SIMPÓSIO DE LUBRIFICANTES E ADITIVOS
28 e 29 de Outubro de 2008
An Introduction to Synthetic Base Stocks
Symposium on
Lubricants and
Additives
(Brazil, São
Paulo 2008)
Sandra Mazzo-Skalski
ExxonMobil Chemical
October 28, 2008
SIMPÓSIO DE LUBRIFICANTES E ADITIVOS
28 e 29 de Outubro de 2008
Objectives
• Synthetic Basestocks
– Group IV - PolyAlphaOlefins (PAO)
– Group V - Alkylated Naphthalene and Esters
• Trends in
– Automotive Engine Oils
– Automotive Transmission and Gear Oils
– Industrial Oils
• Bio Fuels – Effect on Lubricants
SIMPÓSIO DE LUBRIFICANTES E ADITIVOS
28 e 29 de Outubro de 2008
What are PolyAlphaOlefins (PAO)?
PAOs are high-performance, tailored fluids made by chemically
reacting materials of specific chemical composition to produce
compounds with planned and predictable properties.
• Well-defined structure vs.
multiple component
composition of mineral oil
• Hydrogenated (saturated) olefin
polymers
PAO 4 cSt
• Manufactured by the catalytic
oligomerization of linear
alphaolefins
• Wax-free combination of
molecules of predetermined
chain length
Mineral Oil 4 cSt
5
10
15
20
25
GC Retention Time (minutes)
30
SIMPÓSIO DE LUBRIFICANTES E ADITIVOS
28 e 29 de Outubro de 2008
What is an Ester?
•
Synthesized from organic acids and alcohols to produce
predetermined molecular structures.
•
Primarily a polar hydrocarbon which:
– Is thermally and oxidatively stable
– Has a high viscosity index
– Lacks undesirable and unstable impurities found in
conventional petroleum based oils
•
Structurally differentiated from PAO due to the presence of
multiple ester linkages (COOR)
The
Thepolar
polarnature
natureof
ofesters
estersdrives
drivestheir
theirperformance
performancefeatures.
features.
SIMPÓSIO DE LUBRIFICANTES E ADITIVOS
28 e 29 de Outubro de 2008
Polyol Esters
Product Type
Chemistry
Diesters
Diesters&&Aromatic
Aromaticesters:
esters:
TMP C8/C10
Polyol Esters
Performance
PerformanceFeatures
Features
Step-out
Step-outperformance
performancecapabilities
capabilitiesvs
vs
––higher
higherthermal
thermalstabilities
stabilitiesmay
mayextend
extendthe
the
operating
range
of
lubricant
by
as
much
operatingo range of lubricant by as much
as
oC
as50
50-100
-100C
PE Ester
––high
highfilm
filmstrength
strengthand
andincreased
increasedlubricity
lubricity
may
yield
reduced
energy
consumption
may yield reduced energy consumption
ininmany
manyapplications
applications
PE Ester
O
R
C
O
C
O
R
O
H2C
O
H2C
C
CH2
O
R
C
H2
C
CH3
O
H2C
C
CH2
O
O
C
O
R
O
C
C
R
R
O
O
O
CH2
R
TMP
Ester
SIMPÓSIO DE LUBRIFICANTES E ADITIVOS
28 e 29 de Outubro de 2008
Aromatic Esters
Product Type
Application
ApplicationOpportunities
Opportunities
Phthalates
Phthalatesare
areused
usedextensively
extensivelyininreciprocating
reciprocatingair
air
compressor
oils
where:
compressor oils where:
––low
lowviscosity
viscosityindex
indexisisthe
thenorm
norm
––low
lowcost
costclean
cleanoperation
operationisisdesirable
desirable
Chemistry
Diisohexyl
Phthalate Diisononyl
Aromatic
Ditridecyl
Esters
Triisooctyl
Trimellitate
Triisononyl
Trimellitates
Trimellitatesare
areoften
oftenused
usedinstead
insteadofofphthalates
phthalatesifif
aahigher
higherbase
baseoil
oilviscosity
viscosityisisneeded
neededfor
forimproved
improved
lubricity:
lubricity:
––often
oftenblended
blendedwith
withphthalates
phthalatesfor
forhigher
higher VG
VG
oils
oils
Phthalate
Trimellitate
O
O
R
O
O
+
HO
R
+
2
O
O
R
O
HO
O
R
O
O
R
O
O
O
3
HO
O
O
R
R
O
O
SIMPÓSIO DE LUBRIFICANTES E ADITIVOS
28 e 29 de Outubro de 2008
What are Alkylated Naphthalenes (AN)?
