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JSAE 20159037
SAE 2015-01-2048

Methods for Rating the Viscosity-Temperature Behavior


of Polymer-Containing Lubricants
Jack Zakarian
Chevron Products Company

Michael Webb, Brett Hunter


Evonik Oil Addives USA, Inc

Copyright © 2015 SAE Japan and Copyright © 2015 SAE International

ABSTRACT very good viscosity-temperature behavior was


assigned an index of 100.
The Viscosity Index (VI, ASTM D2270) has a long and
widespread history as a rating scale for the viscosity- The Viscosity Index is a relative rating method
temperature behavior of lubricants. However, the because the calculation of VI for any given oil is done
method has serious technical deficiencies which can by comparing the candidate oil to two reference oils –
lead to misleading conclusions. We have examined one reference having 0 VI and the other having 100 VI.
alternatives to the VI scale in an effort to more Many of the problems with the VI arise from the fact
accurately characterize the viscometric behavior of that the reference oil definitions are not consistent and
modern lubricants, which are formulated with highly have been modified over the years [1,2,3].
refined base oils and advanced polymers. We have
found that the VI method can actually mask improved The VI was originally applied to unadditized distillation
viscosity-temperature behavior for certain highly fractions of high quality Pennsylvania crude oil which
additized polymer-containing lubricants. We examine served as lubricating oils in the 1920s and 1930s. The
two different methods, the Roelands Slope Index and rapid evolution of improvements in equipment,
the Proportional VI, as an alternative to VI. It is coupled with more severe demands on the lubricant,
important for lubricant developers and consumers to resulted in a need for oils formulated with
be aware of the limitations of the VI scale in describing performance-enhancing additives. One of the key
the viscometric qualities of modern, high performance advancements in lubricating oil technology was the
lubricants. development of viscosity index improvers (VII), now
often referred to as viscosity modifiers (VM). Kinker [4]
INTRODUCTION notes that a major impetus for the development of VIIs
was the US Government’s search for improved
The Viscosity Index (VI) method was first proposed in materials that could aid the military during World War
1929. Despite its long and universal usage in the II. One of the first applications was the use of
lubricants industry, this method for rating the polymethacrylates (PMA) in the formulation of aviation
viscosity-temperature properties of a lubricating fluid hydraulic fluids. These fluids were subject to
suffers from many problems. Zakarian [1,2,3] has temperature extremes from below -40°C to above
given a comprehensive analysis of how the VI was 150°C. The PMAs are high molecular weight polymers
originally defined and then modified over the years in which, when added to typical lubricating base stocks,
attempts to overcome some of the most egregious impart a relatively higher viscosity at higher
problems with the method. The present method, as temperatures compared to the viscosity increase at
defined by ASTM D2270, is still based on a number of lower temperatures. Thus, a fluid can be formulated
scientific inconsistencies, but it nevertheless performs with sufficiently high viscosity at high temperatures
well enough for practical purposes. (increased film thickness) while retaining the ability to
flow well at low temperatures. Lubricants made with
Perhaps the most important function of the VI is the VIIs had VI ratings much higher than previously
assignment of a single number which gives the user observed for standard petroleum oils. The VI of such
information about the relative rate of change of lubricants ranged from 150 to 300, and hence the
lubricant viscosity with temperature. From the original origin of the name “viscosity index improver” for the
1929 definition, a VI of 0 designated a reference oil polymer component. After the war, the PMAs and
with poor viscosity-temperature behavior (that is, the other materials were essential components in the
oil showed a relatively large increase in viscosity as formulation of the first multigrade (SAE W grade)
temperature decreased). Similarly, a reference oil with engine oils. Since then, increasingly severe demands
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on both low- and high-temperature lubricant both 40 and 100°C. Kinematic viscosities were
