A Combinatorial Approach to Elucidating Tribochemical Mechanisms

A new type of combinatorial tribological experiment is presented, which explores a series of tribological conditions, such as load and relative velocity, spatially separated as a library on one single sample. As an example, a library displaying the results of tribological testing of an additive under a series of different loads has been prepared and analyzed. The tribological information acquired during the testing has been correlated with spectroscopic information from the tribologically stressed surface. The use of imaging and small-area X-ray photoelectron spectroscopy has allowed the identification of the different tribologically stressed areas and the acquisition of detailed spectroscopic information. The composition and the thickness of the tribofilm were found to be dependent on the applied load. The use of the combinatorial approach shows the potential to greatly facilitate rapid characterization of new lubricant additives.     

Pressure Dependence of ZnDTP Tribochemical Film Formation: A Combinatorial Approach

Combinatorial testing has been performed on zinc dialkyldithiophosphate (ZnDTP)-containing lubricants, to investigate the effects of contact pressure on the formation of tribochemical films. Contact pressures ranging from 25 to 500 MPa were applied in ball-on-disc tribotests with oscillating load. Both the ball and the disc were investigated by means of small-area and imaging X-ray photoelectron spectroscopy (XPS). The thickness and the composition of the reaction layer were estimated from the XPS data. The thickness of the reaction layer in the tribologically stressed areas of the ball and of the disc increased with both temperature and contact pressure. The reaction layer mainly consisted of short-chain poly(thio)phosphates, shorter chains being observed at higher contact pressures. At high pressures, the presence of a thick, high-toughness short-chain poly(thio)phosphate layer can explain the lower friction and dimensional wear coefficients observed. On the ball, similar anti-wear film formation mechanisms were observed as on the disc, zinc sulphide being deposited in the post-contact region.     

XPS study of the influence of temperature on ZnDTP tribofilm composition

Antiwear additives, such as zinc dialkyldithiophosphate (ZnDTP), find application in many different industrial sectors. Although it is understood that certain ZnDTP concentrations need to be used to achieve an effective antiwear performance, there has been very little work published concerning the effect of temperature on the interactions of the additive and its adsorption mechanism on steel. In this article, 100Cr6 (52100) steel ball-on-disc experiments under solutions of zinc dialkyldithiophosphate (ZnDTP) in poly-α-olefin (PAO) were performed at different temperatures, ranging from 25 to 180 °C. The discs were analysed after the experiments by means of small-area, imaging and angle-resolved X-ray photoelectron spectroscopy (XPS). The composition of the reaction film was found to change as a function of the applied temperature and also to vary within the film as a function of depth: Longer polyphosphate chains were found at higher temperatures as well as towards the outer part of the reaction film.     

Combined in situ (ATR FT-IR) and ex situ (XPS) Study of the ZnDTP-Iron Surface Interaction

Attenuated total reflection infrared (ATR FT-IR) and X-ray photoelectron spectroscopy (XPS) have been used for the in situ and ex situ characterization of thermal and tribological films formed on iron from a commercial zinc dialkyldithiophosphate (ZnDTP). From in situ ATR FT-IR analysis, information on the chemical changes occurring at the iron/lubricant additive interface was obtained during heating and sliding at high temperatures. Different mechanisms and chemical compositions have been found for the thermal and tribochemical reactions between the ZnDTP and the iron surface under the experimental conditions used in this work. Both the ATR FT-IR and the XPS results show the decomposition of ZnDTP with the formation of polyphosphates following thermal testing at 150°C. However, after tribological testing at the same temperature an inorganic phosphate film has been detected on the iron surface instead.     

Triboemission as a basic part of the boundary friction regime: A review

This paper reviews selected phenomena related to the boundary friction process. The central thrust is on triboemission, defined as emission of electrons, charged particles, photons, etc., under conditions of boundary friction and/or surface damage caused by fracture processes. Low‐energy electrons are one of the most important particle components in triboemission. Accordingly, the triboemission process is of particular significance for (i) the boundary friction process as such, and (ii) the tribochemistry of the boundary lubrication process. This review considers all the major issues of triboemission and related phenomena/processes. It is shown that, in the boundary lubrication regime with hydrocarbon lubricants, charge intensities decrease with an increase in lubricant molecular weight. The paper also includes some recent information concerning research on triboemission along with a newly developed apparatus.     

