Film Formation by Colloidal Overbased Detergents in Lubricated Contacts

It has been reported in the literature that overbased detergents can possess good antifriction and antiwear properties although the origins of these properties are not fully clear. In practice, over-based detergents are colloidal dispersions and this may be important in determining their properties and mechanism of action.

In the current study, the lubricating properties of commercial, overbased magnesium and calcium sulfonates were measured in thin film, lubricated conditions and compared to a neutral sulfonate additive. A range of techniques was employed to evaluate the tribological performance of solutions of these additives. Film thickness measurements were carried out using optical interferometry and in-contact visualization, while friction and wear measurements complemented the study.

It has been found that, when operating in thin film conditions, overbased detergents deposit solid-like boundary films on the rubbing surfaces. These films form in both rolling and mixed rolling/sliding conditions and, unlike many other colloidally-formed boundary films, are able to survive in high speed, thick film conditions. During formation, the film rapidly reaches a thickness corresponding to one colloid particle diameter, between 10 and 20 nm. After prolonged rubbing, however, the film thickness reaches the equivalent of three particle diameters. No such thick boundary films are observed with the neutral sulfonate.

The boundary films formed by overbased detergents produce a significant reduction in wear. However, for the very smooth surfaces used in this study, they also result in an effective roughening of the very smooth surfaces studied. This leads to an increase in friction in the intermediate speed region by promoting solid-solid contact in thin fluid film conditions.     

Lubrication of aluminium–silicon surfaces with ZDDP and detergents

Abstract

A review of the lubrication of aluminium–silicon (Al-Si) substrates by zinc dialkyldithiophosphate (ZDDP) and detergent engine oil additives is presented. Greater attention has been paid to understand the interactions of ZDDP, rather than detergents, with the aforementioned non-ferrous substrates. Zinc dialkyldithiophosphate generates tribofilms on both aluminium and silicon regions of aluminium–silicon alloys. However, film formation is believed to occur on silicon grains within the alloy, and those layers observed on aluminium regions are material transfer or the product of ZDDP thermal decomposition. There were many similarities in terms of film thickness, reduced elastic modulus, tribochemistry and topography of ZDDP derived tribofilms on both ferrous and Al–Si substrates. Calcium carbonate based films were observed on silicon grains when the aluminium alloys were lubricated with overbased calcium sulphonate, the tribochemistry and topography of which were similar to layers formed on ferrous substrates. When lubricated with either fully formulated oil or lubricants containing both detergent and ZDDP, the subsequently generated films were of varying chemistry, but often contained zinc or calcium phosphate compounds. The antiwear characteristics of ZDDP and calcium sulphonate tribofilms on ferrous and aluminium–silicon substrates are discussed, with the mechanical and film thickness data for such layers presented.     

Reduction of Friction by Functionalised Viscosity Index Improvers

A range of functionalised polymethacrylate copolymers have been synthesised with different functionalities, polymer architecture and molecular weight. It is shown that appropriately functionalised block copolymers give enhanced film thickness and greatly reduced friction under low entrainment speed conditions, even with polymer concentration as low as 1% wt. This behaviour almost certainly results from the formation of an adsorbed brush-like film of thickness ca 20 nm on each polar surface. These films provide a highly viscous inlet that promotes fluid entrainment and thus maintains a separating film down to very low entrainment speed. The adsorbed polymer films are also able to maintain separation in stationary contact conditions. Randomly distributed copolymers do not show this type of behaviour. The friction reduction observed is more effective in unidirectional, mixed sliding–rolling than in reciprocating, sliding conditions. However, it is found that functionalised polymers and conventional organic and molybdenum-based friction modifiers can be combined to provide effective friction reduction over the whole range of rubbing conditions.     

Characterization of tribofilms derived from zinc dialkyldithiophosphate and salicylate detergents by X-ray absorbance near edge structure spectroscopy

Phosphorous and sulfur L- and K-edge X-ray absorption near edge structure (XANES) spectra were recorded to characterize the surface chemistry of the tribofilms derived from a commercial zinc dialkyldithiophosphate (ZDDP) and its blends with overbased calcium and magnesium salicylate detergents. The results show that the chemical structure of the tribofilms generated from the mixture of ZDDP and detergents is different from that of the tribofilm derived from ZDDP alone. However, the two kinds of detergents inhibit ZDDP from forming tribofilm, producing thinner polyphosphate films. Though XANES analysis does not provide definite evidence to the existence of magnesium element in the tribofilms, it is likely that calcium or magnesium has been incorporated therein. Moreover, ion exchange reaction and the formation of zinc polyphosphate film may occur simultaneously during sliding. However, calcium or magnesium (poly)phosphates do not contribute to reduce friction and wear of a steel–steel pair.     

