.It is found that oils with higher ZDDP concentrations produce more micropitting but less surface wear and that, at a given concentration, a mixed primary-secondary ZDDP results in more severe micropitting than a primary ZDDP. Too rapid formation of a thick antiwear tribofilm early in the test serves to prevent adequate running-in of sliding parts, which subsequently leads to higher asperity stresses and more asperity stress cycles and consequently more micropitting. Therefore, any adverse effects of ZDDP on micropitting and surface fatigue in general are mechanical in nature and can be accounted for through ZDDP's influence on running-in and resulting asperity stress history. The observed correlation between antiwear film formation rate and micropitting should help in the design of oil formulations that extend component lifetime by controlling both wear and micropitting damage.

Journal article

Guegan J, Southby M, Spikes H, 2019, Friction modifier additives, synergies and antagonisms, Tribology Letters, Vol: 67, ISSN: 1023-8883

There is growing interest in reducing friction in lubricated machine components to thereby increase the energy efficiency of machines. One important way to minimise friction is to employ friction modifier additives to reduce friction in thin film boundary lubrication conditions. There are currently three main types of friction modifier additive, organic friction modifiers, oil soluble organomolybdenum friction modifiers and functionalised polymers. In common practice, a single such additive is generally employed in a formulated lubricant, but it is of interest to explore whether combinations of two friction modifier additives may prove beneficial. In this study, the performance of eight commercial friction modifier additives spanning all three main types was first measured in three quite different friction tests. The aim was to identify the contact conditions under which each additive was most effective. Additive solutions in both a base oil and a formulated engine oil were investigated. In general, functionalised polymers were most beneficial in sliding–rolling contacts, while oil soluble organomolybdenum friction modifiers worked best in severe, reciprocating sliding conditions. However, all friction modifier additive response was strongly affected by the other additives present in formulated engine oils. The friction performance of combinations of friction modifier additives was then explored. When two different friction modifiers additives were combined in solution, several possible outcomes were observed. The most common was for one of the additives to predominate, to give friction that was characteristic of that additive alone, while in some cases friction lay between the values produced by either additive on its own. In a few cases the additives behaved antagonistically so that the combination gave higher friction than either additive by itself. In a few cases true synergy was observed, where a combination of two additives produced lower friction in a g

Journal article

Dawczyk J, Morgan N, Russo J, Spikes Het al., 2019, Film thickness and friction of ZDDP tribofilms, Tribology Letters, Vol: 67, ISSN: 1023-8883

Tribofilm formation by several zinc dialkyl- and diaryldithiophosphate (ZDDP) solutions in thin film rolling-sliding conditions has been investigated. A primary, a secondary alkyl and a mixed alkyl ZDDP show similar rates of film formation and generate films typically 150 nm thick. Another secondary ZDDP forms a tribofilm much faster and the film is partially lost after extended rubbing. An aryl ZDDP forms a tribofilm much more slowly. The films all have a pad-like structure, characterised by flat pad regions separated by deep valleys. Three different techniques have been used to analyse the thickness and morphology of the tribofilms: spacer layer imaging (SLIM), scanning white light interferometry (SWLI) of the gold-coated film and contact mode atomic force microscopy (AFM). The SLIM method measures considerably thicker films than the other two techniques, probably because of lack of full conformity of a glass disc loaded against the rough tribofilm. No evidence of a highly viscous layer on top of the solid tribofilm is seen. SWLI and contact mode AFM measure similar film thicknesses. The importance of coating the tribofilm with a reflective layer prior to using SWLI is confirmed. As noted in previous work, the formation of a ZDDP tribofilm is accompanied by a marked shift in the Stribeck friction curve towards higher entrainment speed. For a given ZDDP this shift is found to correlate with the measured tribofilm roughness, proving that it results from the influence of this roughness on fluid entrainment in the inlet.