• Alkylated aromatic fluids
• Reaction of olefins with naphthalene
Catalyst
+ R
CH
CH2
CH
Naphthalene
Olefins
CH3
R
• American Petroleum Institute (API) Group V fluids
• Synthetic Blendstocks for Automotive and Industrial
Lubricants
SIMPÓSIO DE LUBRIFICANTES E ADITIVOS
28 e 29 de Outubro de 2008
Alkylated Naphthalene Characteristics
5 cSt AN
12 cSt AN
0.908
0.887
Viscosity @ 100°C, cSt
4.7
12.4
Viscosity @ 40°C, cSt
29
109
Viscosity Index
74
105
Flash Point, Open Cup, °C
222
258
Pour Point, °C
-39
-36
Noack Volatility, wt% loss
12.7
4.5
< 0.05
< 0.05
0.02
0.02
0.092
0.089
196
180
>1400
>1400
32
90
Specific Gravity @15.6/15.6°C
Total Acid Number (TAN), mg KOH/g
Hydrolytic Stability, TAN increase, mg KOH/g
Oxidation and Corrosion 175°C, 72 hrs
TAN increase, mg KOH/g
RPVOT @150°C without Antioxidant, minutes
RPVOT @150°C with Antioxidant, minutes
Aniline Point, °C
SIMPÓSIO DE LUBRIFICANTES E ADITIVOS
28 e 29 de Outubro de 2008
Automotive Engine Oil Trends
Increased thermal stress
Better oxidation stability
Lower oil volumes
Higher power densities
Reduced airflow/cooling
Longer drain intervals
Improved fuel economy
Lower engine emissions
Improved low
temperature properties
Lower viscosity grades
Improved wear protection
Lower volatility
basestocks
Synthetic
Lubricants
SIMPÓSIO DE LUBRIFICANTES E ADITIVOS
28 e 29 de Outubro de 2008
Key Areas for Synthetic Fluids in Passenger Vehicle Lubricants
Trend
Results in:
Recommended
Synthetic Basestock
PAO
Alkylated Naphthalene
Higher power outputs in
more compact engines
with lower oil volumes
in circulation
Problems with reduced
oil life, increased oil
consumption
Longer oil drain
intervals
Problems with increased PAO
viscosity, increased
Alkylated Naphthalene
deposit formation,
Esters
volatility
Emission legislation and
increasing demand for
fuel economy
Need for lower volatility
and lower viscosity oil,
and problems with
increased wear
PAO
Alkylated Naphthalene
Synthetic
Syntheticbasestocks
basestockscan
canmitigate
mitigatethe
thechallenges
challengesfacing
facingmodern
modernengine
engineoils
oils
SIMPÓSIO DE LUBRIFICANTES E ADITIVOS
28 e 29 de Outubro de 2008
Passenger Vehicle Engine Oil - Key Performance Criteria for Synthetics
Polyalphaolefin (PAO)
•
Low temperature fluidity & high temperature
viscosity retention
•
Low volatility
•
Thermal & oxidative stability
Esters
•
Additive solubility