The Frictional Properties of Newtonian Fluids in Rolling–Sliding soft-EHL Contact

A combined experimental and numerical study has been carried out to explore friction in rolling–sliding, soft-EHL contact. Experimental work has employed corn syrup solutions of different concentrations in water to provide a range of lubricant viscosities and has measured Couette friction in mixed rolling–sliding conditions over a wide range of entrainment speeds. A Stribeck curve has been generated, ranging from the boundary to full film, isoviscous-elastic lubrication regime. In the latter regime, friction coefficient is approximately proportional to the product of (entrainment speed × viscosity) raised to the power 0.55. Numerical solution of the isoviscous-elastic lubrication regime has been used to derive predictive equations for both Couette and Poiseuille friction in circular, soft-EHL contacts. This shows that in soft-EHL the Poiseuille or “rolling” friction can have magnitude comparable to the Couette friction. The calculated Poiseuille friction coefficient can be predicted from non-dimensional load and speed using a simple power law expression similar to that used for film thickness. However accurate prediction of calculated Couette friction coefficient requires a two-term power law expression. Comparison of experimental and numerical Couette friction coefficients shows quite good agreement between the two, with a similar non-dimensional speed dependence, but slightly lower predicted than measured values.     

Study of deposit and friction films of overbased calcium sulphonate by PM-IRRAS spectroscopy

This paper deals with the study of deposit and friction films of overbased calcium sulphonate diluted in mineral oil, on metal surfaces. The technique used for this work is Infrared Reflection Absorption Spectroscopy by Fourier Transform and Polarisation Modulation (PM-IRRAS or PM FTIR). The spectra obtained from this method contain only information on the absorption occurring in the immediate neighbourhood (⩽40 nm) of the metallic substrate and allow the average orientation for molecules adsorbed on metals to be deduced. This study shows that the adsorption of overbased calcium sulphonate on a steel surface leads to a preferential orientation of the sulphonate chains perpendicular to the surface and to a preferential orientation of the carbonate, the c axis being perpendicular to the surface. During friction, the sulphonate chains are ejected from the contact zone. We observed that the boundary film consists mainly of calcium carbonate, which crystallises into calcite.     

Friction Characteristics and Topography of Tribofilms from Anti-Wear Additives Applied to Metal V-Belt Type CVT Fluids

This study has investigated potential links between tribological performance and the morphology of tribofilms formed from anti-wear additives with application to metal V-belt pushing type continuously variable transmission fluids (B-CVTFs). The influence of metal–metal tribological properties of anti-wear additives was evaluated using a ball on plate tribometer, enabling friction and lubricant film formation to be monitored during reciprocating tests. Contact mode atomic force microscopy was utilised to investigate the nature of tribofilms at the nanometre scale. As a result, an additive formulation composed of hydrogen phosphite and over-based calcium sulphonate in a hydro-cracked mineral Group II base oil demonstrated a synergism with 8% higher friction coefficient and more stable film formation than the individual additive cases, providing a positive outcome for a B-CVTF. Tribofilm species produced by a chemical reaction between hydrogen phosphite and over-based calcium sulphonate were densely deposited on the wear scar to form a rougher surface, which may explain the higher friction observed.     

Tribological Behaviour of N(C)-Alloyed W–S Films

In this study, sputtered W–S–N(C) films were deposited by rf magnetron sputtering with increasing N or C content. The coatings were tribologically tested in a pin-on-disk apparatus with increasing applied normal loads in two different environmental conditions, normal room atmosphere and dry nitrogen atmosphere. W–S–N(C) films without or with low N(C) addition had high wear rates, whatever the environment was, but induced low wear in the counterbody material and low friction coefficients. The coatings alloyed with high N content showed excellent wear resistance and a very low friction coefficient (<0.05) when tested in dry nitrogen but the opposite behaviour under room conditions. For their part, high C-containing coatings showed an excellent tribological behaviour in both environments, not as good as N-alloyed films in dry nitrogen but much better under room conditions. The wear and friction coefficients were lower in dry nitrogen than in humid air. Globally, the alloying with N(C) resulted in wear rates in W–S–N(C) films two orders of magnitude lower than in an unalloyed one, keeping the friction coefficient at the same level or even lower. The wear behaviour was interpreted as a function of several factors including; the mechanical strength of the coatings, the adhesion of the films to the substrate, the porosity and the structural arrangement of the film.     

