Elaine S. Yamaguchi

Chemical characterization of tribochemical and thermal films generated from neutral and basic ZDDPs using X-ray absorption spectroscopy

X-ray absorption near edge structure (XANES) spectroscopy at the phosphorus L-edge and sulphur L-edge has been used to characterize the chemical nature of tribochemical and thermally generated films from several ZDDP antiwear agents in the neutral and basic forms. Using the P and S L-edge XANES spectra of model compounds with known structure as fingerprints, the chemical structures of P and S species in the films have been identified. P appears in all the films as polyphosphates in different proportions of short and long chain polyphosphates. In some films, polyphosphates are accompanied by unchanged ZDDP. Generally films generated from neutral and basic ZDDPs show similar P and S chemistry (polyphosphates and sulphides) but contain different proportions of unchanged ZDDP. However, the aryl ZDDP films have different polyphosphate structure compared to the alkyl ZDDP films. The sulphur proportion in the tribochemical films is decreased a great deal, but remains in the reduced form. However, S in the thermo-oxidatively generated films, appears both in the reduced and oxidized form, depending on the ZDDP and the temperature.

X-ray absorption study of antiwear films generated from ZDDP and borate micelles

Abstract The possible partial replacement of zinc dialkyldithiophosphate (ZDDP) by a multifunctional additive (borate–sulphonate micellar compound) was studied. X-ray absorption spectroscopy at the phosphorus, sulphur and boron edges was used to determine the chemistry of the tribochemical films, both at the surface and in the bulk. XANES data suggest an interaction between ZDDP and the borate additive. The sulphonate moiety reacts to form sulfite and sulfate, which allows the release of the borate core. However, this process is limited and a substantial proportion of unreacted micelles could be found in the film. The sulphonate moiety seems to play a major role in the interaction between the borate additive and ZDDP. Calcium phosphate was detected in the tribofilm as a result of this interaction. Although the additive contains boron, the film is quite similar to a film generated from ZDDP and calcium sulphonate. The performance of the additives was determined by the Wear Scar Width measurements. The data suggest that the antagonism between ZDDP and sulphonate is similar to the ZDDP–borate mixture. The antiwear function of ZDDP is almost completely retarded by sulphonate or borate–sulphonate additive.

X-Ray Absorption Study of the Effect of Calcium Sulfonate on Antiwear Film Formation Generated From Neutral and Basic ZDDPs: Part 1—Phosphorus Species

Zinc dialkyldithiophosphates (ZDDPs) from very effective antiwear films in boundary lubrication applications. In most cases, however, the ZDDPs do not work alone. They are formulated with many other additives to provide the performance required by todays modern oils. X-ray absorption near-edge spectroscopy (XANES) has been used to study the antiwear films formed from the commonly used combination of ZDDP and calcium sulfonate in both neutral and basic forms. The results are presented in two papers: Part 1 for the phosphorus species and Part 2 for the sulfur species. XANES showed conclusively that in the presence of LOB (low overbased) or HOB (high overbased) calcium sulfonate under sliding conditions, ZDDPs do not form long-chain polyphosphates that have been associated with antiwear action. Instead, short-chain polyphosphates calcium phosphate are formed. The relative amounts of calcium phosphate formed depend on the ester group of the ZDDP: aryl > n-alkyl > sec-alkyl. Interestingly, this order of ester groups is inversely related to the antiwear effectiveness of the ZDDPs. Thus, it is probable that the addition of either LOB or HOB calcium sulfonate to ZDDP will result in a decrease in antiwear effectiveness of the additive mixture compared to the ZDDP by itself. Wear data support this conclusion. It is suggested that the elimination of long-chain polyphosphates and the formation of calcium phosphates in the tribofilm leads to this decrease in antiwear effectiveness, the latter by abrasion of the antiwear film. Presented at the 55th Annual Meeting in Nashville, Tennessee May 7–11, 2000

