External pressure in the hardening of phosphate in tribofilm on iron surfaces

Purpose: In the present work we consider our (in progress) spectroscopy study of zinc and iron phosphates under the influence external high pressure to determine zinc ion change coordination from tetrahedral to octahedral (or hexahedral) structure.----- Design/methodology/approach: The standard equipment is the optical high pressure cell with diamond (DAC). The DAC is assembled and then vibrational or electronic spectra are collected by mounting the cell in an infrared, Raman, EXAFS or UV-visible spectrometer.----- Findings: Mechanism by which zinc and iron methaphosphate material is transformed to glassy meta-phosphate is enhancing mechanical properties of tribofilm. The two decades of intensive study demonstrates that Zn (II) and Fe (III) ions participate to cross-link network under friction, hardening the phosphate.----- Research limitations/implications: Transition metal atoms with d orbital have flexible coordination numbers, for example zinc acts as a cross-linking agent increasing hardness, by changing coordination from tetrahedral to octahedral. Perhaps the external pressure effect on the [Zn–(O-P-)4 ] complex causes a transformation to an [Zn –(O-P-)6] grouping.----- Originality/value: This paper analyses high-pressure spectroscopy which has been applied for the investigation of 3D transition metal ions in solids. When studying pressure effects on coordination compounds structure, we can expect changes in ground electronic state (spin-crossovers), electronic spectra due to structural distortions (piezochromism), and changes in the ligand field causing shifts in the electronic transitions.

Role of in situ generated tribofilm on the tribological characteristics of monolith and TiB2 reinforced MoSi2 intermetallic

Wear experiments performed on steel disc with increasing load for monolithic MoSi2 of different densities and its composite with TiB2 showed three distinct wear regimes. The specimens exhibited severe wear rate below the lower and above the upper critical loads and mild wear in between the two critical loads. The increase in density of the monolith and the reinforcement of TiB2 were effective in reducing the coefficient of friction and the specific wear rate. The wear experiments have been performed in these three regimes (15, 50 and 75 N). The tribofilm formed on the pin surface was found to contain both pin and disc materials. The temperature of the pins during the sliding against EN-24 disc was calculated using one dimensional heat transfer equation at different loads for each composition. The composite experiences lower temperatures compared to the monoliths. (C) 2002 Elsevier Science B.V. All rights reserved.

Some mechanisms of tribofilm formation in metal/metal and ceramic/metal sliding interactions

Tribological interaction often generates new structures and materials which form the interface between the sliding pair. The new material designated tribofilm here may be protective or tribologically deleterious. The tribofilm plays a major role in determining the friction and wear of the interaction. Here, we give three examples: mechanically mixed, chemically generated and thermally activated, of tribofilms formed in three different tribological systems and speculate on the mechanism of their formation.

The mechanical strength of phosphates under friction-induced cross-linking

Purpose: In the present study, we consider mechanical properties of phosphate glasses under high temperatureinduced and under friction-induced cross-linking, which enhance the modulus of elasticity. Design/methodology/approach: Two nanomechanical properties are evaluated, the first parameter is the modulus of elasticity (E) (or Young's modulus) and the second parameter is the hardness (H). Zinc meta-, pyro - and orthophosphates were recognized as amorphous-colloidal nanoparticles were synthesized under laboratory conditions and showed antiwear properties in engine oil. Findings: Young's modulus of the phosphate glasses formed under high temperature was in the 60-89 GPa range. For phosphate tribofilm formed under friction hardness and the Young's modulus were in the range of 2-10 GPa and 40-215 GPa, respectively. The degree of cross-linking during friction is provided by internal pressure of about 600 MPa and temperature close to 1000°C enhancing mechanical properties by factor of 3 (see Fig 1). Research limitations/implications: The addition of iron or aluminum ions to phosphate glasses under high temperature - and friction-induced amorphization of zinc metaphosphate and pyrophosphate tends to provide more cross-linking and mechanically stronger structures. Iron and aluminum (FeO4 or AlO4 units), incorporated into phosphate structure as network formers, contribute to the anion network bonding by converting the P=O bonds into bridging oxygen. Future work should consider on development of new of materials prepared by solgel processes, eg., zinc (II)-silicic acid. Originality/value: This paper analyses the friction pressure-induced and temperature–induced the two factors lead phosphate tribofilm glasses to chemically advanced glass structures, which may enhance the wear inhibition. Adding the coordinating ions alters the pressure at which cross-linking occurs and increases the antiwear properties of the surface material significantly.

