C. Grossiord

MoS2 single sheet lubrication by molybdenum dithiocarbamate

The mechanisms by which Modtc reduces friction in the centirange under boundary lubrication have been investigated using analytical tribometry. First, the SRV friction test was coupled with energy-filtering TEM on wear fragments and spatially-resolved XPS inside the wear scars. Second, we performed UHV friction tests on Modtc tribofilms previously created on a large area. The overall data demonstrate that the mechanisms of friction-reduction by Modtc is attributed to the effect of sliding between single layers of MoS2 only, and not to intra-sliding in MoS2 3-D crystal. Highly-dispersed MoS2 sheets are present in a carbon matrix in the tribofilm material. The growth of the 2-D MoS2 single sheets is thought to be formed by degradation of the Modtc molecule by electron transfer mechanisms activated by the friction process. The lubrication of the uncoated, stationary counterface is attributed to successive transfer of individual sheets towards the friction surface. Practically, in these conditions only a few per cent of dispersed MoS2 is sufficient to lubricate at the same level as pure MoS2.

The two-layer structure of Zndtp tribofilms: Part I: AES, XPS and XANES analyses

The nature and properties of polyphosphate glasses formed in the antiwear action of zinc dithiophosphate (Zndtp) is investigated. Special attention is paid to the advantage of coupling three surface analytical techniques on the same Zndtp tribofilm: Auger (AES), XPS and XANES spectroscopies. The data show the two-layer structure of the Zndtp film and permit a clear identification of the chemical composition of each layer: a polymer-like zinc long chain polyphosphate overlying a mixed transition metal short chain phosphate. A Chemical Hardness model is found to predict the formation of such a layered tribofilm. Moreover, a tribochemical reaction between the zinc polyphosphate and the iron oxides species is proposed on the basis of the Hard and Soft Acids and Bases (HSAB) principle. This reaction explains the anti-abrasive mechanism of Zndtp and also predicts a depolymerisation of the long chain zinc polyphosphate glass, in very good agreement with AES/XPS/XANES analytical data. The role of residual sulphur in the lubricant is also explained and the model is in agreement with the formation of metal sulphides embedded in the short chain phosphate matrix. This first paper serves as a basis for a detailed study of the mechanical properties of each film.

Transfer films and friction under boundary lubrication

The role of transfer phenomena in the mechanisms of friction reduction by organic molybdenum compounds is studied with the aid of ultrahigh vacuum (UHV) analytical tribometry. Additives used are zinc dithiophosphate (Zndtp), molybdenum dithiophosphate (Modtp), molybdenum dithiocarbamate (Modtc) and Modtc/Zndtp combinations. Experiments involve UHV friction tests on tribofilms formed previously and in situ surface analyses by Auger electron spectroscopy (AES) and imaging. In the presence of Modtc, friction reduction was found to be associated with the transfer of highly dispersed MoS2 as isolated sheets, from the tribofilm to the slider. In the presence of Modtp (or the mixture Modtc/Zndtp), a two-step tribochemical reaction is generally observed. First, phosphate from the film is transferred to the oxide on the pin and the friction coefficient is about 0.3, after an induction period of a few cycles, pure MoS2 single sheets are transferred to the pin and the phosphate is eliminated as wear debris from the contact zone. Friction is then at its lowest value (0.02). The chemistry of the transfer phenomena is modeled using the hard and soft acid and base (HSAB) principle as described by Pearson. The overall data suggest that friction behavior under boundary lubrication with additives may be directly related to molecular scale transfer mechanisms in general.

