(10.1.

598)
Use of Themograviametery as a tool to determine the Volatility of
Lubricating oil: Development of method and its application to
Engine Oils
Anju Sharma, Mukul R. Jain, S. Thakoor, D. Ganguli and K. Ravi
Product and Application Development Centre, Bharat Petroleum Corporation Limited,
A Installation, Fort Sewree Road, Sewree (East), Mumbai 400 015.

Abstract
Environmental and government regulations have ensured that the modern day automotive vehicles
and industries causing emissions reduce emissions. One of the key areas of attention has been the
contribution of these and allied industries to particulate emission levels. The impact of fuel on the
particulate emissions around the world has been the primary focus of research. Even though,
lubricating oil also contributes to the particulate emissions, its cause and effect has not been much
subject of research and has got little attention. The volatility of lubricating oil is the controlling factor,
which determines its consumption and its impact on environment. Oil volatility characteristics to a
certain extent contribute and affect the particulate emission levels. Noack volatility test (ASTM 5800)
is the most preferred method to determine the volatility of the lubricating oil and is followed worldwide.
However, the test provides valuable information on oil volatilities; there are concerns about the test
due to health or safety reasons. The present paper deals with the development of a method to
determine the lubricant oil volatility using, Themograviametery analysis (TGA). The conditions for
testing lubricating oil volatility using TGA have been established for various grades of engine oil,
which include both mineral oil and synthetic base.
The conditions established determine the volatility of the lubricating oil was derived after doing an
exhaustive testing of different type of oils & sample size, heating conditions and heating rates. The
percent loss versus time thermo-grams were generated and compared with the Noack results for the
same lubricating oils. It is observed that the set of conditions established are giving identical results of
volatility as observed by the Noack method for all the samples. To ensure the validity of the developed
method the samples of ASTM round robin and Noack reference were also evaluated. It is observed
that the tests demonstrate identical results as reported and documented by ASTM and Noack.
The conditions established by the present work using TGA for determining the volatility characteristics
can be applied to any lubricating oil. The conditions established ensure the use of TGA as an effective
tool in determining the volatility of the lubricating oils. It also offers the precision of Gas
Chromatography test while simultaneously provide real life conditions of the traditional Noack test.
The new method developed overcomes the shortcoming associated with the traditional Noack test.
Moreover, the test requires very less sample and the test can be performed in a very short time with
excellent accuracy and precision. The developed method can be effectively used by researchers
involved in the area of development of lubricating oils and allied fields. The use of this method will
help researchers to have a better understanding on the volatility characteristics of lubricating oils. This
in turn will help in understanding the oil consumption patterns and its impact on the environment.

Introduction
Performance and environmental issues are foremost concerns that have led to continued new efforts
in developing of lubricating oils so as to reduce the particulate emissions from vehicular internal
combustion engines. One important change is a shift to oils with lesser oil volatility and having lower
viscosity to reduce engine friction and thereby improve fuel economy [1]. Loss of oil due to volatility
increases oil consumption as well as evaporative emissions into the environment. The evaporation
loss is of particular importance in engine lubrication. Regions in an engine where oil is exposed to
high temperatures may lead to significant portions of oil to evaporate. Evaporation may contribute to
oil consumption in an engine and can lead to a change in the properties of oil. Researchers in the

automotive and petroleum industries have studied the effects of oil volatility on engine emissions and
oil consumption over the past decade. It is generally accepted that reducing oil volatility should have a
positive impact on emissions and consumption [2]. As emissions and consumption levels are both
being reduced for environmental concerns, engine oil volatility has become an increasingly more
important specification for engine oils. Many engine manufacturers specify a maximum allowable
evaporation loss.
The standard test for assessing oil volatility has been the Noack and Gas chromatographic
techniques. This test exposes the oil to relatively high temperatures in presence of air and simulates
or approximates the conditions in the area around the top piston rings of engines [3]. It is believed that
the majority of the emissions are a result of exposure of the oil to the piston ring region. While the
Noack test does provide valuable information on oil volatilities, there are concerns about the test due
to health or safety reasons. These stem around the fact that the Noack test utilizes a metal cup, for
heating the oil surface of which is exposed to user, further the quantity used is much larger than the
one used in TGA. The Noack test is also imprecise, labor intensive and time consuming to conduct.
Further it can monitor only the total loss of weight after an hour of the test and does not indicate what
changes occurred to the sample during the test. All of these factors contribute to the need for the
development of a safer, less time-consuming test to assess oil volatility. The other common test is the
use of gas chromatography (GC) to indirectly assess oil volatility. The GC method has the oil
absorbed onto a packed column in an inert atmosphere (helium or nitrogen). The column is then
heated to 600C and the de-absorption is then monitored. The oil volatility is defined as the amount of
oil desorbed from the column at a temperature of 371C, relative to the total oil desorbed or relative to
a known quantity of some internal standard. The advantage of the GC method is that it is safer and
less hazardous than the traditional Noack test. The disadvantages are that the GC test is conducted
in an inert atmosphere, as compared to air, and does not truly simulate the conditions to which the oil
would be subjected to in real life conditions [4].
It was desired to have a test that would combine the real life conditions used in the traditional Noack
test with the safety and precision of the GC test. One such a method was developed by E.F. de Paz
and C.B. Sneyd and utilizes thermo-gravimetric analysis, TGA and the test is known as the TGA
Noack test [5, 6]. The major disadvantage of the method is that there are no clear instructions on the
conditions related to heating the sample to the specified temperature. The sample weights indicated
do not hold for the testing of all base oils and lubricants. The present paper deals with the
development of a method to determine the lubricant oil volatility using, Themograviametery analysis
(TGA). The conditions for testing lubricating oil volatility using TGA have been established for various
grades of engine oil, which include both mineral oil and synthetic base.
The objectives of this study were to use TGA to test the volatility of various lubricants in air.