Tribological Performance of Lubricating Greases Based on Calcium Carbonate Polymorphs Under the Boundary Lubrication Condition

In this article, we synthesized the calcium sulphonate grease (CSG) based on the calcite using the bright stock (150BS) as the base oil. In order to investigate the tribological performance of lubricating grease containing different calcium carbonate polymorphs under boundary lubrication condition, a calcium sulphonate complex grease (CSCG) based on the vaterite was used as a reference. An oscillating reciprocating friction and wear tester set at a series of applied loads and frequencies was adopted to evaluate the tribological performance under boundary condition. Results showed that the lubricating grease that was composed of crystalline calcite as the partial thickener had excellent friction-reducing and antiwear (AW) properties, regardless of the applied loads and frequencies. The vaterite in CSCG easily experienced a polymorph transformation into calcite or aragonite characterized by Raman spectroscopy. This polymorph transformation was attributed to the highly local friction temperature and activated hydrogen from water or acids oxidated in the rubbing process at high load or frequency. The physical polymorph transformation corresponded to the fluctuations of the friction coefficients, then contributed to the severe wear. XPS analysis indicated that two calcium sulphonate lubricating greases occurred a tribochemical reaction and boundary tribofilms consisted of CaCO₃, CaO, iron oxide and FeSO₄ were formed on the rubbing surfaces. The tribofilm formed by the introduction of the CSG that mainly depended upon the thickeners of calcite structure contributed to an excellent AW protection. The possible boundary friction mechanism for greases based on various calcium carbonate polymorphs was also proposed. Effect of calcium carbonate polymorphs on the tribological performance was discussed.     

A multi-scale model for friction in cold rolling of aluminium alloy

A simple and robust friction model is proposed for cold metal rolling in the mixed lubrication regime, based on physical phenomena across two length scales. At the primary roughness scale, the evolution of asperity contact area is associated with the asperity flattening process and hydrodynamic entrainment between the roll and strip surfaces. The friction coefficient on the asperity contacts is related to a theoretical oil film thickness and secondary-scale roll surface roughness. The boundary friction coefficient at the “true” asperity contacts is associated with tribo-chemical reactions between fresh metal, metal oxide, boundary additives, the tool and any transfer layer on the tool. The asperity friction model is verified by strip drawing simulations under thin film lubrication conditions with a polished tool, taking the fitting parameter of the boundary lubrication friction factor on the true contact areas equal to 0.1. Predicted values of average friction coefficient, using a boundary friction factor in the range 0.07–0.1, are in good agreement with measurements from laboratory and industrial rolling mill trials.     

Tribological Performance of UHMWPE and PFPE Coated Films on Aluminium Surface

A thin layer of Ultra High Molecular Weight Polyethylene (UHMWPE) or UHMWPE + PFPE is coated onto cylindrical aluminium (Al) pin (4.6 mm diametre) surface with the aim of providing wear resistant coating on this soft and tribologically poor metal. The coefficient of friction and wear life of the coated samples are investigated on a pin-on-disk tribometre under different normal loads (394–622 g) and two sliding speeds (0.1 and 0.31 m/s) against uncoated Al disk as the counterface. Both coatings provide coefficient of friction values in the range of 0.02–0.2 as compared to 0.4–1.0 for uncoated Al. There is tremendous improvement in the wear life of the pin, with UHMWPE + PFPE film giving wear life approximately twice to thrice higher than that with only UHMWPE film. A thin polymer film is transferred to the disk surface during sliding providing very long-term wear life (continuous low coefficient of friction) despite visual removal of the film from the pin surface. The present films will have applications in gears and bearings as solid or boundary lubricants for automotive and aerospace component.     

Carbon Nanotube Reinforced Polyimide Thin-film for High Wear Durability

In this paper, the influence of single walled carbon nano tubes (SWCNTs) addition on the tribological properties of the polyimide (PI) films on silicon substrate was studied. PI films, with and without SWCNTs, were spin coated onto the Si surface. Coefficient of friction and wear durability were characterized using a ball-on-disk tribometer by employing a 4 mm diameter Si₃N₄ ball sliding against the film, at a contact pressure of ∼370 MPa, and a sliding velocity of 0.042 ms⁻¹. Water contact angle, AFM topography, and nano-indentation tests were conducted to study the physical and mechanical properties of the films. SWCNTs marginally increased the water contact angle of PI film. The addition of SWCNTs to PI has increased the hardness and elastic modulus of pristine PI films by 60–70%. The coefficient of friction of PI films increased slightly (∼20%) after the addition of SWCNTs, whereas, there was at least two-fold increase in the wear life of the film based on the film failure condition of coefficient of friction higher than 0.3. However, the film did not show any sign of wear even after 100,000 cycles of rotation indicating its robustness. This increase in the wear durability due to the addition of the SWCNTs is believed to be because of the improvement in the load-bearing capacity of the composite film and sliding induced microstructural changes of the composite film.     

