Mat.-wiss. u. Werkstofftech. 2013, 44, No. 5 DOI 10.1002/mawe.

201300143 403

Theoretical approach to a better understanding of gelation

in the framework of petroleum industry: role played by
different parameters
Theoretischer Ansatz f
r ein besseres Verstndnis der Gelierung in der
Erdlindustrie: ber die Rolle der verschiedenen Parameter

J. A. Maroto-Centeno1, T. P
rez-Guti
rrez2, M. Quesada-P
rez1

Gelation due to the precipitation of paraffins in petroleum oils is a billion dollar problem in the
petroleum industry. The most widely known example in this field is the gelation of crude oil dur-
ing transportation through sub-sea pipelines, which in some cases has caused important reme-
diation cost of pipelines blockages. In the case of lubricant oils, gelation is a latent problem
from the massive failure in automotive engines that took place in North America during the
winter of 1980-81. In this framework, this work uses a recently developed theoretical survey
which has shed light on the physical meaning of the gelation index, that is, the main parameter
involved in test ASTM D 5133. This test is commonly used in the petroleum industry for the eval-
uation of gelation tendency of engine oils at low temperatures. This work analyzes the role
played by different parameters (and particularly the induction period and supersaturation
ratio) in the theoretical evaluation of the gelation index. In spite of the simplifications used in
the theory a qualitative agreement is found when comparing with experimental data, which
opens the possibility (after necessary refinements) of a fully predictive theory for nucleation
which would be very useful for the petroleum industry.
Keywords: Gelation / gelation index / lubricant oils / homogeneous nucleation theory / pour point depres-
sants /

Gelierung durch Paraffinausscheidung in Mineral
len bereitet der Erd
lindustrie Probleme in

Milliardenh
he. Das bekannteste Beispiel hierfr ist die Gelierung von Roh
l whrend des Trans-
ports durch Unterseepipelines. Dieses Problem hat in einigen Fllen erhebliche Kosten fr die Sa-
nierung verstopfter Pipelines verursacht. Im Falle von Schmier
len ist die Gelierung ein latentes
Problem, etwa beim massiven Versagen von Automotoren in Nordamerika, das im Winter 1980-
81 in besonderem Maße auftrat. Vor diesem Hintergrund nutzt die vorliegende Studie die Ergeb-
nisse einer theoretischen Untersuchung, welche die physikalische Bedeutung des Gelierungsin-
dexes, also des wichtigsten Parameters im Test nach ASTM D 5133, analysiert. Der erwhnte Test
kommt in der Erd
lindustrie bei der Bewertung der Gelierungstendenz von Motor
len bei Nied-
rigtemperaturen hufig zum Einsatz. Die vorliegende Studie analysiert die Rolle der verschiede-
nen Parameter (sowie insbesondere der Induktionszeit und des bersttigungsgrads) in der theo-
retischen Bewertung des Gelierungsindexes. Trotz der in der Theorie angesetzten Vereinfachun-
gen kommt es bei einem Vergleich mit den Messdaten zu einer qualitativen bereinstimmung
und diese bietet (nach notwendigen Weiterentwicklungen) die M
glichkeit einer absoluten theo-
retischen Vorhersage fr den Gelierungsprozessbeginn. Letztere wre fr die Erd
lindustrie von
großem Nutzen.
Schl
sselwrter: Gelierung / Gelierungsindex / Schmier
le / homogene Bildungstheorie / Stockpunktver-
besserer /

1 Introduction paraffin molecules precipitate out of the solution, crystallize and

form a gel. The gelation and concomitant deposition of these par-
When the temperature of a solution of paraffins in oil is dropped affin gels in crude oil pipelines poses a major transportation
below the cloud point temperature, the high molecular weight n- problem by reducing the flow efficiency [1]. According to the US

