White Paper

The enhanced oxidative stability

of metallocene polyalphaolefin base stocks
By Michael P. Sheehan, Senior Staff Chemist, Marketing Technical Services,
ExxonMobil Chemical Company
White Paper

The enhanced oxidative stability

of metallocene polyalphaolefin base stocks
By Michael P. Sheehan, Marketing Technical Services,
ExxonMobil Chemical Company

Polyalphaolefin (PAO) base stocks have

long been used to formulate high perfor-
mance lubricants for automotive and
industrial applications. Their high viscosity
indices (VI), very good oxidative stability and
excellent low-temperature properties help
formulators create lubricants that operate
for longer periods under wider operating
temperatures than equivalent viscosity
grade mineral oils. PAO- based lubricants
also typically can offer energy savings
through reduced traction and improved
low-temperature fluidity. When they were
introduced, PAO- based lubricants tended
to be used for very high performance,
top-tier products or for applications
in which mineral oil performance was
insufficient, such as in extreme tempera-
tures. However, over the years, the use
of PAO has increased as industry trends
demand higher lubricant performance.
More compact equipment running under
more severe operating conditions creates
higher stress on the oil, which at the same
time is expected to provide longer drain
intervals. Under these conditions, lubri-
cants are exposed to higher oxidative and
thermal degradation, creating a greater
need for products that offer enhanced
oxidative stability.
In the past few years, a new family of PAO
products has been developed to meet
the rising demand for high viscosity synthetic
base stocks. Based on metallocene catalyst
technology, this new metallocene polyal-
phaolefin (mPAO) base stock can provide
improved properties over conventional
PAO (cPAO) — higher viscosity index,
better low-temperature fluidity and
greater shear stability. The oxidative stability
of these PAOs was initially thought to be
equivalent, but subsequent testing shows
that mPAO offers enhanced capability
in this key performance area.
The importance of oxidative stability
Oxidation is the breakdown of a lubricant
due to aging and operating conditions
in the presence of oxygen (air). Oxidation
results in oil thickening with the formation
of acidic byproducts. Depending on the
severity of the oxidation, the oil could form
polymeric byproducts leading to varnish
and lacquer deposits on metal surfaces.
The rate and ease of a lubricant’s oxidation
depend on:
• Temperature — each 10°C increase
doubles the oxidation rate
• The type of carbon-hydrogen
bond — CH3 primary carbons being
the least reactive
• Concentration of oxygen
• Catalytic effect of metals
• Presence and concentration of antioxidant
and metal passivator additives
Improved oxidative stability leads to less
oil thickening, lower production of acidic
byproducts and better deposit control.
These improvements could translate into
longer service life, better energy efficiency,
longer equipment service with less down-
time and possibly lower maintenance costs.

Learn more at exxonmobilchemical.com/synthetics

 FIGURE 1 Lower residual olefin content
Comparing the structures
of mPAO and cPAO
Given the advantages of greater oxidative
stability, the structure of mPAO suggests
it should provide this enhanced capability
(Figures 1 and 2). Metallocene catalysis
is a very stereospecific reaction, creating a
product with little to no olefin isomerization
during polymerization. The residual olefin is
terminally located. Production of cPAO, on
the other hand, uses a strong acid catalyst,
resulting in extensive isomerization of the
olefin bond during polymerization, which
internalizes the residual olefin.
After polymerization, the base oil is hydro-
genated to remove unwanted residual
olefins to improve stability. Terminal FIGURE 2 Lower tertiary carbon content
olefins are easier to hydrogenate than
internalized olefins, resulting in a base oil
with a lower level of unsaturation, which
improves oxidative stability. Although
the unsaturation level for cPAO is very low,
ExxonMobil tests show that it is two to three
times lower in mPAO.
A second structural difference that could
impact oxidative stability is tertiary carbon
(C-H) content. The reactivity rate of the
C-H bonds shows that tertiary carbons are
next in the ease of oxidation after olefins.
Due to the difference in isomerization rate
(Figure 2), mPAO should have a lower
level of tertiary carbons than the same
molecular weight cPAO.