•
Improved seal compatibility -- balance the
shrinking effect of PAOs
Alkylated Naphthalene (AN)
• Additive solubility
• Improved seal compatibility -- balance the shrinking effect of PAO’s
• Increased additive effectiveness with AN
– AN is less polar versus ester, therefore will not compete with
additive for metal surface
SIMPÓSIO DE LUBRIFICANTES E ADITIVOS
28 e 29 de Outubro de 2008
PolyAlphaOlefins (PAO) Lower Volatility
Noack Volatility, wt%
30
25
20
Typical Group I and II
Mineral Oils
15
Typical Group III
10
5
PAO
0
2
4
6
8
10
12
14
Viscosity @ 100 °C, cSt
PAOs
PAOshave
havelower
lowervolatility
volatilitythan
thanmineral
mineraloils;
oils;Low
Lowvolatility
volatilitymay
mayreduce
reduceoil
oil
consumption
and
emissions
consumption and emissions
SIMPÓSIO DE LUBRIFICANTES E ADITIVOS
28 e 29 de Outubro de 2008
Percent Viscosity Increase
AN Oxidation Resistance in SAE 5W-30 Engine Oils
Sequence III Screener* Results on SAE 5W-30 GF-4 Engine Oils
300%
250%
Add. Pkg #1 Reference
200%
Add. Pkg. #1 with 10% AN
150%
100%
Add. Pkg. #2 Reference
50%
0%
Add. Pkg. #2 with 10%
AN
-50%
0
50
100
150
200
250
Hours
AN
ANimproves
improvesoxidation
oxidationstability
stabilityin
inmarket-general
market-generalGF-4
GF-4engine
engineoils
oils
formulated
with
Group
II
basestocks
formulated with Group II basestocks
*ExxonMobil
*ExxonMobiloxidation
oxidationscreening
screeningtest
test
SIMPÓSIO DE LUBRIFICANTES E ADITIVOS
28 e 29 de Outubro de 2008
Alkylated Naphthalene –
Polarity Effects on Lubricant Additives
E = Ester Molecule A = Additive Molecule AN = AN Molecule
Base oil+AN+Additive
Base Oil+Ester +Additive
E
A
E
E
A
A
E
AN
A
A
A
A
A
A
Alkylated
AlkylatedNaphthalene
Naphthalenecan
canimprove
improveadditive
additiveeffectiveness
effectiveness
through
throughless
lesscompetition
competitionfor
forthe
thesurface.
surface.
SIMPÓSIO DE LUBRIFICANTES E ADITIVOS
28 e 29 de Outubro de 2008
Cam + Lifter Wear, um
Alkylated Naphthalene Improved Antiwear Additive Response
Sequence IIIG
Wear Performance
of
Experimental Low
Phosphorus 0W30 Engine Oils
160
140
120
100
80
60
40
20
0
PAO/Ester
PAO/AN
Synthetic
Synthetic engine
engine oils
oils blended
blended with
with PAO
PAO and
and Alkylated
Alkylated Naphthalene
Naphthalene
demonstrate
demonstrate improved
improved wear
wear performance
performance to
to PAO/ester
PAO/ester formulations.
formulations.