1
Group of Physics and Chemistry of Linares Department of Physics,
Technical College of Linares (University of Jan), Jan, Spain
2
Technology Unit., Repsol, Mstoles, Madrid, Spain
Corresponding author: J. A. Maroto-Centeno, Department of Physics,
Technical College of Linares University of Jan) C/ Alfonso X el Sabio, 28,
23700 Linares, Jan, Spain
E-mail: jamaroto@ujaen.es

i 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.wiley-vch.de/home/muw

404 J. A. Maroto-Centeno et al.
Department of Energy, remediation of pipeline blockages in
water depths of about 400 m can cost 1 million dollar/mile. Over-
all, the paraffin gelation and deposition problem is a billion dol-
lar problem in the petroleum industry. In the case of lubricant
oils, the formation of wax crystals at low temperatures due to
poor solubility of paraffins profoundly affects the oil rheology.
Under cooling both in quiescent and non-quiescent conditions
wax crystals nucleate and grow to form macroscopic structures
that may cause yield stress. This quantity is a measure of the
shear stress required to initiate flow being zero for all Newtonian
fluids and many non-Newtonian fluids. Nevertheless, yield stress
may take values different from zero due, for example, to gelation
resulting from structures formed from wax crystals characterized
by a predominantly elastic behavior. Today, the rapidly increasing
use of mineral base oils having considerably higher paraffinic
content than past solvent-refined base oils calls for careful identi-
fication of gelation tendency because gelation can produce a fail-
ure in the mechanism of engines called air-binding, that is, the
uptake of air into the oil pump rather than lubricant.
In the late 1970s, the low temperature pumpability of engine
oils was extensively studied under the auspicies of ASTM. The
result of this effort was a test method using the Mini Rotary Visc-
ometer (MRV), which was published in 1979 as ASTM D 3829.
Unfortunately, just after the new method had been developed
and added to the SAE J300 viscosity classification, a lot of engines
failed in North America (area of Sioux Falls) and Europe. Investi-
gation of the temperatures prevailing in the area of Sioux Falls
showed that the cooling rate to which the vehicles had been
exposed there differed significantly from that used in the ASTM
D 3829 [2]. The cooling profile was much slower, thus allowing
the development of wax structures. As a result of this unexpected
problem, new efforts to develop a more suitable bench test were
carried out, with two new methods competing to resolve it. On
the one hand, the Mini Rotary Viscometer test ASTM D 4684 was
developed in 1987 to simulate what happened in Sioux Falls [3].
It is based on the assumption that the formation of waxy struc-
tures takes place predominantly between – 5 8C and – 20 8C, a
temperature range which includes the cloud points of most
engine oils. Above – 50 8C, most of the paraffins are still soluble
in the oils, and below – 20 8C, most of them have come out of sol-
ution. The new TP-1 cycle [4] includes a cooling rate of 0.5 8C per
hour between – 5 8C and – 8 8C, which is then reduced to 0.33 8C
per hour down to – 20 8C. Below – 20 8C, the cooling rate is set to
2.5 8C per hour. Therefore, the TP-1 cycle does not promote gel
formation if it takes place above – 5 8C or below – 20 8C. On the
other hand, another test was adopted in 1990 for measuring
pumpability relevant low temperature properties of oils: the
Scanning Brookfield test (SBT), ASTM D 5133 [5]. Its use and
application to reference oils has been extensively described in the
literature [6 – 8]. The technique is based on an earlier observation
in low-temperature capillary viscometer that latent gelation
response of oil at low temperatures could often be induced by
shearing the fluid very slowly and laminarly. The SBT measures
viscosity continuously at a constant shear rate of 2 s – 1as the oil is
cooled at a constant rate of 1 8C per hour from – 5 to – 45 8C.
Selby has suggested that in those mineral oil lubricants which