Boundary film Formation by ZnDTPs and Detergents Using ECR

Overbased detergents and ZnDTPs form insulating boundary lubrication films. Electrical contact resistance (ECR) is therefore a convenient method of monitoring boundary film changes in a sliding contact. Separately, ZnDTPs and overbased detergents rapidly form insulating films. In combination, however, films may form slowly and, furthermore, may be less stable than films formed by the individual additives. Examples of film formation by ZnDTP-detergent combinations are described. ECR provides no information on boundary film chemistry. X-ray photoelectron spectroscopy (XPS) has been used to help identify some of the films. Inferences as to the chemistry of film formation can be drawn in some cases. Presented as a Society of Tribologists and Lubrication Engineers paper at the World Tribology Congress in London, United Kingdom, September 8–12, 1997

Antiwear film formation of neutral and basic ZDDP: influence of the reaction temperature and of the concentration

Both synchrotron radiation-based techniques (XANES) and transmission electron microscopy (EDX, EELS) are used to draw a comparison of antiwear and thermal films generated from neutral and basic ZDDP salts. Antiwear films were created in a pin-on-flat wear machine and the wear debris was collected. The analysis of the tribofilms did not show any substantial difference between neutral and basic ZDDPs. The wear scar diameter and the P and S chemical environment in the tribofilm were very similar. The chemical analysis of the wear debris revealed differences in the chemical composition. Wear debris from basic ZDDP seems to be mostly composed either of unreacted ZDDP or of a linkage isomer of ZDDP (LI-ZDDP), and zinc polyphosphate; whereas the wear debris as far as neutral ZDDP is concerned seems to be exclusively composed of zinc polyphosphate (and sulphur species). More iron was also detected in the wear debris with basic ZDDP – possibly an indication of the iron content of the tribofilm. Differences in chemical structure could also be detected in the thermal films. While neutral ZDDP reacted with the surface to form polyphosphates at 150°C, the same reaction products were obtained with basic ZDDP at 175°C. The concentration of ZDDP in oil is thought to be the main parameter to explain the differences in the thermal film formation.

Interaction of ZDDP with Borated Dispersant Using XANES and XPS

The thermochemical reaction and tribochemical reaction of zinc dialkyldithiophosphate (ZDDP), a borated dispersant, and the mixture of ZDDP and borated dispersant on steel surfaces were investigated. Both pin-on-disk and ball-on-disk were used to generate tribofilms. The chemical state of nitrogen, boron, phosphorus, and sulfur in heated oil solutions, thermal films, and tribofilms were analyzed by X-ray absorption near edge structure (XANES) spectroscopy to obtain the chemical nature of species on the surface and in the bulk of the films. High-resolution X-ray photoelectron spectroscopy (XPS) has also been used to analyze boron (B) in tribofilms. The borated dispersant in base oil by itself yields good anti-wear behavior. This can be attributed to the presence of boron in the dispersant. The wear scar widths (WSW) for ZDDP alone, and in combination with the dispersant, yield similar results within the experimental error. It was found that the borated dispersant facilitates the decomposition of ZDDP and the formation of phosphate in tribofilms and thermal films. B K-edge XANES shows that boron has a trigonal coordination in the untreated additive, but the coordination changes partially to a tetrahedral coordination in the tribofilm upon rubbing. No BN was detected in the film analyzed by B K-edge or N K-edge. Boron 1s XPS also did not show the presence of BN in the film.