Synergistic effects in binary systems of lubricant additives: a chemical hardness approach

Tribochemical interactions between antiwear zinc dithiophosphate (Zndtp), friction modifier molybdenum dithiocarbamate (Modtc) and detergent overbased calcium borate (CB) lubricant additives have been investigated by coupling analytical TEM and micro‐spot XPS in the tribotester Optimol of SRV GmbH (mild wear conditions in boundary lubrication). Synergistic effects have been observed on both friction and wear data, especially in the Modtc/Zndtp combination. Results have been interpreted on the basis of a chemical hardness concept: the hard and soft acids and bases (HSAB) principle, stabilisation of hard–hard pairs and the maximum hardness principle. The performance of the Modtc/Zndtp mixture is mainly due to the generation of MoS2 single sheets and the digestion of MoO3, which is also formed, by the zinc polyphosphate glass. The final result of the tribochemical reaction is a tribofilm composed of MoS2 sheets embedded in a mixed Mo/Zn polyphosphate glass. The CB/Modtc mixture has a similar mechanism except that the oxide is not completely eliminated, due to the softer borate anion compared with the phosphate one.

A dual‐analysis approach in tribochemistry: application to ZDDP/calcium borate additive interactions

Tribochemical interactions between zinc dithiophosphate (ZDDP) and micellar calcium borate (CB) under boundary lubrication were investigated by coupling, in the same location of the wear track, both analytical TEM analysis of collected wear fragments from the tribofilm and XPS surface analysis of the tribofilm directly underneath. This is the so‐called dual‐analysis approach, which improves the interpretation of tribochemical reactions. The elemental composition inside the wear scars was analysed by micro‐spot XPS. By depth profiling, the film thickness could also be determined. In particular, the efficiency of the additive combination could be proven by quantification of iron oxide. The nature of wear particles was investigated in the TEM by using EELS and EDX simultaneously, with the result that phosphorus, boron and sulphur contributions have been carefully distinguished. The technique is very powerful for determining the composition of the material through quantification of both EELS and EDX spectra on the same specimen. The main result, when ZDDP and CB additives are used together, is the formation of a calcium and zinc borophosphate glass tribofilm. The overall data confirm the general friction‐induced glass model as being a unifying concept that explains the mechanisms of antiwear additives under boundary lubrication. Moreover, the analytical results strongly suggest the role of viscous flow of the magma state glass tribofilm above its glass transition temperature to be a main contribution to the antiwear mechanism under mild wear conditions.

Tribochemical interactions between Zndtp, Modtc and calcium borate

Tribochemical interactions between antiwear zinc dithiophosphate (Zndtp), friction modifier molybdenum dithiocarbamate (Modtc) and overbased detergent calcium borate (OCB) lubricant additives have been investigated. Friction tests were performed in mild wear conditions under boundary lubrication, in order to enhance tribochemical surface effects. The nature of tribofilms formed was studied by coupling high‐resolution TEM on wear fragments and inside‐wear‐scar, micro‐spot XPS in the same location of the wear track (so‐called dual analysis). The performance of the Modtc/Zndtp mixture is mainly due to the generation of MoS2 single sheets and the digestion of MoO3 in the zinc polyphosphate glass formed. The final result of the tribochemical reaction is a two‐phase tribofilm composed of (i) non‐oriented MoS2 sheets (friction modifier) embedded in a carbon‐rich phase and (ii) a mixed Zn/Mo polyphosphate glass (antiwear). The Modtc/OCB mixture has a similar antiwear mechanism except that the oxide is not completely eliminated, due to the softer action of borate anion compared with phosphate one. Compared to the data obtained with binary combinations (Modtc/Zndtp, Modtc/OCB and Zndtp/OCB), we show here that the ternary system Modtc/Zndtp/OCB provides both a low wear rate and an ultralow friction value, while adding detergent and anti‐corrosive properties to the formulation. Our analytical data indicate that the synergistic effect can be attributed to an outstanding nanostructure of the tribofilm formed. It is composed of a single‐phase material containing perfectly oriented MoS2 single sheets embedded in a calcium and zinc borophosphate glass. The ternary system produces a smart material in the interface, because both functions (antiwear and friction reduction) are correlated. Compared to phosphate alone, the mechanism by which MoS2 sheets have been oriented in the borophosphate could be related to aligned molecules of the glassy polymer in the direction of sliding.

