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Energy & Fuels 2006, 20, 620-624

Polymeric Surfaces for Heavy Oil Pipelines To Inhibit Wax


Deposition: PP, EVA28, and HDPE
Cristina M. Quintella,*, Ana Paula S. Musse, Martha T. P. O. Castro, J. C. Scaiano,
Larisa Mikelsons, and Yuji N. Watanabe
LabLaser, Instituto de Qumica, UniVersidade Federal da Bahia, Campus de Ondina,
40.170-290, SalVador-BA, Brazil, and Department of Chemistry, UniVersity of Ottawa, Ottawa,
Ontario K1N 6N5, Canada
ReceiVed August 21, 2005

Pipelines for heavy crude oils have recurrent clogging situations due to paraffin deposition that may lower
production rates and be responsible for leakages. This work evaluates the effect of three polymers on crude oil
wettability and on paraffin deposition inhibition: polypropylene (PP), high-density polyethylene (HDPE), and
a vinyl acetate copolymer with 28% oxygen content (EVA28). Under static conditions, the interfacial tension
between the crude oil and the linings was determined by the contact angle being 12% and 17% higher for
EVA28 and HDPE, respectively, than for that of PP. As the crude oil inside the pipelines is flowing at high
rates, the dynamic interfacial tension was also observed for high flow rates when molecular effects overtake
hydrodynamic ones. For this, the perturbation of intermolecular orientation within the flow, caused by the
beginning of deposit formation and by the wettability, was determined using depolarization of the fluorescence
induced by laser. Under flow, EVA28 and HDPE caused an increase of interaction with the crude oil of 79%
and 43%, respectively, compared to that of PP. HDPE yielded globular wax deposits. The higher tendency of
HDPE than PP to form deposits was attributed to the absence of methyl branches in the first. The EVA28
tendency to form deposits was attributed to the oxygen atoms on the surface as well as to its high polycyclic
aromatic hydrocarbon sorption. Thus, under a high flow rate, PP is better suited to inhibit wax deposition than
HDPE and EVA28.

1. Introduction
Heavy crude oils with a low API degree as well as a high
wax or paraffinic content are usually found in aging reservoirs
or in reservoirs of lagoon origin. These oils have the advantage
of allowing the refineries more options according to international
prices. Nevertheless, the same characteristics can lead to
problems during their production, pumping, and transport, as
paraffinic deposits1,2 may lead to low pumping rates and to the
need to increase differential pressure as well as higher pumping
capabilities. This may increase both equipment failures and
leakage probability,3 thus decreasing the profit margin of the
operation and changing the finance forecasts of companies.
The paraffin crystallization depends on the crude oil paraffin
content, on the thermodynamic and fluidynamic conditions, and
on the paraffin molecular structure.4 The increase of intermolecular orientation of paraffins leads to their nucleation and,
consequently, to the beginning of crystal formation.5,6
* Corresponding author. Tel: 55-71-99647876. Fax: 55-71-2355166.
E-mail: cristina@ufba.br.
Universade Federal da Bahia.
University of Ottawa.
(1) Venkatesan, R.; Ostlund, J. A.; Chawla, H.; Wattana, P.; Nyden, M.;
Foler, H. S. Energy Fuels 2003, 17 (6), 1630-1640.
(2) Cosulchi, A.; Garciafigueroa, E.; Garca-Borquez, A.; Reguera, E.;
Yee-Madeira, H.; Lara, V. H.; Bosch, P. Fuel 2001, 80, 1963-1968.
(3) Ajienka, J. A.; Ikoku, C. U. J. Pet. Sci. Eng. 1995, 13, 87-94.
(4) Andreatta, G.; Gonc alves, C. C.; Buffin, G.; Bostrom, N.; Quintella,
C. M.; Arteagalarios, F.; Perez, A.; Mullins, O. C. Energy Fuels 2005, 19
(4), 1282-1289.
(5) Dorset, D. L. Energy Fuels 2000, 14 (3), 685-691.
(6) Rocha, N. O.; Gonzalez, G.; Vaitsman, D. S. Quim. NoVa 1998, 12
(1), 11.