Tribological properties of γ-Y2Si2O7 ceramic against AISI 52100 steel and Si3N4 ceramic counterparts

Reciprocating ball-on-flat dry sliding friction and wear experiments have been conducted on singlephase γ-Y2Si2O7 ceramic flats in contact with AISI 52100 bearing steel and Si3N4 ceramic balls at 5-15N normal loads in an ambient environment. The kinetic friction coefficients of γ-Y2Si2O7 varied in the range over 0.53-0.63 against AISI 52100 steel and between 0.51-0.56 against Si3N4 ceramic. We found thatwear occurred predominantly during the running-in period and it almost ceased at the steady friction stage. The wear rates of γ-Y2Si2O7 were in the order of 10-4mm3/(N m). Besides, wear debris strongly influenced the friction and wear processes. The strong chemical affinity between γ-Y2Si2O7 and AISI 52100 balls led to a thick transfer layer formed on both contact surfaces of the flat and counterpart ball, which changed the direct sliding between the ball and the flat into a shearing within the transfer layer. For the γ-Y2Si2O7/Si3N4 pair, a thin silica hydrate lubricant tribofilm presented above the compressed debris entrapped in the worn track and contact ball surface. This transfer layer and the tribofilm separated the sliding couple from direct contact and contributed to the low friction coefficient and wear rate.

Experimental estimation of friction force in lubricated cutting of steel

Friction force generated in lubricated cutting of steel is experimentally estimated by recording the tangential force experienced by the spherical face of a pin rubbing against a freshly cut surface. The pin and the cutting tool are both submerged in the lubricant and the pin is situated on the cut-track to record the force. The recording shows an instantaneous achievement of a peak in the force curve followed by a decline in time to a steady state value. The peak and not the steady state friction was found to be sensitive to the structure of the hydrocarbon and addition of additive to the oil. The configuration was designed and tested to demonstrate the influence of a reaction film which develops during cutting, on cutting tool friction. Given the strong correlation between the peak friction and the existence of a tribofilm in the cutting zone, the configuration is used to determine the lower limit of a cutting speed regime, which marks the initiation of lubricant starvation, in cutting of steel using an emulsion as a cutting fluid. (C) 2010 Elsevier B.V. All rights reserved.

Microstructure control and wear of Al2O3-SiC-(Al,Si) composites made by melt oxidation

Ceramic matrix composites of Al2O3-SiC-(Al,Si) have been fabricated by directed melt oxidation of aluminum alloys into SiC particulate preforms. The proportions of Al2O3, alloy, and porosity in the composite can be controlled by proper selection of SLC particle size and the processing temperature. The wear resistance of composites was evaluated in pin-on-disk experiments against a hard steel substrate. Minimum wear rate comparable to conventional ceramics such as ZTA is recorded for the composition containing the highest fraction of alloy, owing to the development of a thin and adherent tribofilm with a low coefficient of friction.

Wear of Al2O3-SiC-(Al,Si) melt oxidised ceramic composites

Al2O3-SiC-(Al,Si) cermets are fabricated using the melt oxidation route. The tribological properties of the composites are tested under adhesive sliding and two body abrasion conditions. Under adhesive conditions, the network of residual aluminium in the matrix plays a role in the formation of a thin tribofilm on the interface while in abrasion the hardness of the composite plays a prominent tribological role. The work suggests that microstructural control can make this low temperature composite competitive with the conventional high temperature monolithic ceramics. (C) 1999 Published by Elsevier Science S.A. All rights reserved.

Performance of monolithic and TiB2 reinforced MoSi2 in dry sliding contact with steel

MoSi2 and its composite with TiB2 (10 and 20 wt.%) particulates were synthesized by the hot pressing technique. Dry sliding wear experiments were done on these samples by pin-on-disc method on an EN-24 steel disc. It was observed that the densification and the reinforcement of the matrix are beneficial in reducing the friction and wear Of MoSi2. The tribofilm that was formed during sliding contained both the disc and the pin material. (C) 2002 Elsevier Science B.V. All rights reserved.

Wear of metals: a consequence of stable/unstable material response

Wear of metals in dry sliding is dictated by the material response to traction. This is demonstrated by considering the wear of aluminium and titanium alloys. In a regime of stable homogeneous deformation the material approaching the surface from the bulk passes through microprocessing zones of flow, fracture, comminution and compaction to generate a protective tribofilm that retains the interaction in the mild wear regime. If the response leads to microstructural instabilities such as adiabatic shear bands, the near-surface zone consists of stacks of 500 nm layers situated parallel to the sliding direction. Microcracks are generated below the surface to propagate normally away from the surface though microvoids situated in the layers, until it reaches a depth of 10-20 mum. A rectangular laminate debris consisting of a 20-40 layer stack is produced, The wear in this mode is severe.

Lubricity of an oil in water emulsion in metal cutting: The effect of hydrophilic/lypophilic balance of emulsifiers

A steel disc is cut using a single point tool. The coefficient of friction of the nascent cut surface is measured by a spherical steel pin situated in close proximity of the point of cutting. The tool, disc and the friction pin are immersed in an oil in water emulsion bath during the experiment. The purpose of the experiments conducted here is to record the effect of hydrophilic/lypophilic balance (HLB) of the emulsifier on the lubricity experienced in the cutting operation. The more lypophilic emulsifiers were found to give greater lubricity than what is recorded when the emulsifier is more hydrophilic. XPS and FTIR spectroscopy are used to explore the tribofilm generated on the nascent cut surface to indicate a possible rationale for the effect. (C) 2011 Elsevier B.V. All rights reserved.

