Effect of Chain-Length and Countersurface on the Tribochemistry of Bulk Zinc Polyphosphate Glasses

Zinc polyphosphate glasses are considered to be chiefly responsible for the anti-wear efficiency of ZnDTP tribofilms. In this work, the tribochemical properties of amorphous bulk zinc polyphosphates of different chain lengths (ranging from zinc metaphosphate to zinc pyrophosphate) have been investigated. Tribological tests on bulk polyphosphate discs have been carried out using steel and quartz balls as counter-surfaces in a poly-α-olefin (PAO) bath at room temperature. The composition in the wear track and on the contact region of the balls has been monitored by small-area and imaging X-ray photoelectron spectroscopy (i-XPS). The XPS analysis revealed that the composition of short-chain-length polyphosphates remained unchanged following tribological stress. Long-chain-length polyphosphates are depolymerized in the wear track as a consequence of a tribochemical reaction. By comparing the results obtained using quartz and steel balls, it could be observed that while the reaction of iron oxide with the polyphosphates certainly plays a role in the depolymerization of the samples under sliding conditions, pressure and shear stress alone and also in the presence of water or oil-oxidized species are able to depolymerize the glass when an inert material is used as counterpart; the composition of the wear track, in this case, is dependent on the applied load. All samples were able to form an adhesive, glassy transfer film on both steel and quartz balls, but the short-chain-length polyphosphates showed a lower friction coefficient and wear coefficient. The results suggest a third-body mechanism with the polyphosphates acting as a solid lubricant. Differences in tribological behavior of the different-chain-length polyphosphates are attributable to their mechanical and rheological propertie

Polymer-Brush Lubrication in Oil: Sliding Beyond the Stribeck Curve

We report a highly effective macroscopic, non-aqueous lubrication strategy, employing polymer-brush-based surface modification. Poly(alkyl methacrylates) with hexyl, dodecyl and octadecyl side chains have been prepared on both silicon and iron substrates by means of surface-initiated atom-transfer radical polymerisation. Frictional properties of the three polymers have been evaluated in hexadecane, ethanol and toluene. For the case of the poly(dodecyl methacrylate), the study additionally involved nine base lubricating fluids of different chemical natures, with viscosities ranging from 4 to 2,200cSt at 20°C. By constructing a set of Stribeck curves at low values of speed×viscosity (at constant load), it was possible to identify an extended hydrodynamic lubrication regime and, for P12MA-based coatings, a low-friction, brush-lubrication regime, reinforced by time-dependant effects, which appeared to replace the mixed and boundary regimes observed for conventional lubricants. Self-mated poly(dodecyl methacrylate) brushes maintained low coefficient-of-friction values (e.g. 0.012 in hexadecane) over thousands of reciprocating cycles (>100m total distance) under low speed×viscosity conditions (0.1cm/s and 4cSt

Chain-length-identification strategy in zinc polyphosphate glasses by means of XPS and ToF-SIMS

The surface chemistry of amorphous zinc polyphosphates of different compositions (ranging from zinc metaphosphate to zinc orthophosphate) has been investigated by means of X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary-ion mass spectroscopy (ToF-SIMS). The identification of the chain length of zinc polyphosphates by XPS was on the basis of the integrated intensity ratio of the bridging (P-O-P) and nonbridging (P = O and P-O-M) oxygen peaks used for fitting the oxygen 1s signal, the shift of the P 2p3/2 signal towards lower binding energies and the modified Auger parameter towards higher values as the zinc content increases. The discrimination of the polyphosphate chain lengths was also achieved by ToF-SIMS, by comparing the intensities of selected characteristic phosphate fragments. Both techniques appear to be suitable for the investigation of polyphosphate glasses in applications such as tribology, where there is a need to identify the chain length present in the outermost monolayer of the film. Fourier-transform infrared (FT-IR) spectroscopy was used to characterize the bulk compounds. The FT-IR studies showed that long-chain structures linked through P-O-P bonds predominate in the metaphosphate composition, while when the zinc content is increased, the chains become shorter, ultimately being replaced by PO4 monomers in the orthophosphate composition. Figure

Tribochemistry of Bulk Zinc Metaphosphate Glasses

Zinc polyphosphate glasses are the principal component of the antiwear tribofilms formed on steel surfaces in the presence of additives, such as zinc dialkyldithiophosphates. In this work, amorphous, zinc metaphosphate glasses have been synthesized and characterized by means of X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), elemental analysis, and X-ray photoelectron spectroscopy (XPS). Tribological tests were performed by rubbing steel balls against the zinc metaphosphate discs in a poly-α-olefin (PAO) bath at room temperature. XPS was used in order to characterize the tribostressed areas on both metaphosphate discs and steel balls. A transfer film, constituted of iron and zinc polyphosphates, was formed on the contact area of the balls. This transfer film was found to reduce friction and prevent ball wear. A reduction in the relative intensities of XPS signals related to bridging-oxygen species and a binding energy shift of 0.4eV of the P 2p toward lower values demonstrated the presence of shorter-chain-length phosphates inside the tribo-tracks on the discs. Furthermore, iron was transferred to the glass during the tribological tests. A tribochemical reaction between zinc metaphosphate and iron oxide has been proposed as an explanation for the depolymerization of the glass and the formation of iron phosphat

Effect of Chain-Length and Countersurface on the Tribochemistry of Bulk Zinc Polyphosphate Glasses

ISSN:1023-8883ISSN:1573-271

Polymer-Brush Lubrication in Oil: Sliding Beyond the Stribeck Curve

ISSN:1023-8883ISSN:1573-271

Tribochemistry of Bulk Zinc Metaphosphate Glasses

ISSN:1023-8883ISSN:1573-271

Multiple Transmission-Reflection IR Spectroscopy Shows that Surface Hydroxyls Play Only a Minor Role in Alkylsilane Monolayer Formation on Silica

Multiple transmission-reflection (MTR)a recently developed infrared spectroscopy sampling method for surfaceshas been applied to the study of silane monolayer formation on silicon oxide. Thanks to the excellent signal:noise ratio of data obtained by MTR, spectra of silane monolayers on a silica substrate could be readily obtained. This system has been previously difficult to investigate by standard sampling methods. The data is particularly important for gaining insights into the nature of the silica-silane interaction. The results support a model in which the inherent strain caused by the mismatch of alkyl-chain van der Waals radius and Si–O–Si bond distance is relieved in silane monolayers by the formation of a structure resembling snow moguls or closely packed umbrellas

Visualizing the Product of a Formal Cycloaddition of 7,7,8,8-Tetracyano-p-quinodimethane (TCNQ) to an Acetylene-Appended Porphyrin by Scanning Tunneling Microscopy on Au(111)

The applicability of a formal [2+2] cycloaddition between electron-rich alkynes and electron-deficient TCNQ on an atomically clean Au(111) surface was demonstrated by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). At low coverage, monomeric and self-assembled dimeric species of the initial compounds as well as of the reaction product, a TCNQ-conjugated porphyrin, could be visualized.