Several methods have been devised to either remove or inhibit


these deposits; these include injection of water vapor or solvents,
additives to decrease the pour point and improve fluidity,7-10
microwaves and ultrasound irradiation,11 and magnetic fields.6
Recently, plastics, amorphous polymers, and fiber-reinforced
plastics have been used as linings and coatings or as massive
materials in order to reduce the wettability and decrease the
paraffin deposition.12,13 Although they have limitations regarding
maximum operating temperature and creep life,14 they solve
problems such as corrosion, welding, and equipment maintenance cost.
The adhesion capacity and, consequently, the drag increase
when there is an increase of the interfacial tension between the
pipeline walls and the crude oil. They may be evaluated by the
wetting efficiency. As the interfacial interactions take place at
the boundary layers, where the molecular effects overtake
hydrodynamic ones, the flow rate should be a variable with high
significance.
(7) Borthakur, A.; Chanda, D.; Choudhury, S. R. D.; Rao, K. V.;
Subrahmanyam, B. Energy Fuels 1996, 10 (3), 844-848.
(8) Pratap, G.; Shanta, K. L.; Rao, D. V. M. J. Appl. Polym. Sci. 1991,
42 (4), 935-945.
(9) Adewusi, V. A. Pet. Sci. Technol. 1998, 16 (9-10), 953-970.
(10) Machado, A. L. C.; Lucas, E. F.; Gonzalez, G. J. Pet. Sci. Eng.
2001, 32, 159-165.
(11) Bjorndalen, N.; Islan, M. R. J. Pet. Sci. Eng. 2004, 43 (3-4), 139150.
(12) Slack, M. Mater. Perform. 1992, 31 (3), 49-52.
(13) Attou, A.; Benamar, A.; Inglebert, G. Mec. ind. mater. 1997, 50
(3), 109-111.
(14) Boot, J. C.; Toropova, I. L.; Javadi, A. A. Int. J. Solids Struct. 2003,
40 (26), 7299-7314.