Tribofilms Generated From ZDDP and DDP on Steel Surfaces: Part 2 — Chemistry

The chemical constitution of tribofilms, generated from zinc dialkyldithiophosphate (ZDDP) and ashless dialkyldithiophosphate (DDP), has been examined by X-ray Absorption Near Edge Structure (XANES) spectroscopy. The identification of spectral features and interpretation of the results for P, O, Fe, and S species are given, allowing an overall mechanism to be deduced. The role of Fe in these films was investigated in some detail using P L-edge, O K-edge and Fe L-edge XANES spectra. From the P L-edge XANES spectra, the DDP films are uniformly very short chain iron polyphosphates. In contrast, the ZDDP films are formed initially as short chain polyphosphates; but after more rubbing, a bilayer phosphate film is formed with long chain Zn polyphosphates on the surface and shorter chain in the bulk of the film. The O K-edge XANES spectra show that there is, as expected, more Fe in the DDP phosphate films than in the ZDDP phosphate films. The S K-edge spectra of ZDDP films show the presence not only of ZnS as previously observed, but also the presence of FeS for the first time in the early stages of film formation. The predominant S species in the DDP films is FeS.

Antiwear Tribofilm Formation on Steel Surfaces Lubricated With Gear Oil Containing Borate, Phosphorus, and Sulfur Additives

The formation of antiwear tribofilms plays a critical role in the longevity of automotive gears. The focus of this experimental study was on the lubrication efficacy of gear oils with different contents of borate-, phosphorus-, and sulfur-containing additives leading to the formation of protective tribofilms. Experiments were performed with AISI 52100 steel balls sliding against AISI 52100 steel disks in baths of different oils at ambient (∼32 °C) and elevated (∼100 °C) temperatures under load and speed conditions favoring sliding in the boundary lubrication regime. Friction coefficient responses accompanied by electrical contact voltage measurements provided real-time information about the formation and durability of the antiwear tribofilms. The wear resistance of the tribochemical films was quantified by wear rate data obtained from surface profilometry measurements of wear tracks on the disk specimens and sliding tests performed at ambient temperatures after the formation of the tribofilms during elevated-temperature sliding. Results indicate a strong dependence of tribofilm formation on temperature and type of additives. The slightly lower friction and higher wear resistance obtained at elevated temperatures with blended oils is attributed to the increased chemical reactivity of additives containing borate, phosphorus, and sulfur, leading to the formation of durable tribofilms. Relatively higher wear resistance and faster tribofilm formation were obtained with the borate-enriched gear oil formulations. Presented as a Society of Tribologists and Lubrication Engineers Paper at the ASME/STLE Tribology Conference in Cancun, Mexico October 27–30, 2002

Soot Wear in Diesel Engines

Abstract In response to regulatory requirements, lubricant manufacturers are seeking oils that minimize soot thickening and the accompanying soot wear. Formulation technology is being developed by additive manufacturers to satisfy these requirements. For example, such work is in progress at Chevron Oronite Company LLC, using the Cummins M-11 exhaust gas recirculation (EGR) engine test as a surrogate for the anticipated soot wear test for PC-10. Simultaneously, the authors developed bench tests to screen candidate formulations and reduce costs. A ball-on-disc sliding wear test, using a PCS Instruments MTM® tribometer, has been investigated. Sliding conditions at high pressure are required for soot polishing wear. Conditions that correlate tribometer test results with M-11 engine results at high soot concentrations (∼9 per cent) have been found. Both ball wear and Stribeck curves were determined in these tests. The high-wear oil progresses from mixed lubrication conditions to boundary lubrication at higher sliding speeds than the low-wear oil. X-ray photoelectron spectroscopy experiments were also conducted on the ball wear scars, revealing differences in the chemical constitution of the tribofilms from the two oils.

The relative oxidation inhibition performance of some neutral and basic zinc dithiophosphate salts

Recent engine testing on separate neutral and basic zinc dithiophosphates (ZnDTPs) showed a difference in valve train wear performance, with the neutral ZnDTP giving statistically better wear inhibition in Sequence VE tests. Since the literature was lacking on the oxidation inhibition performance of the separate neutral and basic salts, we systematically examined the relative antioxidancy of several neutral and basic ZnDTP salts in various formulations. The results were dependent on the type of base oil and formulation used, and the presence of other additives. 31P NMR Spectroscopy, coupled with Oxidator Bench Test studies, were used to reach these conclusions. Presented at the 54th Annual Meeting Las Vegas, Nevada May 23–27, 1999