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JSAE 20159037
SAE 2015-01-2048
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
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
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
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
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
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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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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