10.1021/ef050267p CCC: $33.50 2006 American Chemical Society


Published on Web 02/21/2006

Polymeric Surfaces for HeaVy Oil Pipelines

In the last 50 years, the interfacial tension has been


determined mostly in static conditions or at very low flows using
the contact angle techniques (c).15 For the same liquid, the
interfacial tension is proportional to the cosine of c. It is known
that c depends on the surface roughness,15 on the chemical
nature of both the solid surface and the liquid,16-19 and on the
relative orientation of the surface chemical groups.20
For very small flow rates, Zhang et all21 studied coatings of
polyurethane, an epoxy resin, two polyvinylidene fluoride
polymers, two silicone rubbers, and a methyl acrylate-styrene
copolymer, and found that the last five were better for drag
reduction and paraffin deposition prevention.
In the past decade, the dynamic interfacial tension (Tsl)
between solid walls and liquids flowing at high rates has been
observed using depolarization of the fluorescence induced by
laser in induced liquid flows (PLF-FI). This technique has
several advantages over the c: (1) it can be used with liquids
at high velocities; (2) when using a transparent window, it is a
noninvasive, nondestructive test (NDT); (3) it can be remotely
applied; (4) it is sensitive to certain wall chemical constitutions
that c is not;22 and (5) it observes processes at a molecular
level, when the preliminary orientation that leads to crystal
formation starts to take place, thus having high potential for a
remote control method of paraffin-deposition prevention.
PLF-FI showed that the wetting of surfaces under high liquid
flow is sensitive to the chemical nature of both the walls and
the liquid17 and to the surface oxygen content.22 For micro
channels 10-m wide, consisting mainly of boundary layers, a
pronounced effect of the wall chemical constitution on the flow
intermolecular alignment was observed.23 It proved also to be
sensitive to the branching degree of polyethylene surfaces,
although the static interfacial tensions evaluated by traditional
c were not.22 This was associated with the wetting of the liquid
flow due to temporary intermolecular interactions between the
liquid and the surface.
Natural crude oil fluorescence is mainly due to its intrinsic
fluorophores, the polycyclic aromatic hydrocarbons (PAHs).4
Usually, crude oil fluorescence is evaluated as a function of
the emission wavelength in order to determine the oil chemical
constitution. There are several studies of fluorescence lifetime
and quantum yield as a function of composition and concentration of components,24 oil classification,25 quantitative analysis,26
and determination of asphaltene molecular size.4,27
(15) Adamson, A. W.; Gast, A. P. Physical Chemistry of Surfaces; John
Wiley & Sons Inc.: New York, 1997.
(16) Extrand, C. W. J. Colloid Interface Sci. 2002, 248, 136-142.
(17) Quintella, C. M.; Gonc alves, C. C.; Castro, M. T. P. O.; Pepe, I.;
Musse, A. P. S.; Lima, A
. M. V. J. Phys. Chem. B 2003, 107 (33), 85118516.
(18) Quintella, C. M.; Gonc alves, C. C.; Pepe, I.; Lima, A. M. V; Musse,
A. P. S. J. Braz. Chem. Soc. 2001, 12, 780-786. Available online, in
English, at http://jbcs.sbq.org.br/jbcs/2001/vol12_n6/14.pdf.
(19) Suda, H.; Yamada, S. Langmuir 2003, 19, 529.
(20) Quintella, C. M.; Lima, A
. M. V.; Gonc alves, C. C.; Watanabe, Y.
N.; Schreiner, M. A.; Mammana, A. P; Pepe, I.; Pizzo, A. M. J. Colloid
Interface Sci. 2003, 262 (1), 221-226.
(21) Zhang, X.; Tian, J.; Wang, L.; Zhou, Z. J. Pet. Sci. Eng. 2002, 36,
87-95.
(22) Quintella, C. M.; Musse, A. P. S.; Castro, M. T. P. O.; Gonc alves,
C. C.; Watanabe, Y. N. J. Colloid Interface Sci. 2005, 281, 201-208.
(23) Quintella, C. M.; Lima, A
. M. V.; Mammana, A. P.; Schreiner, M.
A.; Pepe, I.; Watanabe, Y. N. J. Colloid Interface Sci. 2004, 271, 201205.
(24) Wang, X.; Mullins, O. C. Appl. Spectrosc. 1992, 48 (8), 997-984.
(25) Song, J. M.; Tang, B. L. Spectrosc. Spectral Anal. 2002, 20 (1),
115-118.
(26) Ryder, A. G. J. Fluoresc. 2004, 14 (1), 99-104.
(27) Groenzin, H.; Mullins, O. C. Energy Fuels 2003, 17, 498-503.

