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SRC Users' Meeting - Synchrotron Radiation Center - University of ...

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CHEMOMECHANICAL PROPERTIES OF ANTIWEAR FILMS<br />

USING X-RAY ABSORPTION MICROSCOPY AND<br />

NANOINDENTATION TECHNIQUES<br />

Mark A. Nicholls 1 , G. Michael Bancr<strong>of</strong>t 1 , Peter R. Norton 1 *, Masoud Kasrai 1 , Gelsomina<br />

De Stasio 2 , Bradley H. Frazer 2 , and Lisa M. Wiese 3<br />

1 Department <strong>of</strong> Chemistry, <strong>University</strong> <strong>of</strong> Western Ontario,<br />

London, Ontario, Canada N6A 2B7<br />

2 Department <strong>of</strong> Physics, <strong>University</strong> <strong>of</strong> Wisconsin-Madison, Madison, WI 53706, USA<br />

3 Syncrotron <strong>Radiation</strong> <strong>Center</strong>, Univ. <strong>of</strong> Wisconsin-Madison, Stoughton, WI 53589, USA<br />

ABSTRACT<br />

The first chemomechanical comparison between an antiwear film formed from a solution<br />

containing zinc dialkyl-dithiophophates (ZDDPs) to a solution containing ZDDP plus a<br />

detergent (ZDDPdet) has been performed. X-ray absorption near edge structure<br />

(XANES) analysis has shown a difference in the type <strong>of</strong> polyphosphate, between each<br />

film. The ZDDPdet film has been found<br />

to contain short-chain polyphosphates<br />

throughout and contain a large amount <strong>of</strong><br />

CaCO 3 . X-ray photoelectron emission<br />

microscopy (X-PEEM) has provided<br />

detailed spatially resolved<br />

microchemistry <strong>of</strong> the films. The large<br />

Intensity (arb. units)<br />

[A]<br />

[B]<br />

[C]<br />

[D]<br />

[E]<br />

[F]<br />

1<br />

2<br />

s'<br />

3<br />

b<br />

a<br />

c<br />

s 1<br />

unreacted<br />

ZDDP<br />

Zn 10<br />

P 18<br />

O 55<br />

Ca 3<br />

(PO 4<br />

) 2<br />

ZDDP + Det.<br />

X-PEEM<br />

long-chain<br />

internal model*<br />

shorter-chain<br />

internal model*<br />

map-ave.<br />

long-chain<br />

pads in the ZDDP antiwear film have<br />

[G]<br />

map-ave.<br />

shorter-chain<br />

long-chain polyphosphates at the surface<br />

[H]<br />

and shorter-chain polyphosphates are<br />

130 140 150 160<br />

Photon Energy (eV)<br />

found in the lower lying regions. The

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