Determination of the oxidative stability of perfluoropolyalkyl ethers and correlation with chemical structure

The oxidative stabilities of several perfluoropolyalkyl ethers (PFPAE) with related chemical structures were determined by thermal gravimetric analysis and correlated with their chemical structures. These results show that oxidative stability increases as the number of difluoroformal groups decreases and as trifluoromethyl substituents are added. They are also consistent with a recently proposed intramolecular disproportionation reaction mechanism involving coordination of successive ether oxygens to a Lewis acid. Since polytetrafluoroethylene contains no oxygen, it provides an indication of the upper limit to oxidative stability of PFPAE fluids. These results also show that oxidative decomposition of PFPAE fluids requires the presence of an active metal as well as air. Consequently, it may be possible to minimize decomposition and thus improve oxidative stability by passivating reactive metal surfaces

Determination of the thermal stability of perfluoroalkylethers

The thermal decomposition temperatures of several commercial and custom synthesized perfluoroalkylether fluids were determined with a computerized tensimeter. In general, the decomposition temperatures of the commercial fluids were all similar and significantly higher than those for custom synthesized fluids. Correlation of the decomposition temperatures with the molecular structures of the primary components of the commercial fluids revealed that the stability of the fluids is not affected by intrinsic factors such as carbon chain length, branching, or cumulated difluoroformal groups. Instead, correlation with extrinsic factors revealed that the stability may be limited by the presence of small quantities of thermally unstable material and/or chlorine-containing material arising from the use of chlorine-containing solvents during synthesis. Finally, correlation of decomposition temperatures with molecular weights for Demnum and Krytox fluids supports a chain cleavage reaction mechanism for Demnum fluids and an unzipping reaction mechanism for Krytox fluids

Tribological characteristics of perfluoropolyether liquid lubricants under sliding conditions in high vacuum

Tribological characteristics of three PFPE's (Fomblin Z, Demnum, and Krytox) were studied under high vacuum using a four-ball apparatus with 440C steel specimens. Fomblin Z and Demnum exhibited initial scuffing-like high friction whereas Krytox did not. Steady state friction with Fomblin Z was the lowest among the three oils. Frictional values for Demnum and Krytox were almost the same. The lowest wear rate in air was provided by Krytox regardless of load, and low wear rates in vacuum at high load were achieved with Krytox and Demnum. Results are explained by reactivity and pressure-viscosity characteristics of the oils

Properties of Perfluoropolyethers for Space Applications

The perfluoropolyether (PFPE) class of liquid lubricants has been used for space applications for over two decades. At first, these fluids performed satisfactorily as early spacecraft placed few demands on their performance. However, as other spacecraft components have become more reliable and lifetimes have been extended, PFPE lubricant deficiencies have been exposed. Therefore, the objective of this paper is to review the PFPE properties that are important for successful long term operation in space

The Tribological Behavior of Polyphenyl Ether and Polyphenyl Thioether Aromatic Lubricants

The tribological behavior of several polyphenyl ethers and polyphenyl thioethers is reported. Tribological areas covered include: surface tension and wettability measurements, boundary lubrication, ferrography, thermal and oxidative stability and chemiluminescence

Parched elastohydrodynamic lubrication: Instrumentation and procedure

A counter rotating bearing rig was designed and constructed to study transient elastohydrodynamic lubrication phenomena. New instrumentation is described and test procedures are documented. Ball and race speed measurement systems and the capacitance (film thickness) measurement system were upgraded. Methods for measuring bearing torque and race temperatures were implemented

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-)

Determination of the Thermal Stability of Perfluoroalkylethers

The thermal decomposition temperatures of several commercial and custom synthesized perfluoroalkylether fluids were determined with a computerized tensimeter. In general, the decomposition temperatures of the commercial fluids were all similar and significantly higher than those for custom synthesized fluids. Correlation of the decomposition temperatures with the molecular structures of the primary components of the commercial fluids revealed that the stability of the fluids is not affected by intrinsic factors such as carbon chain length, branching, or cumulated difluoroformal groups. Instead, correlation with extrinsic factors revealed that the stability may be limited by the presence of small quantities of thermally unstable material and/or chlorine-containing material arising from the use of chlorine-containing solvents during synthesis. Finally, correlation of decomposition temperatures with molecular weights for Demnum and Krytox fluids supports a chain cleavage reaction mechanism for Demnum fluids and an unzipping reaction mechanism for Krytox fluids

Tribological Characteristics of Perfluoropolyether Liquid Lubricants Under Sliding Conditions in High Vacuum

Tribological characteristics of three PFPE\u27s (Fomblin Z, Demnum, and Krytox) were studied under high vacuum using a four-ball apparatus with 440C steel specimens. Fomblin Z and Demnum exhibited initial scuffing-like high friction whereas Krytox did not. Steady state friction with Fomblin Z was the lowest among the three oils. Frictional values for Demnum and Krytox were almost the same. The lowest wear rate in air was provided by Krytox regardless of load, and low wear rates in vacuum at high load were achieved with Krytox and Demnum. Results are explained by reactivity and pressure-viscosity characteristics of the oils

Development and Preliminary Evaluation of Aryl Ester Boundary Additives for Perfluoropolyethers

A series of additives were developed for evaluation as boundary lubrication enhancers for perfluoropolyethers. They are composed of a hydrocarbon aryl component (for lubrication improvement) and a fluorinated side chain (for solubility enhancement). The two moieties are joined by an ester linkage. Five boundary additives were evaluated in a perfluoropolyether basestock (Fomblin Z25) using a specially designed four-ball apparatus. Additives were evaluated at a one wt percent concentration. Conditions included: an atmosphere of dry air at atmospheric pressure, a 200N load, a speed of 100 rpm, room temperature, and 440C stainless steel specimens. Two monoesters, 2,4,6-trimethyl E2 and H5PDFO yielded wear rate reductions of approximately 60 and 35 percent, respectively. One diester, H4(E2)(sub 2), had no activity, while two other diesters (a diester of bisphenol A and H4(E4)(sub 2)) were pro-wear