Energy & Fuels, Vol. 20, No. 2, 2006 621

PLF-FI, unlike these other fluorescence methods, does not


resolve the fluorescence in wavelength, but rather on its
polarization components. The irradiation in the visible with laser
is absorbed mainly by crude oil PAHs with a high number of
rings.4 The PAHs become intermolecular alignment probes as,
in the PLF-FI, the detection of the fluorescence is resolved only
in its polarizations and not in wavelength.
The aim of this paper is to evaluate the inhibition efficiency
of crude oil deposits due to three polymeric surfaces: HDPE,
PP, and EVA28. For this purpose we evaluated the interfacial
tension between the crude oil and each of the polymer surfaces:
statically by c and dynamically by PLF-FI.
As far as we are aware, this is the first time that wetting
efficiencies of these polymers under high flow have been
compared and that crude oil PAHs have been used as intrinsic
fluorescent probes of intermolecular alignment within crude oil.
2. Experimental Section
2.1. Materials. The crude oil was from Bacia do Reconcavo
Bahiano and consisted of crude dead oils, that is, as produced at
the well and without the volatile fraction. It was brown-colored
and had a typical composition of algae organic matter from a lagoon
paleolithic environment with 14.7% w/w paraffin content, 0.20%
w/w emulsed water, sediments below traces, 0.8727 g/L density at
15.6 C, 30.64 API, 39.00 C pour point, and 49.22 C cloud point.
Differential scanning calorimetry showed that the oil has two
cloud point regions centered at 30 C and 45 C, corresponding,
respectively, to paraffins with 18-19 carbons and with 22 carbons.
The ramification degree of 0.65 was evaluated by infrared
spectroscopy with Fourier transform through the ratio of the areas
of the peaks corresponding to the terminal CH3 groups and the
lateral CH2 groups. Gas chromatography-mass spectrometry (GCMS) allowed us to identify PAHs peaks which were attributed to
phenanthrenes and choronanes.
The fluorescence lifetime of the natural crude oil was obtained
using an experimental setup described before.28 Briefly, a 0.39-ns
laser pulse at 532 nm excited the sample, and the fluorescence was
detected with time and wavelength resolution. Gaseous nitrogen
was blown within the sample for 15 min prior to the experiment.
The fluorescent emission (Figure 1) ranged from 530 to 753 nm,
had a maximum at 582 nm, and a width at half height of 73 nm.
The crude oil excited lifetime was 3.8 ns as determined by fitting
the emission decay time with a monoexponential (R2 ) 0.996).
The flow solution consisted of a 80% v/v crude oil in heptane
solution.
The wall surfaces consisted of three polymers (Figure 2): two
long aliphatic chain polymers, high-density polyethylene (HDPE,
IA-59 Politeno) and polypropylene (PP, Moltec), and a vinyl acetate
copolymer with an oxygen content of 28% (EVA28, HM0728
Politeno).
The polymer surfaces were made in the same setup by ASTM
D-4703. They had similar roughnesses that varied between 80 and
100 nm, as determined by perfilometry.
The sample surfaces had 2 cm 4 cm with 2 mm thickness.
All surfaces were cleaned with water, then immersed for 10 min
in ethanol and dried at 25 C for at least 15 min before each
experiment.
2.2. Static Interaction through Contact Angle. The static
interaction was measured by c, at (24.0 ( 0.5) C and 1 atm. A
drop of 15 10-6 L was formed with a micropipet on the
substrates, and its image was remotely acquired by a Hitachi VME230A video camera, with 36X zoom, connected to a PC. The
software Image Pro Plus was used to process the images. The final
angle was the average of eight measurements. Borosilicate and tin
dioxide surfaces were used as standards.18
(28) Cosa, G.; Vinette, A. L.; McLean, J. R. N.; Scaiano, J. C. Anal.
Chem. 2002, 74 (24), 6163-6169.

622 Energy & Fuels, Vol. 20, No. 2, 2006

Quintella et al.

Figure 2. Chemical structure of the polymer walls: high-density


polyethylene (HDPE), polypropylene (PP), and a vinyl acetate copolymer with oxygen content of 28% (EVA28).

Figure 3. (A) Scheme of the flow cell for PLF-FI. (B) Experimental
setup for polarized laser induced fluorescence within liquid induced
flows (PLF-FI) to detect fluorescence depolarization. CW - laser, M
- mirrors, L1, L2 - lenses, P1, P2 - Glan-Thompson Polarizer, PD1,
PD2 - photodiodes, I - interface, PC Personal computer, FI - liquid
flow, F- color filter, BS - beam splitter. [Figure 3B reproduced under
permission of Qumica NoVa 2005, 28 (2), 227-339. Sociedade
Brasileira de Qumica].

Figure 1. Fluorescence emission of the paraffinic crude oil excited at


532 nm. (A) Fluorescence intensity as a function of the wavelength
emission and emission time. (B) Fluorescence time decay integrated
over all wavelengths (lifetime of 3.8 ns, R2 ) 0.996). (C) Fluorescence
emission spectrum integrated over time.