viscosities have resulted in widespread application of measured in a capillary viscometer per ASTM D445.
VIIs or VMs for the formulation of engine, transmission, When the dynamic viscosity was desired, it was
axle, hydraulic, and other lubricating fluids. calculated as the multiplication product of the
kinematic viscosity and density. The blend densities
The purpose of the work reported in this paper is to were measured at 15.6°C and converted to densities
examine the effect of adding polymeric viscosity at other temperatures using a temperature change
modifiers to a variety of low viscosity base oils from factor of 0.00065 g/cc/°C.
API Groups II, III, IV, and V. In particular, we are
interested in determining if the VI rating scale shows RESPONSE OF BASE OILS TO PMA
the same type of anomalous behaviors as observed
for lubricating oils which do not contain VMs. We also Table 2 shows viscosity and VI data from blends of
want to test other methods for characterizing the base oils with a PMA VI Improver. The PMA,
viscosity-temperature response for oils containing designated PMA-1, is a commercial material made by
polymers. Evonik. The shear stability index (SSI) of PMA-1 is 35
(measured by the KRL 20-hour shear method,
EXPERIMENTAL CEC-L-45-A-99). The treat rate of PMA-1 was varied
from 0 wt% (neat base oil) to 30 wt% polymer in base
Table 1 shows the properties of both the low viscosity oil.
base oils and the viscosity modifiers. The column
labeled “Type” displays whether the component is a Table 2. Viscosity Data: Blends of PMA-1 with Base
base oil or viscosity modifier (VM). For base oils, the Oil
“Type” column displays the API Group number. As
noted above, we used low viscosity base oils from API Treat Viscosity Viscosity Roelands
Groups II, III, IV, and V. This was done to cover the Rate cSt, 40 cSt, 100 Slope
wide range of formulating options used in modern (%) °C °C VI Index DVI PVI
lubricating oils. The VMs similarly represent a wide 0 19.29 4.232 126 1.13 125 117
range of different chemistries, including PMAs, 2.5 21.67 4.789 148 1.10 132 125
polybutenes (PIBs), high molecular weight PAOs, and 5 24.72 5.495 169 1.06 139 135
others. For this work, we selected VMs commonly Yubase 4 /
10 32.28 7.113 193 1.01 148 152
used to formulate driveline products. We did not PMA-1
15 42.13 9.157 208 0.97 154 170
include VMs typically used in engine oil formulations,
20 57.02 11.74 207 0.96 157 182
such as olefin copolymers (OCPs) and hydrogenated
30 100.7 19.06 212 0.92 162 213
styrene-diene copolymers.
0 18.25 4.094 127 1.13 125 118
Table 1. Properties of Test Lubricants. 2.5 20.3 4.614 150 1.09 133 127
5 22.76 5.213 171 1.06 140 136
PAO-4 /
10 29.02 6.649 193 1.01 149 153
V.I. PMA-1
Vis, Vis, (Visco 15 37.8 8.51 212 0.97 155 170
cSt, cSt, -sity 20 50.1 10.89 216 0.94 158 185
Name Manufacturer Type 40°C 100°C Index)
30 91.52 17.72 213 0.92 161 210
Esterex ExxonMobil
A41 Chemical Gr.V 13.81 3.542 142 0 13.81 3.542 142 1.05 142 125
2.5 16.33 4.156 167 1.02 147 135
Motiva
Star 3 Enterprises Gr.II 13.07 3.141 101 Esterex 5 19.19 4.858 192 0.99 152 145
A41 / PMA- 10 26.77 6.588 214 0.94 158 164
Motiva
1 15 37.02 8.804 230 0.91 163 183
Star 12 Enterprises Gr.II 109.4 12 98
20 50.87 11.61 231 0.89 166 201
ChevronPhillips
Synfluid 4 Chemical Gr.IV 18.21 4.068 125 30 94.6 19.55 231 0.86 169 236
0 13.07 3.141 101 1.14 123 111
Yubase 4 SK Lubricants Gr.III 19.29 4.232 126 2.5 15.32 3.659 126 1.11 130 119
Indopol
5 17.7 4.23 150 1.07 137 128
Star 3 /
H-1900 Ineos VM 162,000 4,000 267 10 23.37 5.62 192 1.01 149 148
PMA-1
ChevronPhillips 15 32.56 7.534 211 0.97 155 164
mPAO 100 Chemical VM 992 100 194 20 44.31 9.905 219 0.94 159 182
30 82.8 16.64 218 0.91 163 212
PMA-1 Evonik VM 16,500 610 195 0 109.4 12 98 1.25 95 98
Spectrasyn ExxonMobil 2.5 119.8 13.42 108 1.22 104 106
PAO 100 Chemical VM 1240 100 170 5 132.1 14.99 116 1.19 111 113
Star 12 /
Viscobase 10 161.6 18.68 130 1.14 123 129
PMA-1
11-522 Evonik VM 14,100 500 180 15 199.4 23.1 142 1.11 131 144
20 247.7 28.46 151 1.08 137 158
30 391 42.58 163 1.04 144 183
The experimental work consisted simply of blending a
particular low viscosity base oil with a selected VM Table 2 also displays the Roelands Slope Index (RSI),
and then measuring the resulting blend viscosity at Dynamic VI (DVI), and Proportional VI (PVI) for each
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blend. The RSI is calculated from the following Figure 1 – VI versus PMA-1 Treat Rate
equation [5,6]:
VI vs. PMA-1 Treat Rate
Log(log η + 1.2) = -S*log(1 + t/135) + log G (1) 240