SIMPÓSIO DE LUBRIFICANTES E ADITIVOS
28 e 29 de Outubro de 2008
Automotive Drive Train Fluid Trends
Increased thermal stress
Better oxidation stability
Increased mechanical stress
Improved shear stability
Lower oil volumes
Higher power densities
Longer drain intervals
Improved low temperature
properties
Lower viscosity grades
Improved wear protection
Reduced airflow/cooling
Improved fuel economy
Improved shiftability
Improved seal compatibility
Basestocks with optimised
polarity
Synthetic
Lubricants
SIMPÓSIO DE LUBRIFICANTES E ADITIVOS
28 e 29 de Outubro de 2008
Key Areas for Synthetic Fluids in Automotive Drive train Fluids
Trend
Results in:
Recommended
Synthetic Basestock
Higher power outputs,
more compact designs
with lower oil volumes
in circulation
Problems with higher
temperatures and
reduced oil life,
increased oil
consumption
PAO
Alkylated Naphthalene
Increasing use of group
II & III base oils
Problems with reduced
additive solubility,
deposit formation
Low temperature
properties compromised
PAO
Alkylated Naphthalene
Esters
Increasing demand for
fuel economy
Need for Lower volatility
oils, Lower viscosities,
and problems with
increased wear
PAO
Alkylated Naphthalene
Synthetic
Syntheticbasestocks
basestockscan
canmitigate
mitigatethe
thechallenges
challengesfacing
facingautomotive
automotivedrive
drivetrain
train
fluids
fluids
SIMPÓSIO DE LUBRIFICANTES E ADITIVOS
28 e 29 de Outubro de 2008
Industrial Oil Trends
Lower oil volumes
Increased thermal stress
Better oxidation stability
Increased mechanical stress
Improved shear stability
Better cold start capability
Longer drain intervals
More severe operating
conditions
Improved energy efficiency
Lower viscosity grades
Improved wear protection
Lower traction oils
Synthetic
Lubricants
SIMPÓSIO DE LUBRIFICANTES E ADITIVOS
28 e 29 de Outubro de 2008
Key Areas for Synthetic Fluids in Industrial Lubricants
Trend
Results in:
Recommended
Synthetic Basestock
Higher power outputs,
compact designs with
lower oil volumes in
circulation
Problems with higher
temperatures and
reduced oil life
PAO
Alkylated Naphthalene
Increasing use of group
II & III base oils
Problems with reduced
additive solubility,
deposit formation and
Low temperature
properties compromised
PAO
Alkylated Naphthalene
Esters
Increased oil drain
intervals
Increasing demands on
thermal and oxidation
stability of oil
PAO
Alkylated Naphthalene
Extended maintenance
intervals
Problems with increased PAO
wear
Alkylated Naphthalene
Synthetic
Syntheticbasestocks
basestockscan
canmitigate
mitigatethe
thechallenges
challengesfacing
facingIndustrial
IndustrialLubricants
Lubricants
SIMPÓSIO DE LUBRIFICANTES E ADITIVOS
28 e 29 de Outubro de 2008
Alkylated Naphthalene in Compressor Oil Formulation
Turbine Oil Stability Test (TOST) ASTM D 943
Limit 2.0
1.6
PAO / Polyol Ester / Additive
PAO / 5 cSt AN / Additive
1.2
Total Acid Number,
mg KOH/g
ISO VG 46
Compressor Oil
0.8
0.4
0.0
0
500
1000
1500
2000
2500
3000
3500
Time, hr
Alkylated
AlkylatedNaphthalene
Naphthaleneimproves
improvesoxidative
oxidativeand
andhydrolytic
hydrolytic
stability
stabilityof
ofcompressor
compressoroils.
oils.
SIMPÓSIO DE LUBRIFICANTES E ADITIVOS
28 e 29 de Outubro de 2008
PolyAlphaOlefins (PAO) Oxidative Stability
•
Oxidative stability of PAO
exceeds mineral oil
Oxidation Stability Test
PAO Vs. Mineral Oil (2% Antioxidant)
•
•
Good oxidative stability for
applications at elevated
temperatures with air contact
PAOs show excellent
oxidative stability when
formulated with suitable
antioxidants
Product
Mineral Oil 6 cSt 40 cSt 100 cSt
Group II PAO PAO
PAO
% Vis Change @ 100°C 215.7
14.5
TAN change, mg
160.7
Lead loss, mg
moderate
Sludge
3.5
0.1
0.9
nil
2.6
0.08
0.1
nil
Test Conditions: 163oC (325oF), 72 hours
•
PAOs are more responsive
to antioxidants than mineral
oil.......also to antiwear and
other performance additives
1.8
1.1
0.2
trace
SIMPÓSIO DE LUBRIFICANTES E ADITIVOS
28 e 29 de Outubro de 2008
Alkylated Naphthalene - Synergistic Blends with Group II Basestock
250
Rotary Pressure Vessel Oxidation Test (RPVOT)
Time (min)
200
150
100
50
0
0%
20%
40%
60%
80%
100%
Synesstic™ 5 in Group II Basestock
Alkylated
Alkylated Napthalene
Napthalene shows
shows aa synergistic
synergistic effect,
effect, yielding
yielding improved
improved
Group
Group IIII oxidation
oxidation performance.
performance.