exhibit an abrupt increase in viscosity over a narrow temperature
range the strength of the viscosity increase positively correlated
i 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Mat.-wiss. u. Werkstofftech. 2013, 44, No. 5
with the severity of gelation or gel strength. He established the
term “gelation index”.
It must be underlined that both ASTM methods show evident
advantages and disadvantages. ASTM D 4684 method does not
permit the evaluation of the temperature at which gelation, if any,
takes place; also, this method reports a poor reproducibility in the
evaluation of yield stress which causes important differences
between measurements carried out for different laboratories [9].
With regard to ASTM D 5133 there are still important doubts
about both the physical meaning and utility associated to the
gelation index, which is the main parameter provided by this test.
Recently [10] it has found no correlation between gelation index
and yield stress (parameter with a physical meaning closely
related to a gelation phenomena), in apparent contradiction to
Selby work based on the study of a number of reference Oils
(PRO) used in an industry wide study in the mid-1980's [11].
Also, this study has come to the conclusion that the gelation index
from ASTM D 1533 is not an adequate relative measure of gelat-
ion in mineral oils. Nowadays, test ASTM D 4684 is incorporated
in the SAE J300 viscosity classification and both test methods are
part of ILSAC GF-4 and GF-5 standards. Obviously, the simulta-
neous use of two test methods (which could not be correlated) to
evaluate the same phenomena (gelation) would have the risk of
reducing the range of lubricants available to the formulator.
This work uses a recently developed theoretical survey which
has shed light on the physical meaning of the gelation index, that
is, the main parameter involved in test ASTM D 5133 [12]. The
inclusion of the induction period in the equation for the nuclea-
tion rate and the additional use of the Bachelor equation permit-
ted finding a mathematical expression that provides the gelation
index of an engine lubricant versus the temperature. Neverthe-
less, the evaluation procedure is not simple and the development
of a C++ program was necessary in order to obtain quantitative
results. It was proven that the pulse-shaped region of the gelation
curve can be explained as the relief of supersaturation of the solu-
tion, that is, a nucleation process that finishes when the satura-
tion ratio takes a value equal to 1. Also it was shown that the max-
imum displayed by this pulse-shaped region (gelation index) is
due to two competitive effects: on the one hand, the decrease of
the nucleation rate with the decrease in the temperature and, on
the other hand, the increase of the radius of the critical cluster
with the decrease of the temperature. This work enlarges this ini-
tial survey by analyzing the role played by different parameters in
the evaluation of both the gelation index and the gelation temper-
ature of a lubricant oil. In spite of the simplifications carried out
in the development of the formalism, qualitative agreement is
found when comparing with experimental data. As conclusion,
the increment in the content of pour point depressant (PPD) of a
lubricant oil can be successfully modeled from the theoretical
point of view as a simultaneous increment of both the induction
time and the temperature interval of relief of supersaturation in
the solution.
2 Materials
The results shown in this paper are part of a wide research pro-
ject carried out by Repsol YPF in cooperation with the Research
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Mat.-wiss. u. Werkstofftech. 2013, 44, No. 5 Theoretical approach to a better understanding of gelation in the framework of petroleum industry
Group of Physics and Chemistry of Linares (University of Ja
n,
Spain). The experimental measurements were carried out in the
Repsol advanced laboratory of lubricants, which is placed in the