2.3. Dynamic Interaction through PLF-FI. 2.3.1. Flow Cell.


An in-house developed cell29 (Figure 3A) was used in order to
emphasize the boundary layer where the interaction between the
wall and the liquid flow is stronger.
Each cell consists of two juxtaposed plates with 2.4 mm between
them. The frontal plate is the borosilicate visor, and the bottom
plate is the material to be evaluated. The cell body is made of
polyester resin. The liquid enters the cell at its top and exits at its
bottom. The crude oil velocity was fixed at 2.8 cm s-1. This high
velocity was chosen in order to emphasize the molecular hydro(29) Castro, M. T. P. O.; Quintella, C. M. Quim. NoVa 2005, 28 (2),
337-337.
(30) Feofilov, P. P. The Physical Basis of Polarized Emission; Consultants
Bureau: New York, 1961.

dynamic effects that become predominant at high velocities over


the macroscopic fluid dynamic effects that predominate at low
velocities.15
2.3.2. Depolarization of the Fluorescence Induced by Laser in
Induced Liquid Flows (PLF-FI). Fluorescence depolarization (PLF)
consists of a technique known for many years to be a sensitive
probe of molecular alignment in liquid flows.30 Kenyon et al.31,32
applied PLF for the first time to free liquid laminar jets at high
velocity and found that the intermolecular alignment is between
one and three orders of magnitude greater than that achieved by
conventional flow or electric field alignment techniques.33 For
liquids flowing at a high flow rate inside and after exiting the thin
slit, it proved possible34,35 to visualize directly the boundary layer
at a molecular level, to infer the macroscopic velocity gradient, to
(31) Kenyon, A. J.; McCaffery, A. J.; Quintella, C. M. Mol. Phys. 1991,
72, 965.
(32) Kenyon, A. J.; McCaffery, A. J.; Quintella, C. M.; Winkel, J. F.
Mol. Phys. 1991, 74, 871.
(33) Bain, A. J.; Chandna, P.; Butcher, G. Chem. Phys. Lett. 1996, 260,
441-446.
(34) Quintella, C. M.; Gonc alves, C. C.; Musse, A. P. S.; McCaffery,
A. J. Exp. Fluids 2003, 35, 41-48.

Polymeric Surfaces for HeaVy Oil Pipelines


generate the velocity profiles along the whole of the flow, and to
discuss macroscopic fluid dynamical concepts in terms of interactions between the molecules that comprise the flowing liquid.
PLF-FI consists basically of the irradiation of the fluorescent
molecular probes within a liquid flow by a laser polarized vertically
and in the detection of their fluorescent emission as a function of
the light polarization components.
The depolarization of the fluorescence, compared to the laser
polarization, can be interpreted as a bi-dimensional phenomenon
in terms of polarization (P)1,2,16:
P)

