Date of Award

4-14-2017

Degree Type

Dissertation

Degree Name

Ph.D.

Department

Mechanical, Automotive, and Materials Engineering

First Advisor

Alpas, Ahmet

Keywords

Coatings, Friction, Graphene, Powertrain, Tribolayers, Wear

Rights

CC BY-NC-ND 4.0

Abstract

This study aims at understanding the micromechanisms responsible for reduction in friction and wear in the engine cylinder bore/liner materials when tested under lubricated and unlubricated conditions. The tribolayers formed in-situ during sliding contact are unique to each tribosystem and a detailed study of these tribolayers will shed light on the friction reduction mechanisms in powertrain materials. Boundary lubricated tribological performance of grey cast iron (CI) tested against non-hydrogenated diamond-like carbon coating (NH-DLC) resulted in 21% lower coefficient of friction (COF) and an order of magnitude lower volumetric wear compared to CI and steel counterfaces. Dilution of the engine oil by ethanol containing E85 biofuel, consisting of 85% ethanol and 15% gasoline, was beneficial as COF and volumetric wear losses were further reduced. TEM/EELS studies of the NH-DLC counterface provided evidence for OH adsorption of the dangling carbon bonds at the coating surface leading to low friction. Advantage of E85/engine oil blend was also evident during boundary lubricated sliding of eutectic Al-12.6% Si alloy against AISI 52100 steel. The oil residue layer (ORL) formed during boundary lubricated sliding incorporated nanocrystalline regions of Al, Si, ZnS, AlPO4 and ZnO surrounded by amorphous carbon regions. Higher proportions of Zn, S, and P antiwear compounds formed in the ORL when tested using the E85/oil (1:1) blend compared to the unmixed engine oil as the hydroxyl groups in ethanol molecules facilitated ZDDP degradation. Mico-Raman spectroscopy indicated two types of tribolayers formed during unlubricated sliding of thermally sprayed low carbon steel 1010 coating deposited on linerless Al 380 cylinder bore: i) Fe2O3 layer transformed from FeO during dry sliding and ii) Fe2O3 layer with a top amorphous carbon transfer layer when run against H-DLC coated TCR with COF of 0.18. The NH- and H-DLC coatings, that provide low friction under room temperature conditions, fail at temperatures > 200 °C. It was shown that W containing DLC (W-DLC) coatings offered low and stable COF of 0.07 at 400 °C while a Ti incorporated multilayer MoS2 (Ti-MoS2) coating maintained COF between 0.11 at 25 °C to 0.13 at 350 °C. The low friction provided by these coatings was attributed to formation of high temperature lubricious oxides: tungsten trioxide (WO3) in case of W-DLC and MoO3 in case of MoS2, as revealed by Raman analyses of the tribolayers formed on counterface surfaces. Tribolayer formation during sliding friction of multuilayered graphene (MLG), a potential lubricant, depended on the material transfer and relative humidity (RH). Sliding friction tests performed on MLG in air (10- 45% RH) and under a dry N2 atmosphere showed that progressively lower friction values were observed when the RH was increased, with maximum COF of 0.52 in dry N2 and lowest COF of about 0.10 at 45% RH. Microstructural studies including cross-sectional FIB/HR-TEM determined that sliding induced defects which comprised of edge fracture, fragmented/bent graphene stacks compared to pristine graphene and disordered regions between them. In summary, this work shows that delineating the micromechanisms responsible for reduction in friction and wear is critical for development of appropriate materials and coatings for powertrain components.

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