Repsol Centre at Mstoles (Madrid, Spain). The rheology of eight
lubricants oils has been evaluated by means of the tests ASTM D
5133 and ASTM D 4684. These eight lubricant oils were selected
from a group of commercial base oils commonly used by Repsol
YPF. In some cases a standard pour point depressant additive
(PPD) was used in order to change the rheological properties of
the oils at low temperatures.
3 Theoretical foundation
3.1 Homogeneous nucleation theory
Wax precipitation is a particular case of crystallization, which is
the process of formation of solid crystals precipitating from a sol-
ution. The most important requirement for crystallization is
supersaturation, which is the driving force for nucleation to
occur. Nucleation is the first stage in the crystallization process.
Simply defined, it represents the birth of a new crystal. Primary
nucleation is believed to be initiated in a series of bimolecular
collisions that forms an aggregate of a small number of mole-
cules (embryos) of the dissolved material. Embryos below a crit-
ical cluster size (rc), are unstable and may disintegrate, whereas
embryos that exceed this critical cluster size will become stable
nuclei and will grow.
The classical nucleation theory states that the change in the
Gibbs free energy (DG) required to form a nucleus of radius r is
given by the following equation [13, 14]:
4pr 3
DGðrÞ ¼
kB T ln b þ 4pcr 2 ð1Þ
3X
where X is the volume of a molecule inside the crystal, c is the
solid-liquid interfacial energy, kB is the Boltzmann constant, T is
the absolute temperature and b is the saturation ratio, which is
given by:
C gelation curve
b¼ ð2Þ
Ceq
where C is the solute concentration and Ceq the equilibrium solu-
bility of the solute at the temperature and pressure of the solu-
tion.
The first term in Eq. (1) is a bulk term which is negative if b > 1
and decreases as r3, and the second term is a surface term which
is positive and increases as r2. As result of both the surface and
volume terms DG passes through a maximum, denoted as DGmax.
Taking the derivative with respect to r and setting this equal to
zero allows calculation of rc. This value of rc is called the critical
cluster size:
2Xc
rc ¼ ð3Þ
kB T ln b
By replacing this value of rc into Eq. (1) the activation energy
necessary to form a nucleus of the critical size, DGmax , is
obtained:
16pX2 c3
DGmax ¼ ð4Þ
3½kB T ln b 2
i 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
405
This equation shows the dependence of DGmax on the satura-
tion ratio ß. As ß increases, both the barrier for the critical activa-
tion energy (DGmax) and the value of the critical size decrease.
Eventually, as the degree of supersaturation increases (that is, b
is large enough), the activation energy becomes so low that spon-
taneous and rapid nucleation occurs.
The rate of nucleation, J, e. g., the number of nuclei formed
per unit time per unit volume, can be expressed in the form of
the Arrhenius reaction velocity equation commonly used for the
rate of a thermally activated process [15, 16]:
J¼Jmax expð
DGmax =kB TÞ ð5Þ
where Jmax is the pre exponential factor.
A period of time usually elapses between the achievement of
supersaturation and the appearance of crystals. This time lag,
,
named as induction period’, is considerably influenced by the
level of supersaturation, state of agitation, presence of impur-
ities, viscosity, etc. The existence of an induction period in a
supersaturated system is contrary to expectations from the classi-
cal theory of homogeneous nucleation, which assumes ideal
steady-state conditions and predicts immediate nucleation once
supersaturation is achieved. The induction period may therefore
be considered as being made up of several parts [16]. For exam-
,
ple, a certain relaxation time’, tr, is required for this system to
achieve a quasisteady-state distribution of molecular clusters.
Time is also required for the formation of a stable nucleus, tn,
and then for the nucleus to grow to a detectable size, tg. So the
induction period, tind, may be written as:

ind ¼ tr þ tn þ tg ð6Þ
The final expression for the nucleation rate that includes the
nucleation period takes the form:

ind
J¼Jmax expð
Þ expð
DGmax =kB TÞ ð7Þ
t
where t is the time.
3.2 Equations for predicting the main features of the
The Scanning Broofield test (SBT) provides the gelation curve of
an engine oil. The McCoull-Walther-Wright (MWW) is an empir-
ical equation that has been widely used for the description of the
variation in viscosity as a function of temperature in engine oils
([17] – [19]) and it takes the form:
LnLnðTÞ ¼ a
GLnT ð8Þ
where g is the viscosity, T the absolute temperature and both a
and G are constants. More specifically, the positive constant G is
called gelation value in the context of the Scanning Brookfield
Technique [20]. The MWW equation successfully reproduces the
behaviour of engine oils in the Newtonian regime. In fact, this
equation forms the basis for the ASTM viscosity-chart, one of the
most popularly methods used to determine the viscosity of oils
[21]. With regard to the behaviour of engine oils at low tempera-
tures, Selby and McGeehan have proven experimentally that the
MWW equation fits the variation of the viscosity with tempera-
ture of an engine oil at temperatures lower than the gelation
index temperature, that is, for an oil which is supposed to be
undergoing a crystal growth process [22].
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406 J. A. Maroto-Centeno et al.
Figure 1. Gelation curve for a gelating oil.
Bild 1. Gelierungskurve fr ein l beim Ausgelieren.
The MWW equation is incorporated in the software of the
Scanning Brookfield Viscometer in order to draw the gelation
curve and evaluate some important parameters such as gelation
index and gelation index temperature. In a gelation curve the
incremental derivative of the MWW equation (that is, G in Eq.
(8)) is plotted as a function of the temperature. Figure 1 shows
the main features of the gelation curve for a gelating oil [23]. This
system behaves like a perfect Newtonian oil in a wide interval of
temperatures in which G takes a constant value (zone I). It exhib-
its a quick (pulse-shaped) change of G values at lower tempera-
tures (zone II). This behaviour has been traditionally attributed
(without further proof) to the appearance of a nucleation pro-
cess.
On the other hand, Tsat is commonly known as saturation tem-
perature and it is the onset temperature for nucleation [24]. The
maximum gelation value in zone II is called the gelation index,
GI, and the temperature for the gelation index is commonly
known gelation index temperature, TG. On the other hand, a typi-
cal gelating oil usually takes a new constant value of G for a fur-
ther decrease in temperature (zone III).
Recently, it has been developed a theoretical survey that sheds
light on the physical meaning of the gelation index, that is, the
main parameter involved in the test ASTM D 5133 [12]. More
specifically, it was proven that the pulse-shaped region of the
gelation curve (zone II) can be explained as the relief of supersa-
turation of the solution, that is, a nucleation process that finishes
when the saturation ratio takes a value equal to 1. The main fea-
tures of this theoretical survey are shown in this section.
First of all, we assume that during the nucleation process an
oil behaves like a polydisperse suspension containing spherical
particles of paraffin with radius rc which depends on the satura-
tion ratio (see Eq. (3)) and, therefore, on the temperature. In this
framework, the rheological behavior of a dilute suspension of
hard-spheres (with no interactions) in which the hydrodynamic
interaction between the particles is taken into account is
described by the Bachelor equation [25]:
rel ðTÞ ¼ 1 þ 2:5uðTÞ þ 6:2uðTÞ2 ð9Þ
i 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Mat.-wiss. u. Werkstofftech. 2013, 44, No. 5
where grel is the relative viscosity of the suspension at tempera-
ture T (that is, the absolute viscosity of the suspension, gs, divided
by the viscosity of the solvent at the same temperature, go) and
u (T) is the volume concentration of solid paraffins at tempera-
ture T. It is important to take into account that the Bachelor equa-
tion can be used for u = 0.2.
The following expression permits evaluating the gelation value
of an engine oil, G, in the zone II of the gelation curve. It can be
obtained by applying the chain rule to the double logarithm of gs
in Eq. (9):
dLnLns
G¼

