An XPS study of the stability of Fomblin Z25 on the native oxide of aluminum

Thin films of Fomblin Z25, a perfluoropolyalkylether lubricant, were vapor deposited onto clean, oxidized aluminum and sapphire surfaces, and their behavior at different temperatures was studied using x ray photoelectron spectroscopy (XPS) and thermal desorption spectroscopy (TDS). It was found that the interfacial fluid molecules decompose on the native oxide at room temperature, and continue to decompose at elevated temperatures, as previous studies had shown to occur on clean metal. TDS indicated that different degradation mechanisms were operative for clean and oxidized aluminum. On sapphire substrates, no reaction was observed at room temperature. Our conclusion is that the native oxide of aluminum is neither passive nor protective towards Fomblin Z25. At high temperatures (150 C) degradation of the polymer on sapphire produced a debris layer at the interface with a chemical composition similar to the one formed on aluminum oxide. Rubbing a Fomblin film on a single crystal sapphire also induced the decomposition of the lubricant in contact with the interface and the formulation of a debris layer

Interfacial chemistry of a perfluoropolyether lubricant studied by XPS and TDS

The interfacial chemistry of Fomblin Z25, a commercial perfluoropolyether used as lubricant for space applications, with different metallic surfaces: 440C steel, gold and aluminum was studied. Thin layers of Fomblin Z25 were evaporated onto the oxide-free substrates and the interfacial chemistry studied using XPS and TDS. The reactions were induced by heating the substrate and by rubbing the substrate with a steel ball. Gold was found to be completely unreactive towards Fomblin at any temperature. Reaction at room temperature was observed only in the case of the aluminum substrate, the most reactive towards Fomblin Z25 of the substrates studied. It was necessary to heat the 440C steel substrate to 190 degree C to induce decomposition of the fluid. The degradation of the fluid was indicated by the formation of a debris layer at the interface. This debris layer, composed of inorganic and organic reaction products, when completely formed, passivated the surface from further attack to the Fromblin on top. The tribologically induced reactions on 440C steel formed a debris layer of similar chemical characteristics to the thermally induced layer. In all cases, the degradation reaction resulted in preferential consumption of the difluoroformyl carbon (-OCF2O-)

The Effects of Acid Passivation, Tricresyl Phosphate Pre-Soak, and UV/Ozone Treatment on the Tribology of Perfluoropolyether-Lubricated 440C Stainless Steel Couples

The boundary-lubrication performance of perfluoropolyether (PFPE) thin films in the presence of passivated 440 C stainless steel is presented. The study utilized a standard ball-on-disc tribometer. Stainless steel surfaces were passivated with one of four techniques: 1) submersion in a chromic acid bath for 30 minutes at 46 C, 2) submersion in a chromic acid bath for 60 minutes at 56 C, 3) submersion in a tricresyl phosphate (TCP) bath for 2 days at 107 C, or 4) UV/Ozone treated for 15 minutes. After passivation, each disc had a 400 A film of PFPE (hexafluoropropene oxide) applied to it reproducibly (+/- 20%) and uniformly (+/- 15%) using a film deposition device. The lifetimes of these films were quantified by measuring the number of sliding wear cycles required to induce an increase in the friction coefficient from an initial value characteristic of the lubricated wear couple to a final, or failure value, characteristic of an unlubricated, unpassivated wear couple. The lubricated lifetime of the 440 C couple was not altered as a result of the various passivation techniques. The resulting surface chemistry of each passivation technique was examined using X-ray Photoelectron Spectroscopy (XPS). It was found that chromic acid passivation altered the Cr to Fe ratio of the surface. TCP passivation resulted in a FePO4 layer on the surface, while UV/Ozone passivation only removed the carbonaceous contamination layer. None of the passivation techniques were found to dramatically increase the oxide film thickness

Spectroscopic Analysis of Perfluoropolyether Lubricant Degradation During Boundary Lubrication

