Evolutionary Trends in Additive

Technologies:
Environmentally Superior ZDP
Additives 2007: Applications for Future Transport

Dr. Ewa A. Bardasz, Fellow, Engine Oils Technology

© The
TheLubrizol
LubrizolCorporation 2008,
Corporation all rights
2008, reserved
all rights reserved
 Outline

• Technology Drivers:
– Increased performance severity
– Emissions regulations / Aftertreatment devices
– Increasing elemental constrains
• Novel ZDP technology:
– Overall field performance
– Exhaust catalyst and emissions performance
• Summary

2 © The Lubrizol Corporation 2008, all rights reserved

Technology Drivers

© The
TheLubrizol
LubrizolCorporation 2008,
Corporation all rights
2008, reserved
all rights reserved
 Challenges & Opportunities
• Emission regulations are driving change globally
• Base Oil quality/supply changing, viscosity grades
changing
• Changes in fuels,
– Biofuel becoming more prevalent in Europe
– Push to use E85 in North America
• 2010 to 2012 we will be in the midst of overlapping
upgrades ---GF-5, ACEA 2010, PC-11, AP Upgrades.
• Chemical and physical property changes are narrowing
our formulating flexibility

4 © The Lubrizol Corporation 2008, all rights reserved

 Historical Oil Severity Factor Trends

600

500
Oil Severity Factor

400

300

200

100

0
1940 1950 1960 1970 1980 1990 2000 2010

5 © The Lubrizol Corporation 2008, all rights reserved

 Contributing Factors to Increased Oil Severity Trend
Include:
• Extended oil drain intervals
• Potential issues related to use of EGR impact on TBN
levels and increased corrosion
• Increased oil temperatures from higher power density
engines and smaller oil sumps
• Increased contaminant levels like soot - need for soot-
induced antiwear protection

6 © The Lubrizol Corporation 2008, all rights reserved

 Overall Picture for Transportation Industry

• Keeping the oil longer, exposing it to a harsher

environment, and restricting the use of multifunctional
components like ZDP to address emissions
requirements

• Advancements in engine design and lubricant

technology have enabled our industry to meet these
challenging times

7 © The Lubrizol Corporation 2008, all rights reserved

Global Emissions Regulations
Impact on Formulation
Strategies

© The
TheLubrizol
LubrizolCorporation 2008,
Corporation all rights
2008, reserved
all rights reserved
 Light-Duty Emissions

Euro IV Euro V US Tier 2 Bin 5

Jan. ’05 Mid.' 08 Jan. ’04-’07

PM 0.025 (g/km) 0.005 (g/km) 0.010 (g/mile) or

0.006 (g/km)

NOx+HC 0.30 (g/km) 0.25 (g/km) n/a

0.07 (g/mile) or
NOx 0.25 (g/km) 0.20 (g/km) 0.04 (g/km)

HC n/a n/a 0.09 (g/mile)

4.2 (g/mile) or
CO 0.50 (g/km) 0.50 (g/km) 2.6 (g/km)

9 © The Lubrizol Corporation 2008, all rights reserved

Aftertreatment Technology and Lubricant Interactions
Application Solution Concern

Passenger Car LNT / DPF SCR S/P/Ash

Euro IV / V
Heavy Duty Diesel / DPF S/P/Ash

GF-4 / GF-5 Passenger Car TWC P

API CJ-4 Heavy Duty Diesel DPF S/P/Ash

Work is ongoing to validate which elements are detrimental to some

systems, the effects of phosphorus on TWC is well documented

Can ZDP’s be optimized for emissions to help mitigate phosphorus

deactivation of TWC?

10 © The Lubrizol Corporation 2008, all rights reserved

 Primary Performance Effects of Elemental Restrictions

Chemical Formulation
Concern The elements
Restraint Restraint
that are targeted for
Wear
Sulphur ZDP
Oxidation
restriction form the
Piston Deposits
very basis of
Detergents
Corrosion today’s lubricants
Base Oil Capacity Flexibility
for over 50 years
Wear
Phosphorus ZDP
Oxidation

Piston Deposits
Ash Detergents Corrosion, Drain
Intervals

Wear
ZDP
Oxidation

11 © The Lubrizol Corporation 2008, all rights reserved

Lubricant Specifications Engine Lubricant Specifications: Timeline

PCDO- (NA) ?