Study of the Interaction of ZDDP and Dispersants Using X-ray Absorption Near Edge Structure Spectroscopy—Part 2: Tribochemical Reactions

The antiwear properties of zinc dialkyldithiophosphate (ZDDP), dispersants, and mixtures of ZDDP and different dispersants have been evaluated using a pin-on-flat Plint wear machine. Tribochemical interactions between ZDDP and dispersants have been investigated under boundary lubrication conditions by means of X-ray absorption near edge structure (XANES) spectroscopy, probing the phosphorus, sulfur and nitrogen absorption edges. The results show that the dispersants do not give any wear protection by themselves in the base oil. The dispersants also do not affect the antiwear property of ZDDP under the given testing conditions. The N K-edge XANES analysis indicates that dispersants contribute to the chemical composition of the tribofilms and form mixed ammonium/zinc polyphosphates. Phosphorus in the tribofilms is present mainly in the form of medium-chain polyphosphate on the surface and short-chain polyphosphate in the bulk. Sulfur appears in the tribofilms mainly as sulfide S^-II, possibly zinc sulfide. The presence of dispersants in oil blends does not disturb the polyphosphate (and sulfide) formation, but it does decrease the chain length of the polyphosphate in the tribofilms.     

Study of the Chemistry of Films Generated from Phosphate Ester Additives on 52100 Steel Using X-ray Absorption Spectroscopy

X-ray absorption near-edge structure spectroscopy (XANES) has been used to investigate the chemistry and thickness of thermal and antiwear (AW) films generated on steel from oil solutions containing phosphate ester additives. DPP, a diaryl phosphate, reacted with steel to form a thermal phosphate film at lower temperatures than TPP, a triaryl phosphate and Irgalube 349, an amine phosphate. This phosphate film formation at lower temperatures resulted in better wear protection to the metal in tribochemical experiments, as indicated by a smaller wear-scar measurement for oil solutions containing the DPP additive. For TPP, a brief period of wear to the metal was necessary to initiate the tribochemical reaction between the additive and substrate. Once the tribochemical reaction begins, TPP is able to generate a tribochemical film of relatively the same thickness and chemistry as DPP. Irgalube 349 generated the thickest thermal films at temperatures greater than 150 °C, significantly thicker than any of the films generated from DPP and TPP. The substantial difference in thickness is believed to be due to the availability of alkyl/ammonium cations which enables continued growth of the phosphate film.     

Numerical Study of the Effect of Tribofilm Kinetics and Its Hardness on the Roughness Evolution of the Substrate in Boundary Lubrication Regime

Abstract

A tribochemical modeling framework that considers the growth of a tribofilm on the contacting surfaces has been used in this work. The model couples a fast contact mechanics model with the thermodynamics of interfaces and captures the growth of the tribofilm on the asperities. The model was shown to be able to capture the dynamics of a tribosystem and the evolution of surface topography. The model considers the effect of plastic deformation and wear in modifying the surface geometries. In a recent work by the authors (Ghanbarzadeh et al., Wear, 362–363, 2016), the same numerical model was validated against experiments in a micropitting rig (MPR) and the wear, topography, and tribofilm thickness results were compared. In this work, validation of the model is presented and the effect of tribofilm kinetics and its hardness have been numerically studied to assess the evolution of surface roughness in a rolling sliding contact. Results suggest that the kinetics of the tribofilm growth significantly influence the roughness evolution with higher kinetics resulting in a rougher interface. Similarly, the tribofilm hardness affects the roughness evolution and is more influential in the later stages of roughness evolution.     

Anisotropic oxidation of MoS2 crystallites studied by angle-resolved X-ray photoelectron spectroscopy

The oxidation behavior of the solid lubricant MoS₂ was studied using X-ray photoelectron spectroscopy. MoS₂-containing slip ring brushes were used to take advantage of anisotropic orientation of the plate-shaped MoS₂ crystallites occurring during fabrication of the brushes. Because oxidation occurs preferentially at the edges of the crystallites, greater oxidation fractions are measured when the edges are oriented toward the photoelectron energy analyzer. These results indicate a novel method for separately probing the chemistry on the edge and (lubricious) basal surfaces of MoS₂.     

Determination of oxygen in acid-treated high-purity niobium by X-ray photoelectron spectroscopy

High-purity niobium was immersed in nitric acid and hydrofluoric acid for two minutes and the resulting product was characterized. Scanning electron microscopy was employed to characterize the morphology of the acid treated product. Inert gas fusion was used for determination of oxygen in the high-purity niobium. X-ray photoelectron spectroscopy was employed to characterize the surface ratio of oxygen to niobium. The oxygen concentration was 30 ppm in the acid-treated material and 70 ppm in the untreated material. X-ray photoelectron spectroscopy was employed to characterize the reduction of oxygen at the surface. The ratio of oxygen to niobium decreased from 9.75 to 2.60 without treatment compared to acid treatment for two minutes. The concentrations of adsorbed water and niobium oxide decreased following etching. The acid-treated high-purity niobium was characterized by argon ion bombardment; adsorbed water molecules and niobium oxides were not present but non-lattice oxygen was observed.     