FIGURE 3

Automotive Industrial Industrial Industrial/ Automotive Aviation

Test method CEC L-60 CEC L-48 ASTM D2893 ASTM D5763 ASTM D4636

Test temperature, °C 160 160 95-121 120 175-225

Test duration, hour 50 96-192 312 312 72

Air flow rate, L/hr 10 5-10 10 3 5 to 10

Catalyst Steel, Cu None None None Al, Ag, Steel Cu, Mg

Test cell Gear box Glassware Glassware Glassware Glassware

 FIGURE 4 Test temperature impact on viscosity change ISO VG 320 base oil blend
Demonstrating the difference
To prove that mPAO offered enhanced 40°C Viscosity change
performance, alternate tests were consid-
ered that provide greater flexibility to safely cPAO 100 mPAO 150
stress the oils. ASTM D4636, which is used
140
to evaluate aviation turbine lubricants,

% Viscosity change, 40°C

ASTM D445
121
was chosen because it offered many of
the same parameters found in accepted
industry tests (Figure 3), but allowed safe 76 79
72 72
modifications of the test.

To determine if a performance difference
existed between the two base stocks,
the temperature, test duration and air
flow rate parameters were modified and
examined. The spent samples for viscosity
change (oil thickening), total acid number
change, sludge content and metal catalyst
weight change were tested. The first set
of experiments focused on the impact of
test temperature on oil viscosity change
(Figure 4). The test was limited to ISO VG
320 base oil blend (no additives) to minimize
effects associated with an additive system.
Better
175°C 190°C 204°C
Test temperature
The results showed that a test tempera- The mPAO base oils demonstrated lower
ture of 204°C provided a clear perfor- oil thickening, better acid number control
mance break point, while minimizing and improved corrosion toward magnesium
test duration (72 hrs) and air flow rate metal. Although the test looks at five metals
(5 l/hr air). The neat base oils were then (Al, Ag, Cu, Steel and Mg), the only one
accessed to get a clear understanding impacted was the magnesium. The sludge
of the performance differences without control data was mixed, with mPAO 65
clouding the data with other issues, such providing an improvement over cPAO 40
as co-base oils or additive impact. while the mPAO 150 offered equivalent
The results are shown in Figure 5. performance to cPAO 100.

FIGURE 5 Neat base oil evaluation: 204°C

40°C Viscosity change Total acid number change

% Viscosity change

ASTM D445

TAN change, mg KOH/g

SAE ARP5088
208 5.01
4.18 4.02
156
3.41
110
Better

Better

62

cPAO 40 mPAO 65 cPAO 100 mPAO 150 cPAO 40 mPAO 65 cPAO 100 mPAO 150

Sludge content Magnesium corrosion

Sludge; mg/ 100ml

ASTM D445

Magnesium Loss, mg

SAE ARP5088

14 28.3
13

9.6

6.4
Better

Better

3.9
1.3 0.2
cPAO 40 mPAO 65 cPAO 100 mPAO 150 cPAO 40 mPAO 65 cPAO 100 mPAO 150
Evaluating blends Testing formulated lubricants As expected, the additives in fully formu-
Next, the performance of a combination After testing the neat and base oil blends, lated products negated the differences
of low and high viscosity PAO to make would mPAO offer any benefit to a fully seen in earlier tests. As shown in Figure 7,
a non-additized ISO VG 320 blend was formulated lubricant? ISO VG 320 industrial the formulated samples displayed no
evaluated. Again the results (Figure 6) oil samples were formulated and tested difference in performance because the
show that mPAO blends offer better in the modified method. cPAO 100 and additive package minimized oxidation and
viscosity and sludge control than cPAO- mPAO 150 were compared to keep the extended service life.
based samples. It is notable that the cPAO formulations consistent by maintaining An effort was then made to identify
100 and mPAO 150 are at the same treat the same concentration of the high conditions to offset the additive response.
rate, whereas the blend using cPAO 40 has viscosity component. Wanting to maintain the existing test
a slightly higher concentration compared temperature, test duration was extended.
to the mPAO 65 blend.
FIGURE 6 ISO VG 320 base oil blends: 204°C