GF-5 GF-6 ?
GF-3 GF-4

CI-4 PC-10 (CJ-4) PC-11? PC-12?

PC-9 (CI-4)
Plus

DHD-1 DHD-2

ACEA 99 ACEA 02 ACEA 04 ACEA 06 ACEA 08 ACEA 10?

ACEA 99 ACEA 02 ACEA 04 ACEA 06 ACEA 08 ACEA 10?

JASO DH-1 Update-JASO

JASO DH/ DL?
DH-1 /DH-2/DL-1- 2005
Emissions Regulations

1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015

Japan Japan Japan

Japan Japan Japan
2000 2004 2010?
2000 2004 2010?
USA- USA- USA-
USA- USA- USA-
2002 2007 2010?
2002 2007 2010?

EURO III EURO IV EURO VI?

EURO V

12 © The Lubrizol Corporation 2008, all rights reserved

Environmentally Friendly
ZDP Technology

© The
TheLubrizol
LubrizolCorporation 2008,
Corporation all rights
2008, reserved
all rights reserved
 Emissions-Friendly ZDP

• ZDPs control wear, oxidation and corrosion

• ZDPs can also impact TWC through phosphorus

volatilization

• Lubrizol’s low volatility ZDP is designed to minimize volatile

phosphorus species that can exit the engine and accumulate on
catalyst active sites, reducing their effectiveness.

14 © The Lubrizol Corporation 2008, all rights reserved

 ZDP Alcohol Hydrocarbon Backbone Structures
ZDP properties, including volatilization depend on the starting alcohols,
higher MW alcohols tend to volatilize less

ZDP Type R-Group Chain Structure

Short-Chain Primary ...................................... C C C C

C
C
Short-Chain Secondary ................................. C C

C
Medium-Chain Secondary ............................. C C C
C C
C
Long-Chain Primary ...................................... C C C C C
C C
15 © The Lubrizol Corporation 2008, all rights reserved
 Modes of ZDP Decomposition
The starting alcohol can impact the type of ZDP decomposition, thermal leads
to formation of a protective antiwear film

• Thermal
• Hydrolysis
• Chemical:
9 oxidation
9 acidic
9 nitration

LV-ZDP is made with an optimized mixture of alcohols that minimizes

volatility while maintaining the traditional performance of conventional ZDP
16 © The Lubrizol Corporation 2008, all rights reserved
 ZDP Decomposition Products

Basic ZDP (RO)2P(O)SH (RS)3P(O)

[(RO)2P(S)S] (RO)2P(S)OR’ (RS)2P(O)OR’

(RO)2P(S)SH (RO)2P(O)OR’ RSH

(RO)3(S) (HO)3P(O) H2S

[(RO)2P(S)OH]2S [(RO)2P(S)]2S RSXR’

(RO)2P(S)OH Zn2P2O7 Olefins

(RO)2P(S)SZn(OH) Zn3(PO4)2 ROH

17 © The Lubrizol Corporation 2008, all rights reserved

 Field Drain Analysis
% Change in Elements
30
Ca
P
20
Zn
% Change

10

-10

-20
0 10 20 30 40 50
Miles (1000s)
18 © The Lubrizol Corporation 2008, all rights reserved
 Positive Crankcase Ventilation

19 © The Lubrizol Corporation 2008, all rights reserved

 Summary
• ZDP properties including volatility, depend on starting alcohols

• ZDP decomposes into numerous species, many contain phosphorus

• Catalyst poisoning is a complex process involving

– Decomposition
– Volatilization
– Oil Consumption (minor)

• Catalyst poisoning may be reduced with engine design, changes in

catalysts technologies, and modifications in ZDP alcohol backbone
structure that minimizes phosphorus volatility without sacrificing other
performance attributes

20 © The Lubrizol Corporation 2008, all rights reserved

 New York City Taxi Cab Test - Description

• Vehicles: 2003 T2B7 Ford Crown Victoria 4.6L V8 taxis

• Test duration: 100,000 miles
• Oil change interval: 5,000 miles
• Service: moderate to high-temperature urban driving
• Two oils: ILSAC GF-4, 5W-20, 0.076% P
1) Conventional ZDP
2) Low-volatility ZDP (LV-ZDP)
• Evaluations:
– EOT engine parts inspection
– Used oil analyses
– Aged catalyst FTP emission efficiency tests at SwRI
All catalyst systems evaluated with slave vehicle
– Post mortem aged catalyst analysis

21 © The Lubrizol Corporation 2008, all rights reserved

 Performance Comparison of ZDP Additives

• Extensive engine inspections at EOT indicate both types of ZDP

technologies provide excellent oxidation control, wear protection and
sludge/varnish cleanliness.