Journal article

Peng B, Spikes H, Kadiric A, 2019, The development and application of a scuffing test based on contra-rotation, Tribology Letters, Vol: 67, ISSN: 1023-8883

Scuffing is a surface failure mode that occurs in sliding–rolling contacts subjected to high loads and high sliding speeds, such as those in gears and cam-followers. Owing to its sudden onset, rapid progression and dependence on both fluid and boundary lubricant films, scuffing is difficult to study in a repeatable manner. This paper describes further development of a recently proposed scuffing test method based on contra-rotation, its extension to higher loads using a new experimental set-up and its application to study the onset of scuffing with a selection of model and fully-formulated oils. The method employs two surfaces moving in opposite directions under rolling–sliding conditions, with a fixed load and step-wise increasing sliding speed. By decoupling the entrainment and sliding speeds, the method allows the effects of lubricant formulation on scuffing performance to be isolated from the influence of viscosity. The approach achieves high sliding speeds in parallel with low entrainment speeds, while minimising the undesirable effects of surface wear and frictional heating. The proposed test is relatively fast and economical, with total test time of about 30 min including specimen cleaning and set-up. Results show that the newly implemented modifications have improved the repeatability of the test method, so that the number of repeat tests required for reliable oil ranking results is minimal. Tests with model and fully-formulated oils show that the onset of scuffing is characterised by a sharp and unrecoverable increase in friction and accompanied by the destruction of any boundary films. All tests show that the relationship load × speedn = constant holds at scuffing, with the exact value of the exponent n being dependent on the oil formulation. Additivised oils were shown to have enhanced scuffing resistance, which arises from their ability to postpone the uncontrollable rise in friction to higher sliding speeds. Finally, the critical maximu

Journal article

Reddyhoff T, Schmidt A, Spikes H, 2019, Thermal conductivity and flash temperature, Tribology Letters, Vol: 67, Pages: 22-22, ISSN: 1023-8883

The thermal conductivity is a key property in determining the friction-induced temperature rise on the surface of sliding components. In this study, a Frequency Domain Thermoreflectance (FDTR) method is used to measure the thermal conductivity of a range of tribological materials (AISI 52100 bearing steel, silicon nitride, sapphire, tungsten carbide and zirconia). The FDTR technique is validated by comparing measurements of pure germanium and silicon with well-known values, showing discrepancies of less than 3%. For most of the tribological materials studied, the thermal conductivity values measured are reasonably consistent with values found in the literature. However the measured thermal conductivity of AISI 52100 steel (21 W/mK) is less than half the value cited in the literature (46 W/mK). Further bulk thermal conductivity measurements show that this discrepancy arises from a reduction in thermal conductivity of AISI 52100 due to through-hardening. The thermal conductivity value generally cited and used in the literature represents that of soft, annealed alloy, but through-hardened AISI 52100, which is generally employed in rolling bearings and for lubricant testing, appears to have a much lower thermal conductivity. This difference has a large effect on estimates of flash temperature and example calculations show that it increases the resulting surface temperatures by 30 to 50%. The revised value of thermal conductivity of bearing steel also has implications concerning heat transfer in transmissions.

Journal article

Kontou A, Southby M, Morgan N, Spikes HAet al., 2018, Influence of dispersant and ZDDP on soot wear, Tribology Letters, Vol: 66, Pages: 1-15, ISSN: 1023-8883

Diesel engines and gasoline direct injection (GDI) engines both produce soot due to incomplete combustion of the fuel and some enters the lubricant where it accumulates between drain intervals, promoting wear of rubbing engine components. Currently the most favoured mechanism for this wear is that the anti-wear additives present in engine oils, primarily zinc dialkyldithiophosphates (ZDDPs), react very rapidly with rubbing surfaces to form relatively soft reaction products. These are easily abraded by soot, resulting in a corrosive-abrasive wear mechanism. This study has explored the impact of engine oil dispersant additives on this type of wear using combinations of dispersant, ZDDP and carbon black, a soot surrogate. It has been found that both the concentration and type of dispersant are critical in influencing wear. With most dispersants studied, wear becomes very high over an intermediate dispersant concentration range of ca 0.1–0.4 wt% N, with both lower and higher dispersant levels showing much less wear. However a few dispersants appear able to suppress high wear by ZDDP and carbon black over the whole concentration range. A series of experiments have been carried out to determine the origin of this behaviour and it is believed that high levels of dispersant, and, for a few dispersants, all concentration levels, protect the iron sulphide tribofilm initially formed by ZDDP from abrasion by carbon black.

Journal article

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