The Effects of Fuel Dilution with Biodiesel on

Lubricant Acidity, Oxidation and Corrosion – a

Study with CJ-4 and CI-4 PLUS Lubricants
Simon A.G. Watson and Victor W. Wong
Sloan Automotive Laboratory
Massachusetts Institute of Technology

2008 Diesel Engine-Efficiency and Emissions Research (DEER) Conference

August 7th, 2008

Sloan Automotive Laboratory

 Sources of Lubricant Contamination
• The combustion chamber is the source of most oil
contaminants

Sloan Automotive Laboratory

Fuel Dilution Concerns for 2007+ Engines
and Lubricants
• The aftertreatment regeneration strategy in some engines increases
opportunity for fuel to mix with lubricant
• Interest in the widespread use of Biodiesel fuel

• Known concerns with biodiesel fuel:

– Poor oxidation stability in storage
– Acidic attack on fuel system components
– Viscosity increase due to polymerization of fuel molecules
– Distillation characteristics lead to higher fuel dilution levels
– Polar methyl ester may interfere with ZDDP effectiveness

Sloan Automotive Laboratory

 Experimental Objectives
1. Investigate the effects of fuel dilution with biodiesel on
lubricant degradation and corrosion of engine
components
2. Examine the relative effectiveness of CJ-4 (low ash)
and CI-4+ lubricants in protecting components from
fuel-borne acids and corrosion

Sloan Automotive Laboratory

Test Method
• Bench-scale oxidation
test based on ASTM
D6594
• Mixtures of fuel and oil
heated at 135oC for
160hrs
• Stressed lubricant
analyzed for degradation
• Corrosion of metal
specimens examined

Sloan Automotive Laboratory

 Corrosion Test Specimens
• Copper, tin and lead specimens 25 mm
simulate engine bearings
• Prepared prior to each test by:
– Polishing surfaces to remove oxide Copper 25 mm
layers
– Washing in acetone to rinse away
metallic dust Tin
• Corrosion quantified by
measuring metallic
concentrations in the oil with Lead
ICP

Sloan Automotive Laboratory

 Test Matrix
• Two lubricants were used: Lubricant
- CJ-4 (Low Ash) Fuel Dilution CJ-4 CI-4+
0% X X
- CI-4+
5% ULSD X X
• Examined 14 cases: 10% ULSD X X
- 0%, 5% and 10% by mass of 5% B-20 X X
fuel mixed with oil 10% B-20 X X

- Diluted with ULSD, B-20 and 5% B-100 X X

B-100 10% B-100 X X

• Six 0% fuel dilution cases

also used as controls Controls
3x 0% Fuel Dilution CJ-4
3x 0% Fuel Dilution CI-4+

Sloan Automotive Laboratory

 Fuel and Lubricant Properties
Lubricant Properties:
API Service CJ-4 CI-4+
API Gravity 29.1 28.9
Viscosity @ 40°C [cSt] 125 146
Viscosity @100°C [cSt] 15.7 14.9
Sulfated Ash (D874) [%] 1.0 1.35
TBN (D2896) [mg KOH/g] 9.6 10.2

Biodiesel Properties:
Property Value Limit (D6751)
Type Soy Methyl Ester (SME)
TAN [D664] 0.22 0.5

Sloan Automotive Laboratory

 Mass Loss Due to Evaporation
CJ-4
20
CI-4+

15
Mass Loss [%]

10

0
0% 5% ULSD 10% ULSD 5% B-20 10% B-20 5% B-100 10% B-100

• Reduced mass loss is seen in the B-100 cases due to the higher B-
100 boiling point
• Higher fuel dilution levels are expected in engines fueled with
biodiesel
Sloan Automotive Laboratory
 Increase in Acidity
180
CJ-4
165
CI-4+
% Increase of TAN at 160 hours

150
135
120
105
90
75
60
45
30
15
0
0% 5% ULSD 10% ULSD 5% B-20 10% B-20 5% B-100 10% B-100

• Fuel dilution with B-100 significantly increases the acidity of the

stressed lubricants
• TAN increases at a faster rate in the CJ-4 lubricant
Sloan Automotive Laboratory
 Total Base Number Retention
7 CJ-4 (D4739)
CI-4+ (D4739)
6
CJ-4 (D5984)
TBN at 160 hours [mgKOH/g]