• Used oil analysis of wear metals and oil condition indicated

equivalent performance of the two test oils.

22 © The Lubrizol Corporation 2008, all rights reserved

 Used Oils Analysis @ 100K miles
Fluid Performance LV-ZDP vs. Conventional ZDP
% P Loss Better
Pentane insolubles Equivalent
C=0 Equivalent
RONOx Equivalent
MRV-35, CCS Equivalent
Wear metals Equivalent
TAN/TBN crossover Equivalent
% Viscosity increase Equivalent

23 © The Lubrizol Corporation 2008, all rights reserved

 % Phosphorus Retention in Oil Drains: Phosphorus
Retention of Conventional ZDP is 50% lower than
Phosphorus Retention of LV-ZDP

125.0
Avg. % P Retention Oil 1
120.0 Avg. % P Retention Oil 2
115.0 Poly. (Avg. % P Retention Oil 1)
Poly. (Avg. % P Retention Oil 2)
110.0

105.0
LV-ZDP
Percent

100.0

95.0

90.0

85.0
Conventional ZDP
80.0

75.0
0 2,500 5,000
Oil Miles

24 © The Lubrizol Corporation 2008, all rights reserved

 Crown Victoria: Exhaust System
Light-Off Catalyst (right side)

25 © The Lubrizol Corporation 2008, all rights reserved

 Used Catalyst Efficiency Assessments: FTP-75

Data Examined: CO, NOx, THC, and THC Light-Off Time (Bag 1)

26 © The Lubrizol Corporation 2008, all rights reserved

 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.

27 © The Lubrizol Corporation 2008, all rights reserved Time (sec)

 Maximum Amount of Phosphorus (grams) Catalysts Could
be Exposed to from OC and Volatility

LV-ZDP

Conventional
ZDP

28 © The Lubrizol Corporation 2008, all rights reserved

 Statistically Significant Improvements in NOx
Efficiency Related to P Exposure Over FTP Cycle
10.3 percentage point difference
100
Cat 1 NOx Efficiency (%

95

90

C o nve ntio na l
85 L o w Im p a c t

80
8 10 12 14 16 18
T o ta l P ( L u b e Im p a c t + O il C o n s
in g ra m s )

29 © The Lubrizol Corporation 2008, all rights reserved

 Field Test Summary

• New York City taxi trial conducted with 0.076 % P, GF-4

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

30 © The Lubrizol Corporation 2008, all rights reserved

Conclusions

© The
TheLubrizol
LubrizolCorporation 2008,
Corporation all rights
2008, reserved
all rights reserved
 Challenges for Future Engine Lubricant Technologies

New aftertreatment
devices
New engine Varied fuels Fuel economy
technologies

Maintenance of
More robust
drain intervals
performance
Emissions
Increased New viscosity
lubricant cost
friendly grades
lubricants
Base oil cost and capacity

Elemental limits and

Product misapplication new formulating
New additive strategies
components

32
EFL
3-03
© The Lubrizol Corporation 2008, all rights reserved
 Summary
• The use of exhaust aftertreatment will result in a significant change in
lubricant design and application

• Future aftertreatment compatible lubricants will require a fine balance to

maintain
– Engine and emissions systems durability
– Oil drain intervals and fuel economy

• Significant advancements in ZDP technology have been made to

establish prototypes meeting these demands.

33 © The Lubrizol Corporation 2008, all rights reserved

 Acknowledgements

I want to thank our colleagues contributing to these studies

at Lubrizol: Lew Williams, Jack Kelley, Doug Jayne, Paul

Adams, and Saleem Al-Ahmad
and
at Ford: Mike Riley, Carolyn Hubbard, Mark Jagner, Eva
Thanasiu, and Dairene Uy.

Thank you very much

34 © The Lubrizol Corporation 2008, all rights reserved