220
where
η = dynamic viscosity, cP 200

ASTM D2270 VI
Star 12
t = temperature, C 180 Star 3
S, G = constants Esterex A41
160 PAO 4
Yubase 4
The RSI is simply the value of S calculated from 140
Equation 1. This number represents the rate of
change of dynamic viscosity with temperature. 120
0 5 10 15 20 25 30
Roelands equation was designed so that n-paraffins Wt.% PMA-1 in Blend

display RSI values approximately equal to 1.0. The


lower the value of RSI, the less change in viscosity
Figure 2 displays the PVI of the same blends shown in
with temperature (that is, as RSI decreases, the
Figure 1. Because the PVI uses the more rational
ASTM VI increases). The DVI is simply a calculation Fenske 100-VI series, the oils all show the behavior of
proposed by Roelands to convert RSI values to a steadily increasing VI with increasing VII content. Both
number more comparable to the ASTM VI. The DVI is
VI and PVI are relative rating systems for viscosity-
calculated as follows:
temperature behavior and both use roughly the same
S type of reference oils. However, the two rating
DVI = 220 – 7*10 (2)
methods give widely different results for the oils in
Table 1.
The PVI value in Table 2 is calculated as:
Figure 2 – PVI versus PMA-1 Treat Rate
PVI = [2.611*(vis at 100°C)^1.4959]*100 / [vis at 40°C]
(3)
Proportional VI vs. PMA-1 Treat Rate
240
Where the (vis at 100°C) and the (vis at 40°C) in
Equation (3) represent the kinematic viscosities of the 220

oil that is being rated. The PVI [2] uses the 100-VI 200
series proposed by Hersh, Fisher, and Fenske [7] Star 12
instead of the 100 VI series adopted by ASTM. The
PVI

180 Star 3
Esterex A41
Fenske 100-VI reference oil series has the following 160 PAO 4
three technical advantages compared to the ASTM Yubase 4

100-VI series: (1) The Fenske oils span a much wider 140

range of viscosity; (2) The Fenske viscosities were


120
more accurately measured; (3) The Fenske reference 0 5 10 15 20 25 30

samples came from a very large number of Wt.% PMA-1 in Blend

Pennsylvania crude lubricating fractions. For any


given value of test oil viscosity at 100°C, the PVI is the The RSI is an absolute rating method in the sense that
ratio (multiplied by 100) of the Fenske 100-VI it is not based on comparison with reference oils, but
reference oil viscosity at 40°C to the test oil viscosity rather represents the actual slope of a viscosity-
at 40°C. temperature plot. Figure 3 plots the DVI of the same
blends as shown in Figures 1 and 2. The DVI does
Figure 1 plots the VI of the blends in Table 1 as a show similar behavior for all base oils, and all curves
function of the treat rate of PMA-1. As the show a decreasing slope as PMA-1 treat rate
concentration of PMA-1 approaches 100%, the VI of increases.
the blend should approach the VI of PMA-1, which is
195. There is one oil, Star 12, that displays the Figure 3 – DVI versus PMA-1 Treat Rate
behavior of increasing VI with increasing VII content.
All of the other base oils show a rapid increase in VI Roelands Dynamic VI vs. PMA-1 Treat Rate
above 195, reaching a plateau which must eventually 170

