ADHESION, COHESION AND FREE SURFACE ENERGY ANALYSIS OF ASPHALT

MODIFIED WITH CARBON NANOTUBES

Jaime Tovar1, Tatiana Bermudez2, Jose Pablo Aguiar3, Fredy Reyes4

1
Magister, School of civil engineering, Pontificia Universidad Javeriana - Colombia, Geotechnical
specialist PUJ, Projects management specialist EAN, Roads and Transport engineer UPTC.
jtovar@engineer.com
2
Magister Candidate, School of civil engineering, Pontificia Universidad Javeriana - Colombia,
Roads infrastructure specialist UPTC, Roads and Transport engineer UPTC.
tatianabermudzcas@gmail.com
3
Professor, School of Engineering of the Costa Rica University, Coordinator of Lanamme
investigations. jose.aguiar@ucr.ac.cr
4
Associate Professor, Department of civil engineering, Pontificia Universidad Javeriana. Investigator
of pavements in CECATA group. fredy.reyes@javeriana.edu.co

ABSTRACT: One of the main reasons of pavement damage is the effect produced by
water inside of joints between aggregate and asphalt (Caro-Spinel & Alvarez-Lugo, 2011),
known as Stripping and to minimize this damage by water at same time improving the
asphalt performance, nanomaterials have been generally used. This document presents
the results of the tests performed in the laboratory of Civil Engineering, Pontificia
Universidad Javeriana, with asphalt from Barrancabermeja (Colombia), which was
modified by the addition of carbon nanotubes without purifying (also produced in the
laboratory of the PUJ). Asphalts were modified with 2% of the weight with carbon
nanotubes. Different ratios of copper (Cu) and nickel (Ni) were used to produce the carbon
nanotubes.

Two kinds of sandstone and one kind of limestone were used as aggregates for asphalt
mixtures in Bogotá (Colombia). To measure the adhesion and cohesion, detachment tests
were conducted by tension (AASHTO, 1991) and to measure the rates of resistance to
humidity, surface free energy (Little & Bhasin, 2006) analyses were made. Using stress
tests and analysis of surface free energy, is intended to identify a group of asphalt and
aggregates, those that produce better results to be mixed, i.e. that they are more resistant
to the Stripping, because both techniques are done in dry and wet environments.

Keywords: Carbon nanotube, stripping, adhesion, cohesion, free surface energy.

Abbreviations: BBS (Bitumen Bond Strength), CNT (carbon nanotubes), PATTI

(pneumatic adhesion tensile testing instrument), POTS (pull-off tensile strength).

INTRODUCTION
In Colombia the entities which are in charge of national and local road mesh, reported high
percentages of the road network as regular and bad state, (48.7% of the national road
network (INVIAS, 2014)). These high percentages of deterioration can be attributed to
multiple causes such as design failure, material, environmental conditions, construction
processes and increasing charges among others (F. Reyes, 2003). Premature pavement
damage may come from the water effect inside of the asphalt mixtures, the result can be
seen in the loss of adhesion between asphalt binder and aggregate, this failure
mechanism is known as Stripping. To explain the effect of water on the performance of
asphalt mixtures, during last years, different techniques where developed, to measure
adhesion between aggregate and asphalt in wet and dry state, among others, visual
inspection test, simple mechanical tests on compacted specimens, qualitative methods to
evaluate adhesion/cohesion (without mechanical tests), different kinds of wheels and
spreads of testing etc. (Mehrara & Khodaii, 2011)

The glass was included as substrate, because it can be a reference material, due to the
possibility to find glass all over the world, this material is recommended to create a general
data as reference.

MATERIALS AND METHODS

Carbon nanotubes (CNT) modified Asphalt

The asphalt used in tests, corresponds to a Barrancabermeja asphalt type 60-70, which
was modified with carbon nanotubes unpurified (CNTs) with 2% of the weight, to generate
the best resistance to the permanent deformation (Jiménez, 2012). Initially the relationship
of Cu/Ni = 1 gave best results(Jiménez, 2012), then the decision was to use a ratio at the
top Cu/Ni = 2 and two ratios below: Cu/Ni = 0.25 and Cu/Ni = 0.25 (Rubio & Martínez,
2014), was settled four relations Atomic Cu/Ni, for the manufacture of nanotubes : 0.25,
0.33, 1 and 2. Modification of asphalt with carbon nanotubes was carried out at a
temperature of 153 ° C at 2000 rpm by 60 minutes (Rubio & Martínez, 2014)

Sandstone from the Mondoñedo quarry

It is a rock formed in the upper Cretaceous (Kgad), its hard and resistant sandstones
arranged in solid and thick strata interspersed with lydits and claystones which are
removed during the aggregate production (IDU, 2000). These are rocks of sedimentary
origin composed of clasts of quartz sandstone, feldspathic sandstones, lithic sandstones,
siltstones and chert mainly (O. Reyes, Camacho, & Londoño, 2013)

Sandstone rock from the Laguna (FUSCA) quarry

The materials on this site are described as sandstones with interbedded claystones
(Correa, 2000), in its physical appearance rock presents voids at its factory. It corresponds
to the Group No. 1, La Laguna spread and is a site of exploitation for the production of
asphalt materials, accepted by the municipal government (IDU, 2000).