Study of the Lubrication Mechanism of Overbased Ca Sulfonate on Additives Containing S or P

The influence of the addition of overbased calcium sulfonate detergent (OBCaSu) on the antiwear properties of sulfuride olefin (SO) and tricresyl phosphate (TCP) was studied with wear tests and surface analyses. Wear tests were conducted on a four-ball wear test machine. The formation of a protective film on the worn surface was examined using scanning electron microscopy (SEM) and X-ray photoelectron spectrometry (XPS). Test results indicate that OBCaSu can improve the antiwear properties of SO and TCP. Surface analyses found that the lubricating mechanism of OBCaSu and TCP is different from that of OBCaSu and SO. In the case of the lubrication of OBCaSu plus SO, the improved antiwear property is caused by the formation of a surface deposition film containing CaCO₃ from the OBCaSu and the neutralization of OBCaSu, which could prevent excessive corrosion wear. In the case of the lubrication of OBCaSu plus TCP, calcium phosphate was formed and incorporated into the surface film, which possesses good antiwear characteristics.     

The Lubricating Properties of Human Whole Saliva

We demonstrate the efficient boundary lubricating properties of human whole saliva (HWS) in a soft hydrophobic rubbing contact, consisting of a poly(dimethylsiloxane) (PDMS) ball and a PDMS disk. The influence of applied load, entrainment speed and surface roughness was investigated for mechanically stimulated HWS. Lubrication by HWS results in a boundary friction coefficient of μ ≈ 0.02, two orders of magnitude lower than that obtained for water. Dried saliva on the other hand results in μ ≈ 2–3, illustrating the importance of hydration for efficient salivary lubrication. Increasing the surface roughness increases the friction coefficient for HWS, while it decreases that for water. The boundary lubricating properties of HWS are less sensitive to saliva treatment than are its bulk viscoelastic properties. Centrifugation and ageing of HWS almost completely removes the shear thinning and elastic nature observed for fresh HWS. In contrast, the boundary friction coefficients are hardly affected, which indicates that the high-M _w (supra-)molecular structures in saliva, which are expected to be responsible for its rheology, are not responsible for its boundary lubricating properties. The saliva-coated PDMS surfaces form an ideal model system for ex-vivo investigations into oral lubrication and how the lubricating properties of saliva are influenced by other components like food, beverages, oral care products and pharmaceuticals.     

TOF-SIMS analysis of boundary films derived from calcium sulfonates

Tribological properties of over-based and neutral calcium sulfonate were examined under boundary lubrication conditions by using a ball-on-flat type tribo-tester. It was found that over-based calcium sulfonate reduced friction and wear of steel–steel contacts, whereas the neutral calcium sulfonate did not. It was found that boundary film composed of calcium oxide plays significant role on improving the tribological properties. Surface analyses by XPS and Time-of-flight secondary mass spectroscopy (TOF-SIMS) revealed that the major component of the film on upper surfaces is calcium carbonate and that at subsurfaces are composed of calcium oxide. A depth profile of the film obtained by TOF-SIMS using an etching technique revealed that thickness of the film is up to 240 nm. A static pyrolysis of the over-based calcium sulfonate on steel surface affords a thin film composed of calcium oxide, indicating that rubbing process is essential for the formation of the boundary film.     

Lubricant film formation properties of alkyl imidazolium tetrafluoroborate and hexafluorophosphate ionic liquids

The film thickness and friction properties of four imidazolium ionic liquids (1-butyl-3-methyl tetrafluoroborate and hexafluorophosphate and 1-hexyl-3-methyl tetrafluoroborate and hexafluorophosphate) were measured for mixed rolling-sliding conditions and the results compared to an additised mineral oil. Film thickness results showed that three of the fluids demonstrated classical EHL behaviour; however, the 1-butyl-3-methyl fluids gave anomalously thick, time-dependent films at low speeds (<0.3 m/s). Post-test inspection of the specimens revealed a loosely bound brown film deposited in the track. Film formation appeared to originate in the bulk fluid where brown “fibrous” agglomerations were observed. These were flocculated by shear flow and deposited in the track after passing through the contact. Overall the RTIL friction coefficients were less than the mineral oil for all conditions investigated. In the absence of thick film formation all RTILs gave a similar friction coefficient of 0.03 in the boundary regime, which is thought to be due to electrical double layer formation. In the fluid film regime traction was determined by the nature of the anion.     