dLnT


du 2:5 þ 12:4u
GIo expðao
GIo LnTÞ
T dT 1 þ 2:5u þ 6:2u2
¼ ð10Þ
expðao
GIo LnTÞ þ Lnð1 þ 2:5u þ 6:2u2 Þ
where ao and GIo are the parameters that characterizes the oil in
region I (Newtonian behavior) as described by Eq. (8).
In order to evaluate both u (T) and du/dT in Eq. (10) we have
assumed that nucleation is the only process involved in wax pre-
cipitation in region II. Therefore, we have neglected the role of
growth in this region due to the impossibility to evaluate it theo-
retically. Anyway, it must be underlined that this theoretical sur-
vey can be considered a semi-quantitative description of the
gelation curve (and, concretely, of region II) but not a fully pre-
dictive procedure, which would require further improvements.
By assuming the previous hypothesis it can be easily found the
following relationship between du/dT and the rate of nucleation
J:
du
¼ b
1 Vc J ð11Þ
dT
where b is the cooling rate used in the experiments (expressed in
K N s – 1) and Vc is the volume of a sphere of radius rc.
At viewing Eq. (11) it is evident that u(T) can be obtained by
evaluating the following integral:
ZTsat
uðTÞ ¼ b
1 Vc JdT ð12Þ
T
As can be seen by reviewing Eqs. (3), (5), (11) and (12), the eval-
uation of Eq. (10) is not simple at all, which encouraged us to
develop a C++ program in order to obtain quantitative results.
4 Results and Discussion
Figure 2 shows the experimental gelation curve for oil D5 (20W/
50) which was obtained by applying test ASTM D 5133. A stand-
ard pour point depressant additive was used in order to change
the rheological properties of the oil at low temperatures. On the
other hand, Table 1 shows important parameters that character-
ize this oil. In the light of Fig. 2 it is evident the huge influence
played by the pour point depressant additive in the rheology of
the oil. Concretely, it is patent that both the gelation temperature
and the gelation index decrease with the increment of pour point
depressant additive percentage. On the other hand Table 1 shows
that the cloud point of this oil takes a value of – 7 8C which is
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Mat.-wiss. u. Werkstofftech. 2013, 44, No. 5 Theoretical approach to a better understanding of gelation in the framework of petroleum industry
Figure 2. Content of PPD in oil D5 (20W/50). ( –– ) 0% PPD; (- - -) 0.2%
PPD; ( N N N ) 0.5% PPD.
Bild 2. Inhalt des PPD in l D5 (20W/50). ( –– ) 0% PPD; (- - -) 0,2%
PPD; ( N N N ) 0,5% PPD.
Table 1. Rheological parameters that characterize oil D5.
Tabelle 1. Rheologische Parameter fr das l D5.
% PPD Gelation Index Cloud Point ( 8C) Pour Point ( 8C)
0 27.5@ – 7.8 8C –7 –9
0.2 11.5@ – 9.9 8C –7 – 27
0.5 8.6@ – 10.6 –7 – 30
independent of the pour point depressant additive percentage. If
we have a look at Fig. 1 we will notice that the pour point, which
is the temperature below which the oil exhibits a cloudy appear-
ance, is not equivalent to the gelation temperature (TG) but to the
saturation temperature (Tsat) because Tsat is understood as the
onset temperature for nucleation. Despite the fact that the soft-
ware of the Scanning Brookfield Viscometer reports the temper-
ature TG but not Tsat a simple visual inspection of Fig. 2 shows
that Tsat takes a value, independent of the% pour point depressant
additive, very close to – 7 8C.
Figure 3 shows the viscosity versus the Celsius temperature for
the oil D5. In the light of Fig. 3 is evident that the measurements
provided by the SBT and the Mini Rotary are rather different.
Concretely, the Mini Rotary reports viscosities lower than the
SBT in absence of yield stress and larger for measured values of
yield stress. The first behaviour mentioned above has been
reported in the literature [23] and it has been attributed to the
effect of the shearing on the rheology of the oil [20]. On the other
hand, it is evident that the continuous shearing of the oil carried
out in the scanning slows down the formation of the volume-
spanning crystal network which entrains the remaining liquid
oil among the crystals. This late stage of the gel formation is not
prevented in the Mini Rotari, due to the cooling of the oil is car-
ried out in quiescent conditions.
As conclusion, when the gel is completely formed the Mini
Rotary measures a high viscosity and a yield Stress different to
zero while the scanning slows down or prevents the oil to reach