Experimental
The volatility of the samples was evaluated by two methods as mentioned below:
Evaporation Loss of Lubricating Oils by Noack Method (ASTM D5800-96):
The Noack test conditions, in particular, seems to be recognized as being more representative of
those experienced by oils in engines during operation. The Noack volatility of oil is defined as the
weight loss of the oil when it is held under isothermal conditions at 250C for a period of 1 hour under
a constant flow of air.
TGA Noack Test (ASTM D 6375)
The TGA Noack test offers the precision and safety of the GC test while simultaneously providing real
life conditions (exposure to air at an elevated temperature) of the traditional Noack test. In addition,
the TGA Noack method is fast and easy to perform and provides an excellent means of characterizing
oil volatilities.
The tests were carried on different types of fluids. This included base oils as well as finished engine
oil formulations and reference oils. Base fluids were obtained from commercial sources. Mineral oil
base fluids were selected to represent API groups II and III and synthetic polyalphaolefin base fluids
were selected to represent API group IV. ASTM round robin samples and commercially procured
Noack volatility standard was used as reference oil. The details of the samples used are given in
Table 1.

Results and Discussion

An understanding of the relationships between the molecular structure of lubricant base fluids and the
properties and performance of these materials is directly related to reducing oil volatility. Lubricants
degrade thermally when components boil off due to volatilization or by the changes in fluid structure at
elevated temperatures. Comparison of the volatilization profiles of base fluids can give useful volatility
information about each fluid. Studies have reported that typical operating temperatures for bearings,
gears and piston rings rarely exceed 150C [7]. The automotive industry is designing for more fuelefficient and low emission vehicles, which have resulted in engines running at much higher
temperatures. This is partly attributed to industrys use of smaller engines and smaller oil sumps to
reduce weight. Additionally, exhaust gas recirculation (EGR) has become more popular and
contributes to elevated temperatures potentially exceeding the 150C temperature. Lubricant volatility
restricts the maximum operating temperatures of these components [8, 9]. A study of lubricant fluid
thermal and oxidative stabilities will need to address this issue. Based on reported temperatures in
combustions engines, it is likely that lubricants are exposed to temperatures above 150C. It is
possible that for short periods of times, lubricants will experience temperatures as high as 480C.
However, components of these fluids have been reported to boil off at temperatures even below
150C [10, 11].
Table 1: Noack volatility of different oil samples as evaluated by ASTM D 6375,
ASTM D 5800 and modified ASTM D 6375.
Sample
Identity

Sample
Description

KV
@100C

VI

ASTM LU509
ASTM Round Robin Sample 11.94
- 17.28 (Robust mean: 14.61)
CRM W4520002
ISL Noack CRM (16.09 - 18.19)
100 N (MNC)
220 N (MNC)
150 N (INDEGENIOUS)
PAO 4-GRP IV
PAO 6-GRP IV
Lube oil A - SAE 10W 30 (GRP III)
Lube oil B - SAE 10W 30 (GRP II)
Lube oil C - SAE 10W 30 (GRP II)
Lube oil D - SAE 10W 30 (GRP III)
Lube oil E - SAE 10W 30
(GRP II + III)
Lube oil F Synthetic

10.56

136

13.06

13.35

NA

NA

17.14

17.75

3.99
6.56
5.01
4.01
5.78
11
11.1
11.3
11.2
11.1

107
103
110
124
143
146
148
148
150
148

23.66
9.3
22.50
13.6
8.4
7.12
15.95
11.06
7.18
10.28

24.34
9.1
22.33
13.82
8.82
7.43
16.00
11.15
7.26
10.96

11.5

158

8.22

8.82

B
C
D
E
F
G
H
I
J
K
L
M

Noack Volatility
Noack
% by ASTM 5800 Volatility
by TGA*

*as per new conditions established.