return to 195 when the wt% of PMA-1 is 100. We


160
believe that the results in Figure 1 are another
example of the unsuitability of VI as a rating method 150
Dynamic VI

for viscosity-temperature change. The anomalous Star 12


140 Star 3
results are in part due to the different definitions of Esterex A41
ASTM 100-VI reference oils in the regions above and 130 PAO 4

below 7.3 cSt at 100°C. The blends made with Star 12 Yubase 4
120
are rated differently by the ASTM VI compared to
those made with lower viscosity base oils because of 110
all of the Star 12 blends had viscosities above 7.3 cSt. 0 5 10 15 20
Wt.% PMA-1 in Blend
25 30
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RESPONSE OF BASE OILS TO ADDITION OF Figure 4 – VI of PAO 4 Blends versus Treat Rate of
OTHER VISCOSITY MODIFIERS Viscosity Modifier

Table 3 lists the results of blends of PAO 4 VI vs. Treat Rate of Viscosity Modifier
180
(ChevronPhillips Synfluid 4) with a variety of other
viscosity modifiers. Viscobase 11-522 is an alkyl 170
methacrylate oligomer. Indopol H-1900 is a
polybutene. We used two types of high viscosity PAO, 160

ASTM D2270 VI
one made by conventional processing (PAO 100) and 150
VB 11-522
mPAO 100
the other made by a newer metallocene catalyst based Ind H1900
process (mPAO 100). 140
PAO 100

130
Table 3. Viscosity Data: Blends of PAO 4 with Various
Viscosity Modifiers 120
0 5 10 15 20 25 30
Wt.% VM Added to PAO 4

Treat Viscosity Viscosity Roelands


Rate cSt, 40 cSt, 100 Slope
Figure 5 – PVI of PAO 4 Blends versus Treat Rate of
(%) °C °C VI Index DVI PVI
Viscosity Modifier
0 18.21 4.068 125 1.13 124 117
2.5 19.89 4.445 139 1.11 129 122
Proportional VI vs. Treat Rate of Viscosity Modifier
PAO 4 / 5 21.89 4.822 148 1.10 132 125 170
Viscobase 10 26.72 5.734 165 1.08 137 133
11-522 160
15 33.27 6.865 172 1.06 140 140
20 42.63 8.281 173 1.05 141 145 150
30 69.6 12.28 176 1.03 146 160
VB 11-522

PVI
140
0 18.41 4.089 124 1.14 124 117 mPAO 100
Ind H1900
5 21.72 4.668 136 1.12 127 120 130
PAO 100
PAO 4 / 10 25.66 5.37 150 1.11 130 126
120
mPAO 100 15 30.32 6.157 157 1.09 133 131
20 36.1 7.081 163 1.08 135 135 110
0 5 10 15 20 25 30
30 51.48 9.414 169 1.06 139 145
Wt.% VM Added to PAO 4
0 18.21 4.068 125 1.13 124 117
2.5 22.15 4.78 141 1.12 128 122
PAO 4 /
5 26.67 5.546 152 1.10 131 127 Figure 6 – DVI of PAO 4 Blends versus Treat Rate
Indopol H- of Viscosity Modifier
10 39.16 7.482 161 1.09 135 135
1900
15 57.77 10.1 164 1.07 137 144
20 85.59 13.6 162 1.06 139 151 Roelands Dynamic VI vs. Treat Rate of Viscosity Modifier
150
30 188.6 24.71 162 1.05 141 168
0 18.21 4.068 125 1.13 124 117 145

2.5 20.27 4.434 133 1.13 126 120


140
PAO 4 / 5 22.53 4.82 140 1.12 128 122
Dynamic VI

VB 11-522
PAO 100 10 27.69 5.68 152 1.11 131 127 135
mPAO 100
15 34.04 6.68 157 1.10 133 131 Ind H1900
130
20 41.83 7.879 162 1.08 135 137 PAO 100