The degradation of a branched perfluoropolyether (PFPE) under boundary lubrication conditions was studied using mu-FTIR and mu-Raman spectroscopies. Stainless steel (440C) discs coated with thin (600A), uniform films of the PFPE were tested in a ball-on-disc apparatus until various levels of friction coefficient were attained. Discs were then examined using the above techniques. When the friction coefficient surpassed the value obtained with an un-lubricated control, the lubricant film had either been physically displaced or partially transformed in to a 'friction polymer'. Infrared analysis of this 'friction polymer' indicated the presence of a polymeric fluorinated acid species (R(sub f)COOH). Raman spectroscopy indicated the presence of amorphous carbon in the wear track and in the friction polymer. Some reaction mechanisms are suggested to explain the results

XPS analysis of 440C steel surfaces lubricated with perfluoropolyethers under sliding conditions in high vacuum

This work presents the results of the X-Ray Photoelectron Spectroscopy (XPS) analysis of AISI 440C ball surfaces lubricated with perfluoropolyether (PFPE) oils after friction experiments under sliding conditions at high load in air and vacuum environments. The PFPE lubricants tested were Demnum S100, Fomblin Z-25, and Krytox 143AB. It was found that all the PFPE lubricants were degraded by sliding contact causing the formation of inorganic fluorides on the metallic surfaces and a layer of organic decomposition products. KRYTOX 143AB was the least reactive of the three lubricants tested. It was also found that metal fluoride formed at off-scar areas. This suggests the formation of reactive species, such as COF2 or R(sub f)COF, during sliding experiments, which can diffuse through the lubricant film and react with the metallic surfaces away from the contact region. Comparison of reference specimens before sliding with those that had undergone the sliding tests showed that the amount of non-degraded PFPE remaining on the surface of the balls after the sliding experiments was greater than that of the balls without sliding

A New Antiwear Additive/Surface Pretreatment for PFPE Liquid Lubricants

Pin-on-disk tribology experiments were conducted on a perfluoroalkylelher (PFPE) liquid lubricant with and without a new PFPE lubricant antiwear additive material, a silane. It was found that the silane provided moderate improvement in the antiwear performance of the PFPE lubricant when applied to the metallic surface as a surface coating or when added to the PFPE as a dispersion (emulsion). Slightly better results were obtained by using the combination of a surface coating and an emulsion of the silane. The silane emulsions or coatings did not affect the friction properties of the lubricant. Micro-Fourier transformation infrared (muFTIR) spectroscopy analysis was performed to study silane transfer films and the degradation of the PFPE. The silane was found to mitigate degradation of the PFPE which may have been the major reason for the improved antiwear performance observed

The Effect of ODC-Free Cleaning Techniques on Bearing Lifetimes in the Parched Elastohydrodynamic Regime

A parched elastohydrodynamic rig was used to determine relative bearing lifetimes as a function of cleaning procedures in a series of accelerated tests. Two ODC-free cleaning procedures (super critical CO2 and ultraviolet-ozone) were compared to a CFC-113 control. Bearings (52100 steel) were run in the counter rotating mode (equivalent to 4600 rpm) with a full complement (i.e. no retainer) and a single charge of lubricant (Krytox 143 AC). Test conditions included: an air atmosphere, 445 N load, approx. 1.0 GPa mean Hertz stress. There was approximately a 50% reduction in life with bearings cleaned with UV/ozone and a 70% reduction in life with SFE CO2 when compared to the Freon control. Possible reasons for these decreases in lifetimes are presented

Evaluation of Boundary-Enhancement Additives for Perfluoropolyethers

Six additives were synthesized and evaluated as boundary lubrication enhancers for perfluoropolyethers. These additives included a phosphonate, a thiophosphonate, a beta-diketone, a benzothiazole, an amide and a sulfite. These additives were evaluated in a vacuum four-ball apparatus, at a one weight percent concentration in a perfluoropolyether based on hexafluoropropene oxide. Tests were performed in vacuum (less than 5.0 x 10(exp 6) Torr), at room temperature (approx. 23 C), at an initial Hertzian stress of 3.5 GPa (200N load), and a sliding velocity of 28.8 mm/sec (100 rpm). Infrared (IR) and Raman spectroscopies were used to analyze the 440 C specimens after testing. Wear rates for each formulation were determined from the slope of wear volume as a function of sliding distance. All additives yielded reductions in mean wear rates of at least 55 percent, with the exception of the benzothiazole which had no effect. Two of the additives, an amide and a sulfite, reduced the mean wear rate by at least 80 percent. IR and Raman analysis indicated the severity of wear can be correlated to the amount of surface fluorinated polymeric acid species (R(sub f)COOH) and amorphous carbon, in and around the wear scar