i 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
407
Figure 3. Oil D5 (20W/50). ( –– ) Viscosity (SBT) 0.5% PPD; (- - -) Vis-
cosity (SBT) 0.2% PPD; ( N N N ) Viscosity (SBT) 0% PPD; (f) Viscosity
(Mini Rotary) 0.5% PPD. (F) Viscosity (Mini Rotary) 0.2% PPD; (h) Vis-
cosity (Mini Rotary) 0% PPD.
Bild 3. l D5 (20W/50). ( –– )Viskositt (SBT) 0,5% PPD; (- - -) Viskosi-
tt (SBT) 0,2% PPD; ( N N N ) Viskositt (SBT) 0% PPD; (f) Viskositt
(Mini Rotary) 0,5% PPD. (F) Viskositt (Mini Rotary) 0,2% PPD; (h) Vis-
kositt (Mini Rotary) 0% PPD.
the late stage of the gel formation and reports a viscosity lower
that one reported by the Mini Rotary. As consequence, the SBT
(at its normal way of running) could not be suitable for evaluat-
ing the yield stress of a gelating oil. From the point of view of the
standard SAE J300 only the oil D5 containing 0.5% pour point
depressant additive is valid for commercial use, which evidences
the utility of pour point depressants to optimize the behaviour of
lubricant oils at low temperatures.
We used the theoretical approach put forward in a previous
section in order to find out if the homogeneous nucleation theory
is useful to fit the gelation curve of a gelating oil which contains
different percentages of pour point depressant additive. We have
supposed a nucleation process in which the supersaturation ratio
decreases linearly from 1.2 at 266 K (the saturation temperature
of oil D5) up to 1.0 at 262 K. Widths of 3 – 5 K for zone II of gelat-
ion curve have been often reported in the literature [26]. A value
of 1.2 for b at nucleation for paraffins has been experimentally
reported [27]. On the other hand, we have carried out an exten-
sive search in the literature in order to evaluate the different
parameters involved in Eq. (3). We have taken, for paraffins, c =
7 N 10 – 4 J N m – 2 [27], X = 1.92 N 10 – 28 m3 N molec – 1 which has been
obtained from the estimation of effective diameters for paraffins
[28].
Figure 4 shows zone II of the gelation curve which has been
drawn by using three different values of the induction time: 60 s,
500 s and 1500 s. In the evaluation of Eqs. (11) and (12) we took a
value for b of 1/3600 K N s – 1 which is usually used during the
experiments carried out in the framework of test ASTM D 5133.
We used a value for Jmax of 1.6 N 1022 m – 3s – 1 which yielded values
for GI similar to that experimentally reported by the test (from
some units up to some dozens). In the case of the Scanning
Brookfield viscometer, Jmax must be understood as the nucleation
rate (and cluster radius associated) at which the change of viscos-
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408 J. A. Maroto-Centeno et al.
Figure 4. Gelation value versus the Celsius temperature. ( –– ) sind = 60
s; (- - -) sind = 500 s; ( N N N ) sind = 1500 s.
Bild 4. Gelierungswerte in Abhngigkeit von der Celsius-Temperatur.
( –– ) sind = 60 s; (- - -) sind = 500 s; N N N ) sind = 1500 s.
Figure 5. Gelation value versus the Celsius temperature at constant
value of sind = 60 s. ( –– ) tf = – 11 8C; (- - -) tf = – 7 8C – 4 (1 + 0.02) 8C;
( N N N ) tf = – 7 8C – 4 (1 + 0.05) 8C.
Bild 5. Gelierungswerte in Abhngigkeit von der Celsius-Temperatur
auf einem konstanten Wert von sind = 60 s. ( –– ) tf = – 11 8C; (- - -) tf =
– 7 8C – 4 (1 + 0,02) 8C; ( N N N ) tf = – 7 8C – 4(1 + 0,05) 8C.
ity due to the nucleation process is recorded by the viscometer.
Figure 4 shows a decrease of the gelation index with the incre-
ment of the induction time. Nevertheless, the gelation tempera-
ture remains constant and the induction time does not affect the
width of zone II of the gelation curve. As consequence, the mere
increment of the induction time is not equivalent to an incre-
ment in the content of pour point depressant additive, Fig. 2.
Anyway, it is logical to assume an increment of the induction
time due to the action mechanism played by the pour point
depressant additive in the crystal morphology [29]. More specifi-
cally, this work proved that the composition and weight of the
i 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Mat.-wiss. u. Werkstofftech. 2013, 44, No. 5
Figure 6. Gelation value versus the Celsius temperature. ( –– ) sind = 60
s and tf = – 11 8C; (- - -) sind = 500 s and tf = – 7 8C – 4 (1 + 0.02);
( N N N ) sind = 1500 s and tf = – 7 8C – 4(1 + 0.05) 8C.