30 63.59 10.86 163 1.07 138 146 125

120
Figure 4 shows how the VI of each blend changes with 0 5 10 15 20 25 30
Wt.% VM Added to PAO 4
increasing amount of viscosity modifier. Similar to the
results in Figure 1, the Indopol H-1900 and PAO 100
curves definitely show a plateau as the VM content
rises above 15 wt%. The Viscobase 11-522 and EXTENSION OF VI SCALE TO VALUES
mPAO 100 curves do not completely level off, but ABOVE 100
rather show a modest increase in VI as VM content
rises to 30 wt%. Figure 5 plots the PVI for the same We have noted in this work and previous papers [1,2]
blends as shown in Figure 4. In this case, there is a that the ASTM 0 VI and 100 VI reference oils are
dramatic difference in the shapes of the curves technically flawed in their definition. In addition, when
compared to Figure 4. The PVI for each blend rises in the VI scale was first defined, the inventors did not
a linear manner with increasing VM content. This is the envision oils having VIs well above 100. However, the
behavior expected for addition of high-VI components advent of VMs and other synthetic base oils soon
to the PAO 4 base oil. Figure 6 plots the DVI versus made it obvious that many newer materials used for
VM treat rate for the same blends as in Figures 4 and lubricating oils were vastly superior in their
5. The DVI also shows the expected behavior of viscosity-temperature properties compared to
increasing value with increasing treat rate. However, Pennsylvania crude oil. Unfortunately, the poor
the increases in DVI are not as large as those definition of the original 100-VI reference oils resulted
measured by the PVI or VI. in very erratic behavior for oils having VIs above 100
[2]. To rectify this problem with the VI scale, the ASTM
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introduced in 1964 a revised VI calculation method, SUMMARY


based on a proposal by Wright [8], for oils with VI
values above 100. This new definition for VI was In this work we examined the effect of adding
termed D2270 and it replaced the previous method, increasing amounts of VII to low viscosity base oils
D567. from API Groups II, III, IV, and V. The results
demonstrated that the ASTM D2270 VI of the final
Figure 7 plots the log(vis40) versus the log(vis100) for blend, in most cases, failed to increase with increasing
the 0-VI and 100-VI reference oils according to ASTM amount of VII. We believe that this effect is mainly due
D2270. Figure 7 also shows the plots for oils having to the inconsistent definition of the ASTM reference
constant VI values above 100, calculated by Wright’s oils. If we use different methods of measuring
method [8]. Because the size of Figure 7 is not large, it viscosity-temperature response, we get completely
is difficult to see that the constant-VI lines are not different results. Both the PVI and DVI show the
linear on a log-log scale. Rather the lines show a bend behavior of increasing VI with increasing amount of
in the region of log(vis100) ≈0.85. This nonlinear VII. The PVI uses a 100-VI reference oil series which is
behavior for all oils above 100 VI is a direct technically superior and more consistent compared to
consequence of the criteria established by ASTM for the ASTM reference series. The DVI is based on an
the revised scale. These criteria included ASTM’s actual measure of the slope of the viscosity-
desire to retain the well-established 0 to 100 VI scale temperature curve for each blend.
in its original form and also to have a smooth transition
in VI calculations for the region immediately above 100 In previous work we have emphasized the importance
VI. On the other hand, Fenske’s proposed 100-VI of having a more rational definition of VI. This is
reference series [7] has a more rational definition. The because the VI has a large economic influence on the
Fenske series has the interesting property that a plot lubricants industry. For example, the API base oil
of log(vis40) versus log(vis100) for the 100-VI series is classifications are determined by VI. The API Group
a straight line [2], unlike the ASTM 100-VI line in ratings are used to determine the amount of
Figure 7. readacross and testing required in very expensive
engine oil qualification programs. The VI has a large
We believe that the nonlinear behavior in Figure 7 for impact on the economics of base oil manufacture.
high-VI oils serves to explain some of the results Because VI has been used as a quality indicator, the
observed in Figures 1 and 4. As the viscosity at 100°C rating also has a large impact on lubricant pricing.
of a blend increases, the amount of viscosity change
needed at 40°C, for a given change in VI, gets Either the PVI or DVI methods are worthy of further
progressively larger. For example, suppose that a consideration by the industry in order to attain a more
finished blend VI is equal to 150. The following rational definition of VI. Each method has its
changes in vis(40) are needed in order to increase the advantages and disadvantages. Perhaps the biggest
VI of the blend from 150 to 155: For a blend with disadvantage for either method is that adoption will
vis(100) = 4 cSt, we need a decrease in vis(40) of result in rating numbers which are different than the
1.55%; for vis(100) = 10 cSt, we need a decrease in current D2270 VI. However, this is exactly why we
vis(40) of 2.55%; for vis(100) = 20 cSt, we need a want to change the rating system – because the
decrease in vis(40) of 3.33% to achieve the same 5 current system is misleading and inconsistent. For
number increase in VI. example, the PVI method will give values below 120

