Effect of ZDP Chemistry on Three Way Catalysts (TWC) Phosphorous Exposure and Emissions Performance E. Bardasz, L. Williams - Lubrizol Corporation C. Hubbard, M. Riley - Ford Motor Company Presented to ESCIT Ann Arbor, MI August 8th, 2006

The Phosphorous Issue in TWC Problem Definition ZDPs compounds are very effective antiwear/antioxidant/anticorrosion agents As ZDPs decompose to protect engine parts, certain volatile P species exit engine, interact with TWCs and reduce their effectiveness/service life

NYC Taxi Test Vehicles: 2003 Ford Crown Victoria with Ford 4.6 L V-8 Test Duration: 100,000 miles Oil Change Interval: 5,000 miles Service: moderate to high temperature urban driving Two lubricants GF-4, 5W-20, 0.076% P: Conventional ZDP Low Impact ZDP (LIZDP) Evaluations: EOT Engine Parts Inspection Used Oils Analysis Aged Catalysts Emissions Efficiency Assessments: FTP-75 Post Mortem Aged Catalyst Analysis

Camshaft Lobes @ 100K miles Conventional ZDP Low Impact ZDP Equivalent wear protection

Cylinder Heads @ 100K miles: Clean Engines, No Differences in Deposits & Sludge Conventional ZDP Low Impact ZDP

Low Impact vs. Conventional ZDP Summary of Used Oils Analysis @ 100K miles Fluid Performance Low Impact vs. Conventional ZDP Pentane Insolubles Equivalent C=0 RONOx MRV-35, CCS Low Impact ZDP Better Wear Metals % Viscosity Increase

Drain Oil Analysis: TBN/TAN Crossover

TWC Exposure Based on Measured P Retention in Drains 52% less P exits engine from LIZDP containing fluids!

Aged Catalysts Efficiency Assessments: FTP-75 Data Examined: CO, NOx, THC, and THC Light-Off Time (Bag 1)

Crown Victoria: Exhaust System - Light-Off Catalyst (right side) Emissions Measurements: Right + Left side samples probes were teed together

Positive Effect of Low Impact ZDP on THC Light-Off Cat Efficiency: Observed Statistically Significant Differences % Efficiency Fresh catalyst = 29.1 secs Low Impact ZDP =30.9 secs Conventional ZDP = 32.7 secs. Time (sec)

Statistically Significant Improvements in NOx Efficiency Related to P Exposure over FTP Cycle 10.3 percentage point difference

Aged Light off Catalyst Analysis: Observed 30 % Reduction in P Concentration measured by XRF INLET OUTLET Inlet : Exhaust gases generated by Low Impact ZDP deposited significantly smaller amount of P (30% reduction) containing compounds than conventional ZDP Outlet: Detected minimal amounts of P ¼ Brick ¼ Brick % P measured by XRF

Conclusions NYC Taxi Trial Conducted with 0.076 % P, GF4 Fluids Demonstrated that Lubrizol’s Environmentally Superior ZDP: Keeps P in crankcase oil Maintains excellent antiwear/antioxidancy performance in the field Deposits less P on the catalyst resulting in statistically significant Improved THC light-off time Lowered NOx emissions . Lubrizol’s low impact ZDP clearly shows improvements in TWC efficiencies and protects engines in real world field service.