ISO VG 320 blends Sludge content

Sludge, mg/100 ml

ASTM D4636
Component A B C D 13

cPAO 6 8.00% 16.80% 37.20% 36.60%

9
cPAO 40 92.00% 8
7
cPAO 100 62.80%

Better
mPAO 65 83.20%
mPAO 150 63.40%
Viscosity, 40°C, cSt 316 321 319 321
cPAO 40 mPAO 65 cPAO 100 mPAO 150

Total acid number change Viscosity change, 40°C

TAN change, mg KOH/g

SAE ARP5088

% Viscosity change

ASTM D445
9.6 9.6
9.6 9.6
148 145

93
78

Better
Better

cPAO 40 mPAO 65 cPAO 100 mPAO 150 cPAO 40 mPAO 65 cPAO 100 mPAO 150

FIGURE 7 ISO VG 320 industrial gear oil (IGO): 144 hours

Component Blend A Blend B

cPAO 8 28.2% 29.4%
cPAO 100 60.3%
mPAO 150 59.1%
Synesstic™ 5 10.0% 10.0%
Additive package 1.5% 1.5%
Viscosity, 40°C, cSt 339 314

Viscosity change, 40°C Total acid number change Sludge & varnish content
% Viscosity Change

ASTM D445

TAN change, mg KOH/g

SAE ARP5088

Sludge & Varnish

Content, mg/100 ml

ASTM D4636

9.6
9.5 953
420

278 756
Better

Better
Better

cPAO 100 mPAO 150 cPAO 100 mPAO 150 cPAO 100 mPAO 150
 FIGURE 8
Viscosity change vs Test duration
% Viscosity change, 40°C
ISO VG 320 industrial gear oil (IGO): 204°C
By extending it from 72 hours to 144 hours,
the antioxidant additive was sufficiently
consumed, and the difference in perfor-
Solid mance between the base oils was seen.
In fact, when the test duration was

1413
extended to 168 hours, the cPAO formu-
lation was solid at room temperature
while the mPAO-based sample flowed.
After identifying the new 144-hour test
444
condition, several experiments were run

Better
311 to assess performance of the formulated
183 154 cPAO 100
61 54
samples (Figure 8).The results indicated
mPAO 150
the mPAO-based formulation offered
72 120 144 168
enhanced viscosity and sludge control,
Test time, hour as well as lower total acid number change
compared to the cPAO-based product.

Conclusions
Through alternate test methods that conditions of temperature and stress. With this new awareness of enhanced
create more severe operating conditions, The mPAO also reduced sludge and oxidative performance under severe
mPAO was found to offer performance varnish generation. Before these tests, conditions, formulators can now make
advantages over cPAO base stocks it was known that mPAO provides higher a more informed decision when choos-
(Figure 9). viscosity index, improved low-temperature ing which PAO base stock is right for
The enhanced oxidative stability of performance and superior air release and the lubricant they want to blend.
mPAO lessens oil thickening, allowing foaming properties when compared to
a formulated lubricant to better retain its cPAO.
lubrication capabilities even in extreme

FIGURE 9 mPAO compared to cPAO

Neat base oils ISO 320 base oil blend ISO 320 IGO formulation

Viscosity change, 40°C ++ ++ ++

Total acid number change + = +

Sludge/varnish content +/= + +

Metal corrosion (mg) + + =

©2018 ExxonMobil. ExxonMobil, the ExxonMobil logo, the interlocking “X” device and other product or service names used herein are trademarks of ExxonMobil, unless indicated otherwise. This document may
not be distributed, displayed, copied or altered without ExxonMobil’s prior written authorization. To the extent ExxonMobil authorizes distributing, displaying and/or copying of this document, the user may do
so only if the document is unaltered and complete, including all of its headers, footers, disclaimers and other information. You may not copy this document to or reproduce it in whole or in part on a website.
ExxonMobil does not guarantee the typical (or other) values. Any data included herein is based upon analysis of 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, freedom from patent infringement, 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. This document is
not an endorsement of any non-ExxonMobil product or process, and we expressly disclaim any contrary implication. The terms “we,” “our,” “ExxonMobil Chemical” and “ExxonMobil” are each used for
convenience, and may include any one or more of ExxonMobil Chemical Company, Exxon Mobil Corporation, or any affiliate either directly or indirectly stewarded.