Figure 7 – Log(Vis40) versus Log(vis100) for Lines of Constant ASTM VI

Lines of Constant VI
2.2

2
log10(Vis), cSt @ 40 C

1.8
200 VI
175 VI
1.6
150 VI
125 VI
1.4 100 VI
0 VI

1.2

1
0.5 0.6 0.7 0.8 0.9 1 1.1 1.2 1.3 1.4 1.5
log10(Vis), cSt @ 100 C
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for current Group III base oils [2]. A disadvantage of 4. Kinker, B.G., “Polymethacrylate Viscosity
the DVI is that dynamic viscosities are required for the Modifiers”, Chapter 11 in “Lubricant Additives:
calculation. This will require the use of different Chemistry and Applications”, ed. L.R. Rudnick,
viscometers compared to current, or it will require the Marcel Dekker, (2003).
measurement of density for each blend. A further 5. Roelands, C.J.A., “Correlational Aspects of the
disadvantage of DVI is that it is less discriminating; Viscosity-Temperature-Pressure Relationship of
that is, the VI boost upon adding VII is not as large as Lubricating Oils”, Ph.D. thesis, University of
observed with either the VI or PVI method (Figures 3 & Technology, Delft (1966).
6). The authors caution that, even though VI is widely 6. Roelands,C.J.A., Blok, H. & Vlugter, J.C., “A New
used as a measure of viscosity-temperature behavior, Viscosity-Temperature Criterion for Lubricating
the actual number is based solely on viscosity
Oils”, paper presented at ASME-ASLE
comparisons at 40 and 100°C. For a more meaningful
International Lubrication Conference, Washington,
measure of lubricant viscosity-temperature behavior,
D.C., October 13-16, 1964. ASME Paper No.
the viscosity over a wide range of temperature needs
to be characterized. This is an advantage of the RSI 64-LUB-3.
because it defines the slope of a viscosity-temperature 7. Hersh, R.E., Fisher, E.K. & Fenske, M.R.,
curve. “Viscosity of Petroleum Products: Viscosity
Temperature Characteristics of Pennsylvania
REFERENCES Lubricating Oils”, Ind. Eng. Chem., v27, 1441
(1935).
1. Zakarian, J.A., “The ASTM Viscosity Index and 8. Wright, W.A., “A Proposed Modification of the
Other Systems for Classifying Lubricating Oils”, ASTM Viscosity Index”, Proc. API, v44, III, 535
Nat. Petr. Ref. Assoc. Paper FL-82-85 (1982). (1964)
2. =DNDULDQ - 7KH /LPLWDWLRQV RI WKH 9LVFRVLW\
,QGH[ DQG 3URSRVDOV IRU 2WKHU 0HWKRGV WR 5DWH
9LVFRVLW\7HPSHUDWXUH %HKDYLRU RI /XEULFDWLQJ CONTACT
2LOV 6$( ,QW - )XHOV /XEU   
 GRL For more information, the authors request you contact
3. Zakarian, J.A., “VI – Too Resistant to Change?”, Dr. Jack Zakarian by email at JAZA@Chevron.com .
Lubes’n’Greases, v19, n10, p55 (October, 2013).

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