Bild 6. Gelierungswerte in Abhngigkeit von der Celsius-Temperatur.
( –– ) sind = 60 s and tf = – 11 8C; (- - -) sind = 500 s and tf = – 7 8C – 4(1 +
0,02); ( N N N ) sind = 1500 s and tf = – 7 8C – 4(1 + 0,05) 8C.
paraffins precipitated at the same temperature are the same with
or without pour point depressant additive. In contrast, the
appearance of the crystals changes as the proportion of pour
point depressant additive increases and the pour point is low-
ered. Pour point depressant additive molecules play the role of
impurities, inserting themselves on the edges of the growing
crystal and preventing its growth. Due to tg, which is a term of
the induction time (Eq. (6)), is interpreted as the time required
for the nucleus to grow to a detectable size, it is evident the corre-
lation that can be expected between the content of pour point
depressant additive and the induction time.
We additionally looked into the role played by the supersatura-
tion ratio in the theoretical curves. It is also logical to imagine
that the presence of pour point depressant additive molecules
impedes or delays the relief of supersaturation because a real
nucleation phase involves simultaneous nucleation and crystal
growth processes. Therefore, we supposed a nucleation process
in which the supersaturation ratio decreases linearly from 1.2 at
– 7 8C (the saturation temperature of oil D5) up to a 1.0 at a final
temperature, tf, which increases linearly with the content of pour
point depressant additive (it was supposed tf = – 7 – 4(1 + %PPD)
( 8C). We decided to keep constant the saturation temperature of
the oil, Tsat, because it has been widely reported that this temper-
ature is only dependent of the composition of the oil [29]. Figure
5 shows the results obtained and it is obvious that an increase in
the temperature interval of relief of supersaturation causes a
decrease of both gelation temperature and gelation index in a
similar way that was obtained experimentally. This fact suggests
that the content of pour point depressant additive in a lubricant
oil is correlated with the temperature interval of relief of supersa-
turation. In any case Figs. 2 and 5 still show remarkable qualita-
tive differences, especially in the vicinity of the saturation tem-
perature.
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Mat.-wiss. u. Werkstofftech. 2013, 44, No. 5 Theoretical approach to a better understanding of gelation in the framework of petroleum industry
Finally, Fig. 6 shows the gelation curve of a lubricant oil which
has been drawn by supposing a nucleation process in which a
simultaneous increment of both the induction time and the tem-
perature interval of relief of supersaturation take place. At the
light of Figs. 2 and 6, the qualitative agreement is better than that
found between Figs. 2 and 5. As conclusion, our results suggest
that the induction time and the temperature interval of relief of
supersaturation are coupled magnitudes which are correlated
with the content of pour point depressant additive in a lubricant
oil.
We can only report qualitative agreement between theory and
experiments but we should keep in mind the important simplifi-
cations assumed in the theoretical approach (a nucleation pro-
cess without crystal growing). On the other hand, future
improvements or refinements in the theoretical approach
showed in this work could be very useful for the understanding
of the physical processes involved in the gelation of petroleum
oils. In fact, potential applications of a fully predictive theory of
nucleation in the framework of petroleum industry are evident.
5 Conclusions
The theoretical approach shown in this work achieves good qual-
itative agreement when comparing with real lubricant oils. Par-
ticularly, the effect of a pour point depressant additive in the
rheological properties of a lubricant oil can be explained as a
simultaneous increment of both the induction time and the tem-
perature interval of relief of supersaturation in the solution. This
work increases our confidence in this theoretical formalism
which, nevertheless, should be improved in order to obtain quan-
titative agreement.
Acknowledgements
This work is supported by the Spanish Petroleum Company
“Repsol”.
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Received in final form: January 30th 2013 T 143
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