In situ MoS2 formation and selective transfer from MoDPT films

Abstract UHV friction tests and complementary analyses using AES, XPS, TEM and EELS give a global view of the friction reduction mechanisms of MoDTP antiwear and friction-reducing additive. The study was performed with MoDTP tribofilms composed mainly of an amorphous phosphate glass containing flexible and highly dispersed MoS 2 single sheets. The transfer films created under UHV friction were studied by AES. The hard and soft acids and bases (HSAB) principle was used to exploit the data. We observed that relatively high friction ( μ ∼0.3) was associated with the transfer of the whole tribofilm from the flat to the pin by a chemical reaction between the phosphates present in the tribofilm and the native oxide layer on the pin. When the oxide layer was removed, the MoS 2 sheets reacted with the nascent metal surface of the pin. The transfer film observed on the pin is very thin (4 nm) and it can clearly be seen that only a few single sheets of MoS 2 are needed to achieve friction at the centirange.

Role of nitrogen in tribochemical interaction between Zndtp and succinimide in boundary lubrication

Tribochemical interactions between zinc dithiophosphate (Zndtp) and polyisobutene succinimide (PIBSI) were studied in the mild wear regime by a dual analysis approach. Both TEM analyses of wear fragments and inside wear scar XPS on tribofilms were obtained in the same location of the wear track. In presence of the succinimide, there are notable modifications in the composition of the zinc polyphosphate tribofilm which is classically formed in presence of Zndtp alone. Apart from amorphous zinc polyphosphate glass, the film contains also large amounts of oxidised species (oxides, sulphates and nitrates) together with residual succinimide function groups. The atomic ratio N/P is about 0.3. Moreover, compared to Zndtp, less tribofilm is produced due to some competition in adsorption process. The results highlight the role of the tribochemical reaction to explain the antagonism between the two additives. The presence of some iron oxide in the tribofilm material indicates that the anti-abrasive wear mechanism of Zndtp is hindered by the presence of the succinimide. The lower content of the tribofilm in sulphide species also suggests a lower efficiency to control the anti-seizure properties of the mixture of the two additives.

Friction-reducing mechanisms of molybdenum dithiocarbamate/zinc dithiophosphate combination: New insights in MoS2 genesis

The friction-reducing properties of the Modtc/Zndtp combination were studied using a ultrahigh vacuum (UHV) analytical tribometer. The friction tests were performed on a previously formed tribofilm. Transmission electron microscopy observation shows that this tribofilm is composed of a mixture of zinc phosphate zones containing molybdenum and carbon-rich zones containing zinc and MoS2 single sheets. After UHV friction, the wear scars of both the sliding surfaces were characterized by in situ analytical tools like Auger electron spectroscopy, scanning Auger spectroscopy, and microspot x-ray photoelectron spectroscopy. Low friction is associated to the transfer of a thin MoS2 film to the pin. Zinc, phosphorous, and oxygen are localized in the wear debris surrounding the pin wear scar. The friction-reducing phenomena is explained on the basis of the hard and soft acids and bases principle.

UHV friction of tribofilms derived from metal dithiophosphates

The friction‐reduction mechanisms of Modtp and Zndtp were highlighted by submitting tribofilms to friction in ultra‐high vacuum (UHV). The use of an UHV tribometer to understand these phenomena is justified by the fact that the friction coefficient recorded in UHV is close to the friction coefficient obtained in traditional tests in oil. After UHV friction, the transfer films on the pin were analyzed by in situ AES, XPS and AES mapping. Low friction is associated with the transfer to the pin of a sulfur‐rich film. In the case of Modtp, we observe a very thin MoS2 film. The UHV friction coefficient approaches 0.04. In the case of Zndtp, the transfer film contains ZnS together with some phosphates. Because of the poor capacity of ZnS to reduce friction, the UHV friction coefficient recorded is near 0.15. A global model of the action of dithiophosphates in reducing friction is described on the basis of the hard and soft acids and bases (HSAB) principle.