Lubricants with continuous exposure to elevated temperatures, as seen in combustion engines, break
down, decreasing their life expectancy. Deposits from these fluids cause increases in stresses and
wear, reducing the performance of the engine. These high temperatures are sufficient to break
covalent bonds and permit reactions that would not occur at lower temperatures. Volatility of an oil to
a certain extent decides the performance of oil when it is in use. In the present study we tool different
oils to develop a method to determine the volatility of wide range of oils. The details of the oil used are
shown in Table 1.
The results of volatility of the oil sample A, B, E and I are shown in Table 2. The results were obtained
by both the methods. The TGA thermo grams of the same samples are shown in Figure 1. This was
done in order confirm and validate the outcome of results by both the methods. It can be observed
that there is an appreciable difference in the volatility measurements by both the methods, i.e. by the
Noack method and the TGA Noack method. Several runs were done to reconfirm this. This clearly
indicated that the TGA Noack conditions employed for the determination of volatility were not

appropriate for the samples tested. Thus, several runs were done on different kinds of samples and
new set of conditions were established on the TGA. The conditions were established varying sample
mass, flow rate of air, different heating rates and isothermal temperatures. The results are shown in
Table 2 and the thermo grams are shown in Figure 2 and 3. The volatility for standard samples (A&B),
finished engine oils (H, I, J, K and L) and base oils both synthetic and mineral based (C, D, E, F, G
&M) were determined by the new conditions established. It can be observed that the volatility
determined for the broad range of samples and standards are comparable with the results as obtained
by the Noack ASTM D5800-96 method. This proves the validity of the established conditions to
determine volatility of different oils. The new set of conditions established can be used for different
kind of oil for which volatility has to be determined.
The recommended conditions for the evaluation of volatility by TGA are:

Sample mass of 23 to 28 mg in a 6 mm diameter Aluminum vial

Air purge at a flow rate of 150 mL/min
Heat sample from 70 to 240 C at 65 C/min
Heat sample from 240 to 249 C at 10 C/min
Hold sample at 249 C for 15 minute isothermal period
Measure mass loss (%) at certain time interval, Noack Reference Time, as specified by analyzing
a Noack reference oil (NRO)
We have used ISL Noack CRM (ASTM 5800, method B). Sample ID W4520002, Noack
Evaporation 17.14%, Limits 17.14 (mean) +/- 2 x 0.53 (RDS);Control Limits : 16.09 18.19
Menu
Table 2: Noack volatility of different oil samples as evaluated by ASTM D 6375,
ASTM D 5800 and modified ASTM D 6375.
Sample
Identity

Sample
Description

ASTM LU509
ASTM Round Robin Sample
11.94 - 17.28
(Robust mean: 14.61)
CRM W4520002
ISL Noack CRM
(16.09 - 18.19)
150 N
(INDEGENIOUS)
Lube oil B - SAE 10W 30
(GRP II)

B
E
I

*as per new conditions established.

Noack Volatility Noack Volatility

Noack
by TGA as per by ASTM D 5800 Volatility by
ASTM D 6375 (%)
(%)
TGA*(%)
10.85
13.06
13.35

16.99

17.14

17.75

18.64

22.5

22.33

13.56

15.5

16.00

Figure 1: Volatility of samples A, B, E and I F and G as determined ASTM D 6375

ASTM conditions: Sample weight: M=350(internal diameter)3 for our vial it would have been ~75 mg
Heating rates: 100C to 220 and 10C from 220 to 249.
Time above 7 min.

Figure 2: Volatility values as determined by new set of conditions established on TGA

Figure 3: Volatility of samples H, I, J, K, L, M and B as determined by the new conditions

established.

Conclusions
The results of these studies indicate the importance of using more than one test to measure lubricant
volatility. The NOACK test is really an oxidation test, which is a sufficient method of measuring
volatility for specific applications. The new set of conditions established can be used for determining
the volatility of different kind of oils. This will not only help researchers in this field but also help
formulators to develop products effectively.

Acknowledgement
The authors are thankful to the management of Bharat Petroleum Corporation Limited for giving
permission to present this work.

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