Tribological performances of heterocyclic‐containing ether and/or thioether as additives in the synthetic diester

The load‐carrying capacity, wear and friction properties of 2‐octoxyl methylthio‐benzothiazole (DEOY) and 2‐dodecylthio methylthio‐benzothiazole (DEMB) added to a synthetic lubricant (diester) were evaluated using a four‐ball test machine. The results indicate that the two compounds added to the diester possess good load‐carrying capacities and excellent anti‐wear and friction reduction properties. The thermal stability of the two compounds under nitrogen atmosphere was investigated by thermogravimetric analysis (TGA). It was found that the compounds DEOY and DEMB possess excellent thermal stability. The surface topography of the rubbed surface was investigated with scanning electron microscopy, the elemental chemical nature of the anti‐wear films generated on steel counterface were investigated with X‐ray photoelectron spectroscopy. Copyright © 2009 John Wiley & Sons, Ltd.     

The Tribological Properties of Monolayer KCl Films on Iron in Ultrahigh Vacuum: Modeling the Extreme-Pressure Lubricating Interface

The friction coefficients of thin KCl films deposited onto clean iron in ultrahigh vacuum are measured using a tungsten carbide tip. A rapid decrease is found in the friction coefficient from 2 for clean iron to 0.27 ± 0.03 after the deposition of 40 Å of KCl. Based on previous contact resistance measurements, this was proposed to be due to the completion of the first layer of KCl. The first-layer KCl coverage was measured by adsorbing deuterium onto an iron surface partially covered by KCl, where deuterium selectively adsorbs onto the iron. This revealed that the first monolayer is complete after the deposition of 40 Å of KCl and that the first-layer KCl film coverage _KCl ⁽¹⁾ is given by _KCl ⁽¹⁾ = 1 - exp(-0.39±0.02t), where t is the film thickness. XPS data suggest that heating a KCl film to 550 K causes it to wet the surface. This leads to decreases in the friction coefficients for thin KCl films in accord with the idea that friction is reduced by the first monolayer of KCl on iron. Temperature-programmed desorption data indicate that KCl in the first monolayer is 5 kJ/mol more stable than the multilayer consistent with the wetting behavior. Finally, the kinetic data are analyzed to suggest that the first-layer film is 2.6 Å thick.     

A molecular-beam study of the tribological chemistry of carbon tetrachloride on oxygen-covered iron

Dc molecular-beam methods are used to examine the reactivity of carbon tetrachloride with oxide films grown on iron in ultrahigh vacuum. The incident CCl₄ beam flux is sufficiently low that the nature of the surface oxide is dictated by the annealing temperature allowing the reactivity of Fe₂O₃, Fe₃O₄ and FeO films to be examined. Carbon tetrachloride reacts rapidly with Fe₂O₃ and reaction with Fe₃O₄ commences at 620 K to evolve CO. The activation energy for this process is 20.6±1.0 kcal/mol. CCl₄ reacts with FeO above 790 K, also to evolve CO, and the activation energy for this reaction is 5.7±0.4 kcal/mol. X-ray photoelectron spectroscopy shows the formation of a halide after reaction at 900 K. These results are in accord with film-growth kinetics measured using a microbalance at high pressures, where it was found that it was not necessary to remove the oxide layer prior to reaction. This contrasts with the behavior of sulfur-containing molecules, where the oxide layer had to be removed before a film would grow. This effect may contribute to the additive synergies commonly found in extreme-pressure lubricant additives where one of the roles of the chloride may be to reduce the oxide layer.     

A comparison of two models for the characteristic X-ray fluorescence correction in thin foil analysis

It is shown that Philibert & Tixier's calculation for the contribution of characteristic fluorescence in thin foil X-ray microanalysis is in error. The calculation of Nockolds et al. for this contribution is shown to be correct.     

Resolving the Chemical Variation of Phosphates in Thin ZDDP Tribofilms by X-ray Photoelectron Spectroscopy Using Synchrotron Radiation: Evidence for Ultraphosphates and Organic Phosphates

X-ray photoelectron spectroscopy using a synchrotron source (SR-XPS) with variable photon energy has been used to non-destructively elucidate the variations in surface chemistry from ~5 nm to ~10 nm into the tribofilm derived from zinc dialkyldithiophosphate (ZDDP) in a mineral oil under boundary lubrication conditions. The elemental ratio of P/Zn and “bridging” oxygen (BO)/“non-bridging” oxygen (NBO) decrease as a function of distance from the top surface of the film, suggesting a decrease of the polyphosphate chain-length into the film, as shown in many recent XPS and XANES studies. More importantly, the measured P/Zn ratio of ~3, the BO/NBO ratios of >0.5, the P 2p spectra, and the absence of other balancing cations such as iron, show the first strong evidence for an ultrapolyphosphate (such as ZnP₄O₁₁), organophosphates along with other Zn polyphosphates. The existence of ultraphosphates and/or organophosphates in this film appears to be the long-awaited answer to the apparent deficiency of cations in these antiwear films.     