The effects of ion implantation on the tribology of perfluoropolyether-lubricated 440C stainless steel couples

The lubricating lifetime of thin films of a perfluoropolyether (PFPE) based on hexafluoropropene oxide in the presence of ion implanted 440C stainless steel is presented. Stainless steel discs, either unimplanted or implanted with N2, C, Ti, Ti + N2, or Ti + C had a thin film of PFPE (60-400 A) applied to them reproducibly (+/- 20 percent) and uniformly (+/- 15 percent) using a device developed for this study. The lifetimes of these films were quantified by measuring the number of sliding-wear cycles required to induce an increase in the friction coefficient from an initial value characteristic of the lubricated wear couple to a final, or failure value, characteristic of an unlubricated, unimplanted couple. The tests were performed in a dry nitrogen atmosphere (less than 1 percent RH) at room temperature using a 3 N normal load with a relative sliding speed of 0.05 m/s. The lubricated lifetime of the 440C couple was increased by an order of magnitude by implanting the disc with Ti. Ranked from most to least effective, the implanted species were: Ti; Ti+C; unimplanted; N2; C approximately equals Ti+N2. The mechanism postulated to explain these results involves the formation of a passivating or reactive layer which inhibits or facilitates the production of active sites. The corresponding surface microstructures induced by ion implantation, obtained using x-ray diffraction and conversion electron Mossbauer spectroscopy, ranked from most to least effective in enhancing lubricant lifetime were: amorphous Fe-Cr-Ti; amorphous Fe-Cr-Ti-C + TiC; unimplanted; epsilon-(Fe,Cr)(sub x)N, x = 2 or 3; amorphous Fe-Cr-C approximately equals amorphous Fe-Cr-Ti-N

Hyperoxemia and excess oxygen use in early acute respiratory distress syndrome : Insights from the LUNG SAFE study

Publisher Copyright: © 2020 The Author(s). Copyright: Copyright 2020 Elsevier B.V., All rights reserved.Background: Concerns exist regarding the prevalence and impact of unnecessary oxygen use in patients with acute respiratory distress syndrome (ARDS). We examined this issue in patients with ARDS enrolled in the Large observational study to UNderstand the Global impact of Severe Acute respiratory FailurE (LUNG SAFE) study. Methods: In this secondary analysis of the LUNG SAFE study, we wished to determine the prevalence and the outcomes associated with hyperoxemia on day 1, sustained hyperoxemia, and excessive oxygen use in patients with early ARDS. Patients who fulfilled criteria of ARDS on day 1 and day 2 of acute hypoxemic respiratory failure were categorized based on the presence of hyperoxemia (PaO2 > 100 mmHg) on day 1, sustained (i.e., present on day 1 and day 2) hyperoxemia, or excessive oxygen use (FIO2 ≥ 0.60 during hyperoxemia). Results: Of 2005 patients that met the inclusion criteria, 131 (6.5%) were hypoxemic (PaO2 < 55 mmHg), 607 (30%) had hyperoxemia on day 1, and 250 (12%) had sustained hyperoxemia. Excess FIO2 use occurred in 400 (66%) out of 607 patients with hyperoxemia. Excess FIO2 use decreased from day 1 to day 2 of ARDS, with most hyperoxemic patients on day 2 receiving relatively low FIO2. Multivariate analyses found no independent relationship between day 1 hyperoxemia, sustained hyperoxemia, or excess FIO2 use and adverse clinical outcomes. Mortality was 42% in patients with excess FIO2 use, compared to 39% in a propensity-matched sample of normoxemic (PaO2 55-100 mmHg) patients (P = 0.47). Conclusions: Hyperoxemia and excess oxygen use are both prevalent in early ARDS but are most often non-sustained. No relationship was found between hyperoxemia or excessive oxygen use and patient outcome in this cohort. Trial registration: LUNG-SAFE is registered with ClinicalTrials.gov, NCT02010073publishersversionPeer reviewe