I | - I
I | + I

where I| and I are, respectively, the fluorescence components


parallel and perpendicular to the axis defined by the direction of
laser polarization.
The polarized laser photo selects the fluorescent sensors oriented
along the flow, as the absorption probability is proportional to the
square cosine of the angle between the laser electrical field and
the molecular dipoles. The flow velocity gradient induces an inner
stress that changes the chemical environment, that is, the intermolecular interactions and the molecular electronic cloud shape,
increasing the local anisotropy, hindering the fluorescent sensors
rotation. This increases the probability of the sensors being still
aligned along the flow when they suffer fluorescent decay, thus
increasing the polarization of their fluorescence emission.
When the interaction of the liquid flow with the solid surface
increases, the liquid intermolecular network that was previously
aligned vertically by the vertical flow starts to have stronger
interactions along the horizontal, misaligning the molecular domains
and the fluorescent sensors within, decreasing I|, thus decreasing
P.
The experimental setup for PLF-FI was described before.22,29
Briefly, a Coherent Inova60 argon laser (Figure 3B) at multimode,
multiline, and 100 mW is reflected by two mirrors (M) through a
biconvex borosilicate lens (L1) of 400-mm focal length that focus
the laser into the sample (FI) on a 0.02-mm2 diameter spot. To
monitor the laser intensity fluctuations in real time, 10% of the
laser beam was diverted by a beam splitter (BS) onto a BPW-21
RS-Electronics photodiode (PD1) with 7.5-mm2 active area, operating as a current-to-voltage converter with seven optional sensibility
ranges. A vertical Glan-Air polarizer (P1) ensured 100% polarization.
The florescence is induced with a 100% vertically polarized laser
that enters parallel to the vertical of the frontal window, thus
ensuring that only vertically polarized light enters the flow cell.
The fluorescence is collected frontally, perpendicularly to the frontal
window, thus ensuring that no polarization orientation is privileged.
Fluorescence was collected within a 0.02-sr solid angle by a
biconvex borosilicate lens (L2) of 50-mm focal length and focused
on to a detector consisting of an OPT 202 Burr-Brown photodiode
(PD2) with a 5.22-mm2 active area, operated as a current-to-voltage
converter with four optional sensitivity ranges. A 550-nm cutoff
filter (F) blocked the laser radiation. The Glan-Thompson polarizer
(P2) was manually rotated to select either the vertical (I|) or the
horizontal (I) fluorescence intensities. The outputs of both PD1
and PD2 were captured by an interface (I) connected to a PC. A
QBasic program controlled both data acquisition and sample
positioning.
The flow cell position was varied uniformly in relation to the
horizontal of the laser beam direction, using a two-axis translation
frame36 with 10-m resolution and repeatability better than 0.1%
that was remotely controlled by a PC through interface (I). Both I|
and I were obtained cross-stream at 3.0 cm downstream from the
(35) Quintella, C. M.; Musse, A. P. S.; Gonc alves, C. C. J. Phys. Chem.
B 2004, 108 (8), 2751-2755.
(36) Quintella, C. M.; Gonc alves, C. C.; Pepe, I.; Lima, A. M. V.; Musse,
A. P. S. J. Autom. Methods Manage. Chem. 2002, 24, 31-39. Available
online in English at http://taylorandfrancis.metapress.com.

Energy & Fuels, Vol. 20, No. 2, 2006 623


Table 1. Data of Interfacial Tension between the Paraffinic Crude
Oil and Polypropylene (PP), High Density Polyethylene (HDPE),
Vinyl Acetate Copolymer with 28% Oxygen Content (EVA28),
Borosilicate (BSi) and Tin Dioxide (SnO2): Static Interaction,
Obtained by Contact Angle (c), and Dynamic Interaction Obtained
by Polarization of the Fluorescence Induced by Laser in Liquid
Flow (PLF-FI)
surfaces

c
((2)

cos c
((0.01)

PP
HDPE
EVA28
BSi
SnO2

42
30
28
22
27

0.743
0.866
0.829
0.891
0.927

polarization (%)
77 ( 2
44 ( 4
16 ( 2

cell input. Polarization profiles acquired further downstream did


not change significantly (<0.2%,); thus, only one profile was
acquired for each cell. Each profile was acquired at least three times
for the same cell and their average used.
Each polarized fluorescence profile (obtained by PD2) was
divided by the laser intensity (obtained in real time by PD1) in
order to correct laser intensity fluctuations.

3. Results and Discussion


3.1. Static Liquid (Contact Angle). The contact angles
(Table 1) are bigger for PP than for HDPE and EVA28, thus
PP has lower static interfacial tension with the crude oil. The
cos c ratio shows that the interaction with HDPE is 17% more
intense than that with with PP. This may be due to the PP methyl
groups (Figure 2) that hinder the interaction of the crude oil
paraffins with the PP main polymeric chains and the consequent
smaller surface density of hydrogen atoms.
It was possible to observe yellowish stains on the EVA28
surfaces after removal of the crude oil drops. This was attributed
to the sorption of the colored components of the crude oil,
mainly PAHs, by the EVA28 surfaces. The EVA28 drops have
the lowest c, thus having the strongest Tsl with the crude oil,
which may be attributed the crude oil aromatic group sorption
in the EVA28.
3.2. Flowing Liquid-Fluorescence Depolarization. The
flow within the cells is considered highly laminar as it has a
Reynolds number below 15 (the critical Reynolds number is of
the order of thousands). Table 1 shows the polarization for the
flow on each surface constitution. It was 77%, 44%, and 16%
for PP, HDPE, and EVA28, respectively.