CI-4+ (D5984)
5

0
0% 5% ULSD 10% ULSD 5% B-20 10% B-20 5% B-100 10% B-100

• Fuel dilution with B-100 results in higher TBN depletion for both
lubricants

Sloan Automotive Laboratory

 Percent Reduction in TBN
70.00
CJ-4
% Reduction of TBN at 160 hours

60.00 CI-4+

50.00

40.00

30.00

20.00

10.00

0.00
0% 5% ULSD 10% ULSD 5% B-20 10% B-20 5% B-100 10% B-100

• Accounting for different initial TBN levels, fuel dilution with biodiesel
only slightly increases TBN depletion
• The rate of TBN depletion is similar for the CJ-4 and CI-4+
lubricants
Sloan Automotive Laboratory
 Viscosity Increase
• Adding fuel to fresh lubricants results in an initial decrease in
viscosity
• Dilution with B-100 significantly increases CJ-4 viscosity at 160 hrs
• Viscosity increase shows similar trends as TAN increase
6
CJ-4
CI-4+
5
Viscosity Increase [mm2/s]

0
0% 5% ULSD 10% ULSD 5% B-20 10% B-20 5% B-100 10% B-100
Sloan Automotive Laboratory
 TBN and TAN Crossover
10
9 CJ-4, 10% ULSD
T B N ,T A N U n its [m g K O

8 CI-4+, 10% ULSD

TBN
7
6
5
4
TAN
3
2
1
0
0 20 40 60 80 100 120 140 160
Time [hours]

• TAN never exceeds TBN for the cases with no fuel dilution and the cases
diluted with only ULSD fuel
Sloan Automotive Laboratory
 TAN and TBN Crossover
10
9 CJ-4, 10% ULSD
T B N ,T A N U n its [m g K O

8 CI-4+, 10% ULSD

TBN
7 CJ-4, 10% B-100

6 CI-4+, 10% B-100

5
4
TAN
3
2
1
0
0 20 40 60 80 100 120 140 160
Time [hours]

• Dilution with biodiesel significantly increases the TAN at 160 hours

Sloan Automotive Laboratory

 TBN and TAN Crossover
10
9 CJ-4, 10% ULSD
T B N ,T A N U n its [m g K O

8 CI-4+, 10% ULSD

TBN
7 CJ-4, 10% B-100

6 CI-4+, 10% B-100

5
4
TAN
3
2
1 CJ-4 CI-4+

0
0 20 40 60 80 100 120 140 160
Time [hours]
• TAN crosses TBN earlier in the tests with the CJ-4 oil
• This observation alone would seem to indicate that corrosion in the CJ-4 oil
will be higher than with CI-4+ oil
Sloan Automotive Laboratory
 Corrosion
Unused 0% 5% ULSD 5% B-20 5% B-100

Copper

Tin

Lead

Increasing Biodiesel Concentration in the CJ-4 Lubricant

Sloan Automotive Laboratory
 Copper Corrosion
20
CJ-4, Cu
18
CI-4+, Cu
16
Mass of Copper [mg]

14
12
10
8
6
4
2
0
0% 5% ULSD 10% ULSD 5% B-20 10% B-20 5% B-100 10% B-100

• CJ-4 lubricant reduces corrosion of copper in all cases

• Copper corrosion increases substantially in the CI-4+, B-100 cases
• Low to zero levels of tin found in stressed oil
Sloan Automotive Laboratory
 Lead Corrosion
250
CJ-4, Pb
CI-4+, Pb
200
Mass of Lead [mg]

150

100

50

0
0% 5% ULSD 10% ULSD 5% B-20 10% B-20 5% B-100 10% B-100

• A 10 times increase in lead corrosion is observed in the B-100 cases

• The CJ-4 lubricant appears to give improved corrosion protection

Sloan Automotive Laboratory

 Conclusions
• Higher fuel dilution levels are expected with biodiesel
fuel
• In this test, fuel dilution appears to reduce TBN retention
and ultimately increase viscosity of the stressed oil
• Dilution with B-100 further decreases TBN and increases
TAN, reduces lubricant life and increases viscosity
• B-100 substantially increases corrosion of lead (10x) and
copper in the stressed lubricant
• Reduced corrosion was observed with the CJ-4 oil,
although acidity was increased
• TBN and TAN crossover was an unreliable indicator of
relative lubricant performance
Sloan Automotive Laboratory
 Acknowledgements
This research is supported by the MIT Consortium to
Optimize Lubricants and Diesel Engines for Robust
Emission Aftertreatment Systems

We thank for the following organizations/companies for

their support:

• Caterpillar • Komatsu
• Chevron • Lutek LLC.
• Ciba Specialty Chemicals • Sud-Chemie
• Cummins • Valvoline
• Department of Energy • Ford
Sloan Automotive Laboratory