Nanostructure and Composition of Tribo-Boundary Films Formed in Ionic Liquid Lubrication

Since the idea of using ionic liquids (ILs) as lubricants was raised in 2001, many studies have been conducted in this area and results have demonstrated superior lubricating performance for a variety of ILs. It is widely believed that a protective tribo-boundary film is formed on the contact area by tribochemical reactions between the metal surface and the IL during the wear process and, as a result, reduces friction and wear. However, the study of this critical boundary film in the literature has been limited to two-dimensional topography examination and chemical analysis from the top surface. This study demonstrates a multi-technique three-dimensional approach to characterize the boundary films on IL-lubricated metallic surfaces. The complementary characterizations at the top surface, cross-section, and different layers of the boundary film provide direct measurement of the film thickness, visualization of the nanostructure, and analysis of the composition change. The boundary films observed on different alloys are substantially distinct from both physical and chemical perspectives. The measured mean film thicknesses for cast iron, steel, and aluminum worn surfaces are 300, 60, and 200 nm, respectively. The boundary films on ferrous alloys are dominated by amorphous phase mixing with well-dispersed very fine (a few nm) nanocrystals, while the film on aluminum contains many larger size (tens of nm) metallic particles in a less organized manner.     

Micellar calcium borate as an antiwear additive

The mechanisms of action of a new generation of antiwear additives is studied here by means of energy‐filtering transmission electron microscopy (EFTEM) carried out on the wear particles generated during friction tests between two ferrous surfaces (under boundary lubrication conditions). This paper deals with the structural and physico‐chemical changes that colloidal particles, calcium carbonate (CC) and calcium borate (CB) overbased salicylates detergents, have undergone during the build‐up of the interfacial antiwear tribofilm. EFTEM allowed us to investigate the nature of wear fragments originating from the film, stemming from CC and CB micelles, and to make a comparison regarding the tribofilm formation mechanisms. It appears that the CC wear debris are mainly crystalline and contain a high concentration of iron (as abrasive iron oxide Fe₂O₃), limiting their antiwear action. Consequently, CC micelles do not lead to an effective protective tribofilm. On the other hand, CB micelles do have an antiwear action, which we explained by the formation of a glassy iron borate tribofilm during the friction tests. Many of the CB wear fragments are composed of this amorphous material containing very small crystallites of residual calcite. Boron (contained in the CB micelles) is responsible for the presence of amorphous zones of the film and acts as a glass former, in a comparable way to phosphorus in zinc dithiophosphate. This revised version was published online in July 2006 with corrections to the Cover Date.     

Amorphous hydrogenated carbon films for tribological applications II. Films deposited on aluminium alloys and steel

This paper describes the methods for the deposition of AHC films on aluminium alloys (2024, 7075 and an additional Al-Si alloy) and AISI 4340 steel. Both unmodified and silicon modified AHC films were deposited. AHC films could be deposited on aluminium alloys without any interlayer. The deposition of AHC films on steel required an interlayer which could be aluminium, silicon or chromium. Thin films (1–2 μm) deposited on aluminium alloys and steel influenced durability of films and friction coefficients in contact with steel. These were believed to be due to plastic deformation of substrates. Deposition of a thicker coating system (interlayer + AHC) reduced friction coefficients and also improved film durability. The durability of films deposited on steel substrates was evaluated under both unlubricated and lubricated conditions for 5.5 million cycles under 4.4 N load and up to 2.5 m/s sliding speed. Although there was wear, the films survived 5.5 million test cycles under unlubricated sliding, but in the presence of two lubricants, the film wear was very small and could not be measured. It was observed that the wear of the steel counterface in contact with silicon-containing AHC films could be higher than that against an uncoated steel in the presence of certain lubricants.     

Tunable friction behavior of oriented carbon nanotube films

Measured friction coefficients of carbon nanotubes vary widely from μ < 0.1–μ > 1.0 [1–6], while theoretical studies suggest intrinsically high friction coefficients, approaching unity [7]. Here we report that measured friction coefficients of MWNT films are strong functions of surface chemistry and temperature, but are not dependent on the presence of water vapor. We hypothesize that the origin of the temperature dependence arises from the interaction of the surface chemical groups on the nanotubes [8–12] and rubbing counterface. The friction coefficient of individual films can be easily tuned by changing the surface temperature and chemistry of either the countersurface or the nanotubes, we have demonstrated the ability to create and control high and low friction pairs through plasma treatments of the nanotube films with argon, hydrogen, nitrogen, and oxygen. This behavior is completely reversible, and when coupled with the superior strength, thermal, and electrical properties of nanotubes, provides a versatile tunable, multifunctional tribological system.