Figure 4. Scheme of the crude oil PAHs being aligned within the
flow.

624 Energy & Fuels, Vol. 20, No. 2, 2006

Quintella et al.

than PP, confirming both the static and dynamic interfacial


tension evaluations.
4. Conclusion

Figure 5. Textures of paraffin depositions in the inner walls of the


cell after tests. HDPE favors the formation of globular paraffin
depositions.

The natural crude oil fluorophores4 consist mainly of PAHs


with lateral alkyl chains and, as the number of rings increases,
the alkyl chain length increases proportionally. As in this work,
the excitation was at 532 nm, the number of rings should be at
least over three, and the alkyl chains are long. Within the flow,
the alkyl chains of paraffins and PAHs align themselves along
the flow (Figure 4), aligning the molecular dipoles of PAHs
and producing a highly anisotropic chemical environment; thus
the crude oil PAHs become good intermolecular alignment
sensors.
For HDPE and EVA28, the polarization was 43% and 79%
lower, respectively, than that for PP. The higher polarization
for PP is due to its lower interaction with the crude oil. As
HDPE and PP differ mainly on the presence of the PP methyl
branches (Figure 2), it may be that the existence of methyl
groups in PP and their steric effect hinders the interaction
between the crude oil alkyls and the PP main polymeric chains.
For EVA28, coloring caused by the sorption effect was also
seen. The EVA28 low polarization was due to high interaction
with the crude oil which was attributed to the existence of
oxygen on its surface. As the surface progressively sorbs the
PAHs, there is also a contribution due to the interaction between
the PAHs and the alkyl chains of the crude oil and the PAHs
sorbed on EVA28 surface.
Photos of the deposits after operation can be seen in Figure
5. HDPE showed a higher tendency to form granular deposits

The natural fluorescence of crude oil can be used, without


addition of fluorescence sensors, to monitor the intermolecular
alignment of paraffins and their interaction during flow with
pipeline walls with different chemical constitutions.
The low polarization obtained for flows on EVA28 was
attributed to a stronger interaction with the crude oil due to the
crude oil oxygen content as well as its surface being covered
with adsorbed crude oil PAHs. Both the static and the flow
evaluations of interfacial interaction showed that the interaction
was smaller for PP than that for HDPE and EVA28.
For HDPE, the flow polarization was 43% smaller than for
PP while the static evaluation was only 17% smaller. This
confirms the emphasis of the molecular effects over the fluid
effects when the liquid has a high flow rate.
As both HDPE and PP are linear polymers, the PP smaller
interaction with crude oil and the higher tendency to inhibit
paraffinic depositions were attributed to its branches of surface
methyl groups that reduce the surface density of hydrogen atoms
and hinder the interaction between the crude oil alkyls and the
surface. Thus PP proved to be better in inhibiting paraffin
deposits than HDPE and EVA28.
Acknowledgment. We thank Conselho Nacional de Desenvolvimento Cientfico e Tecnologico (CNPq, Brazil) for the partial
support of this work. We acknowledge Politeno for the samples of
HDPE and EVA28, Prof. Alade Mammana from CenPRA (Centro
de Pesquisas Renato Archer) for the sample of SnO2. A.P.S.M.
acknowledges an undergraduate research fellowship from PIBICCNPq and CNPq. M.T.P.O.C. acknowledges a Postdoc scholarship
from Fapesb. C.M.Q. acknowledges a senior research scholarship
from CNPq.
EF050267P