Lubricant Degradation and Related Wear of a Steel Pin in Lubricated Sliding Against a Steel Disc

In lubricated sliding contacts, components wear out and the lubricating oil ages with time. The present work explores the interactive influence between lubricant aging and component wear. The flat face of a steel pin is slid against a rotating steel disk under near isothermal conditions while the contact is immersed in a reservoir of lubricant (hexadecane). The chemical changes in the oil with time are measured by vibrational spectroscopy and gas chromatography. The corresponding chemistry of the pin surface is recorded using X-ray photoelectron spectroscopy while the morphology of the worn pins; surface and subsurface, are observed using a combination of focused ion beam milling and scanning electron 5 microscopy. When compared to thermal auto-oxidation of the lubricant alone, steel on steel friction and wear are found to accentuate the decomposition of oil and to reduce the beneficial impact of antioxidants. The catalytic action of nascent iron, an outcome of pin wear and disk wear, is shown to contribute to this detrimental effect. Over long periods of sliding, the decomposition products of lubricant aging on their own, as well as in conjunction with their products of reaction with iron, generate a thick tribofilm that is highly protective in terms of friction and wear.

Effect of Layered MoS2 Nanoparticles on the Frictional Behavior and Microstructure of Lubricating Greases

Lithium stearate soap and layered MoS2 nanoparticles encapsulated in lithium stearate soap are prepared in the laboratory, and their lubricating properties are compared with respect to the particle and particle concentration. The tribotracks after friction test was investigated with Raman Spectroscopy, scanning electron microscopy (SEM) and 3D optical profilometry to understand the action mechanism. The status of the soap particles on a tribotrack changes with time, contact pressure and sliding speed. At low pressure and speed, individual solid undeformed soap particle stand proud of the surface and the topography shows marginal difference with sliding time. In these conditions, no frictional difference between the performance of grease with and without the nanoparticles is observed. Increasing the contact pressure and temperature (low speed and high speed) has a dramatic effect as the soap particles melt and the liquid soap flows over the track releasing the hitherto encapsulated nanoparticles. Consequently, the soap smears the track like a liquid, and the nanoparticles now come directly into the interface and are sheared to generate a low-friction tribofilm. At high particle concentration, the sliding time required for melting of the soap and release of MoS2 is reduced, and the tribofilm is more substantial and uniform consisting of smeared MoS2 and carboxylate soap as observed by SEM and 3D optical profilometry. A change in the Raman Spectra is observed with particle concentration, and this is related to morphology and microstructure of the tribofilm generated.

Amorphous W-S-N thin films: The atomic structure behind ultra-low friction

Amorphous W-S-N in the form of thin films has been identified experimentally as an ultra-low friction material, enabling easy sliding by the formation of a WS2 tribofilm. However, the atomic-level structure and bonding arrangements in amorphous W-S-N, which give such optimum conditions for WS2 formation and ultra-low friction, are not known. In this study, amorphous thin films with up to 37 at.% N are deposited, and experimental as well as state-of-the-art ab initio techniques are employed to reveal the complex structure of W-S-N at the atomic level. Excellent agreement between experimental and calculated coordination numbers and bond distances is demonstrated. Furthermore, the simulated structures are found to contain N bonded in molecular form, i.e. N-2, which is experimentally confirmed by near edge X-ray absorption fine structure and X-ray photoelectron spectroscopy analysis. Such N-2 units are located in cages in the material, where they are coordinated mainly by S atoms. Thus this ultra-low friction material is shown to be a complex amorphous network of W, S and N atoms, with easy access to W and S for continuous formation of WS2 in the contact region, and with the possibility of swift removal of excess nitrogen present as N-2 molecules. (C) 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Evaluation of galling resistance for some selected combinations of tool steels/stainless steel sheet materials/lubricants using pin-on-disc testing

Stainless steels are well known to be prone to cold welding and material transfer in sliding contacts and therefore difficult to cold form unless certain precautions as discussed in this paper are taken. In the present study different combinations of tool steels/stainless steels/lubricants has been evaluated with respect to their galling resistance using pin-on-disc testing. The results show that a high galling resistance is favored by a high stainless steel sheet hardness and a blasted stainless steel sheet surface topography. The effect of type of lubricant was found to be more complex. For example, the chlorinated lubricants failed to prevent metal-to-metal contact on a brushed sheet surface but succeeded on a blasted sheet surface of the same stainless steel material. This is believed to be due to a protective tribofilm which is able to form on the blasted surface, but not on the brushed surface.