SIMPÓSIO DE LUBRIFICANTES E ADITIVOS
28 e 29 de Outubro de 2008
Alkylated Naphthalene - Hydrolytic Stability
ISO VG 32
Ester blend
AN Blend
6 cSt PAO
73 %
73 %
Adipate Ester
25 %
---
---
25 %
2%
2%
Copper Corrosion, mg/cm²
0.15
0.00
TAN Change, mg KOH/g
0.22
0.03
Total Acidity of Water, mg KOH
19.9
4.9
5 cSt Alkylated Naphthalene
Additives
ASTM D 2619
Replacing
Replacingadipate
adipateester
esterwith
withAN
ANimproves
improveshydrolytic
hydrolyticstability
stabilityin
inaa
formulated
formulatedoil.
oil.
SIMPÓSIO DE LUBRIFICANTES E ADITIVOS
28 e 29 de Outubro de 2008
Bio Fuels – How Will They Effect Lubricants?*
•
Biofuels in Brazil
– Brazil produces 4.7 billions gallons of
biofuel per year; could double by 2015
– More than 40% of transportation fuels
in Brazil are from renewable sources
•
Ethanol
– Ethanol is a clean-burning, high-octane
fuel that is produced from renewable
sources.
• produced from sugar cane or corn
– Ethanol attracts moisture; lubes need to
have good emulsibility and rust
protection
•
*Compiled from Industry resources
Biodiesel
– Typically, biodiesel fuel is a methyl
ester based on a natural fat or plant oil
such as Rapeseed, (RME) Soy (SME),
Palm Oil (PME).
– Primary lubricant concern is excess fuel
dilution, leading to increased corrosion,
oxidation, deposits and wear
SIMPÓSIO DE LUBRIFICANTES E ADITIVOS
28 e 29 de Outubro de 2008
Thank you
Questions?
©2008 ExxonMobil. To the extent the user is entitled to disclose and distribute this document, the user may forward, distribute, and/or
photocopy this copyrighted document only if unaltered and complete, including all of its headers, footers, disclaimers, and other
information. You may not copy this document to a Web site. ExxonMobil does not guarantee the typical (or other) values. Analysis may
be performed on representative samples and not the actual product shipped. The information in this document relates only to the named
product or materials when not in combination with any other product or materials. We based the information on data believed to be
reliable on the date compiled, but we do not represent, warrant, or otherwise guarantee, expressly or impliedly, the merchantability, fitness
for a particular purpose, suitability, accuracy, reliability, or completeness of this information or the products, materials, or processes
described. The user is solely responsible for all determinations regarding any use of material or product and any process in its territories
of interest. We expressly disclaim liability for any loss, damage, or injury directly or indirectly suffered or incurred as a result of or related
to anyone using or relying on any of the information in this document. There is no endorsement of any product or process, and we
expressly disclaim any contrary implication. The terms, “we”, “our”, "ExxonMobil Chemical", or "ExxonMobil" are used for convenience,
and may include any one or more of ExxonMobil Chemical Company, Exxon Mobil Corporation, or any affiliates they directly or indirectly
steward. ExxonMobil, The ExxonMobil Emblem, the “Interlocking X” Device, Synesstic, SpectraSyn, SpectraSyn Ultra and SpectraSyn
Plus are trademarks of ExxonMobil.
All charts included in the presentation based on ExxonMobil data.