傅立叶变换红外光谱在食用油分析上的应用

近年来,食用植物油的问题越来越多,从地沟油到反式脂肪酸等一系列事件频繁曝光。而传统的检测方法费时费力,本文综述了傅立叶变换红外光谱在食用油分析上的应用。该技术可以对油脂进行分类和掺杂掺假检测,同时运用光谱数据和化学计量学方法还可以对食用油的反式不饱和脂肪酸含量、游离脂肪酸含量、碘值、皂化值及过氧化值等进行快速检测。     

Raman Spectroscopy Techniques for the Detection of Biological Samples in Suspensions and as Aerosol Particles: A Review

This article reviews current scientific literature focusing on Raman spectroscopy modalities that have been successfully applied to the detection of biological samples in aqueous suspensions and in aerosols. Normal Raman, surface enhanced Raman scattering, coherent anti-stokes Raman scattering, resonance Raman and UV-Raman spectropies, allow the detection of biological samples in situ in the near field and as well as in the far field at standoff distances. Applications span from fundamental studies to applied research in areas of defense and security and in monitoring of environmental pollution. A primary focus has been placed on biological samples including bacteria, pollen, virus, and biological contents in these specimens, in suspensions, and in aerosols. Several Raman spectroscopy studies have been reviewed to show how various modalities can achieve detection in these biosystems. Current data generated by our group is also included. Necessary parameters used to accomplish the detection and data analysis, which could also be used to interpret the results and to render the methodologies robust and reliable, are discussed.     

Surface reactivity of tributyl thiophosphate: effects of temperature and mechanical stress

The surface reactivity of tributyl thiophosphate on iron surfaces has been studied in situ by attenuated total reflection Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy and temperature-programmed reaction and desorption spectroscopies. The results show that at temperatures lower than 373 K the molecule forms a physisorbed layer on the iron substrate. At 373 K a reaction takes place with the formation of an organic layer, together with iron polyphosphate and sulfate. At higher temperatures temperature-programmed desorption results suggest that the mechanism involves P–O bond scission to yield butoxy groups. This could be preceded by P=S bond scission to give tributyl phosphite, which then, in turn, undergoes P–O bond scission to produce butoxy groups. The results obtained following tribological testing are in agreement with those of thermal tests: evidence of polyphosphate and sulfate formation is found.     

A synchrotron X-ray study of the changes occurring in the corneal stroma during processing for electron microscopy

Using a high-intensity synchrotron X-ray source, the structural changes occurring in the corneal stroma were monitored during each stage of several different processing runs for the transmission electron microscope (TEM) and scanning electron microscope (SEM). The parameters studied were interfibrillar spacing, intermolecular spacing, D-periodicity and fibril diameter. The processing schedule that produced the least changes in spacings for TEM specimens involved extended fixation in glutaraldehyde followed by low-temperature embedding in Lowicryl K4M resin. However, interfibrillar material was better preserved after embedding in LR White resin or Nanoplast. Almost every processing stage for electron microscopy produced significant changes in one or more structural parameters in the cornea. Glutaraldehyde fixation significantly increased the intermolecular spacings, while resin infiltration and resin polymerization each resulted in shrinkage of all the spacings monitored. Critical-point drying for SEM specimens resulted in considerable shrinkage in all three spacings, but was still preferable to air drying, which caused reduction in the order of the fibril packing, resulting in loss of the interfibrillar X-ray pattern. Perhaps the most drastic effect was caused by post-fixation in osmium tetroxide, which resulted in loss of the intermolecular pattern, and also increased the amount of shrinkage in the interfibrillar spacings and the D-periodicity which occurred during later stages of processing.     

Investigation of Tribo-chemistry by means of Stable Isotopic Tracers: TOF-SIMS Analysis of Langmuir–Blodgett Films and Examination of their Tribological Properties

Deuterium-substituted and ¹³C-substituted octadecanoic acids were applied to study tribo-chemistry of binary-component Langmuir–Blodgett film deposited on Si(100) surfaces. Time-of-flight secondary ion mass spectroscopy was employed to study structure of the film. The isotopic tracers give typical fragment ions composed of the isotopes. Among these typical fragment ions, we paid attention to quasi-molecular ions and deuterium ion as “fingerprint region” of the film structure. The tribological properties of the binary-component film were evaluated by ball-on-plate type tribo-testers. The combination of octadecanol with octadecanoic acid affords good tribological properties, whereas the combination of octadecylamine with the acid gave poor results. The surface analysis of the plate after the tribo-test revealed that the alcohol and the acid were retained on the track even after the rubbing. On the other hand simultaneous removal of the acid and the amine from the surfaces were observed. Interactions between the acid and the amine were considered by the results of the tribo-tests and the surface analysis of the binary-component film.