Limestone from the Coello River quarry

These are rocks composed of quartz, plagioclase, biotite and amphibole, also contains silt,
basalts, andesite’s and andesitic basalts. It can be established that prevalence of the
basalt and the presence of rocks as the Crystal Tuff, diorite and quartz diorite, will improve
the resistance of asphalt mixtures. (O. Reyes et al., 2013)
DETERMINATION OF POTS (PULL-OFF TENSILE STRENGTH)
There were determined detachment´s strength (POTS), for each of the possible
combinations of bitumen and substrates, were read (PSI) directly during the BBS test
(AASHTO, 1991) from the monitor of PATTI computer.

The Pneumatic Adhesion Tensile Testing Instrument (PATTI), is a portable device of

pneumatic type, it controls air pressure which is supplied from a tank of compressed air to
a reaction plate, where a metal element type screw, attached to a surface (substrate). The
material that is going to be studied is performed between the metal element and the
surface, and then it is possible to get a Pull-Off Tensile Strength (POTS) for each sample.
PATTI equipment has an electronic interface that allows obtaining strength data vs. time,
read in the computer that controls the entire operation, including the failure tensile strength
or POTS, that is reported on screen once carried out the test. This procedure is described
in the document of Raquel Moraes "Bitumen Bond Strength Test" (Moraes, Velasquez, &
Bahia, 2011).

Both the substrate and the metal element showed a temperature of 60° C, at the moment
of placing asphalt between them, the correct sample construction was verified, as
described in the procedure (AASHTO, 1991), when asphalt flow through the 4 slots on the
metal base, the sample is done. For the dry test, samples where protected in a plastic
container, to prevent damages and tested 24 hours later. For wet testing, samples were
placed in a double boiler for 96 hours at a constant temperature of 25 ° C before test.

DETERMINATION OF CONTACT ANGLES

The surface tension of the liquid makes to present different angles of contact when a drop
is placed on a substrate. To get the measure of this angle, the drop is exposed to a light
source, then the silhouette´s drop can observe by a lens, the image is captured by a high-
resolution camera and processed electronically, the software measures the angle between
the tangent formed in the contact and the base of the drop, this equipment is called
goniometer.

The contact angles of deionized water, formamide and ethylene glycol drops on the
substrates and asphalts object of this study were measured. Then, by mathematical
processing, the value of the component of surface free energy of the materials was
obtained, and then including the value of the component of surface free energy of water,
the value of energies of the asphalt-substrate pairs was obtained, this performed indices of
damage resistance IR1 and IR2 (Little & Bhasin, 2006), which will be explained later.

Equally using the syringe high temperature goniometer, drops asphalt at 150°C were
prepared and their contact angles were measured on the glass substrates, sandstones
and limestone, the purpose of this last procedure is to determine the asphalt wettability on
each of the aggregates.
RESULTS THE TENSION TEST
The cleaning of the substrates influences the outcome (Moraes et al., 2011) and
depending on whether the test was performed in dry or wet, 24 hours were left and 96
hours, respectively, before proceeding with the strength test in the Patti equipment
(Pneumatic tensile adhesion testing instrument) (AASHTO, 1991), after each test, the
value of tension and failure mode result were recorded among other data.

For marks over the substrate after test, was called failure by adhesion when asphalt
covered less than 50% of the test surface, otherwise failure by cohesion. Some groups of
samples (30) failed by one of the two failure modes, in this case one bar is equal to zero
(0%), and were omitted in the graphs.

Adhesion failure

Figure 1. Test result of adhesion failure strength

A count of the number of samples that failed by adhesion, could also make these data are
shown below:

Figure 2. Percentage of samples that failed by adhesion.

Last two graphs on adhesion mode of failure, are complementary, since they allow
knowing the magnitude with which they reach failure and how often it can be.

The results of tension strength, show that there is improvement in the adhesion than the
original asphalt unmodified (Cely, 2015). In modified Asphalts, failure by adhesion does
not exceed 1.5 MPa, only an exception in a sample that reached 1.85 MPa (Cu/Ni = 0.33
glass/wet) with a low frequency (3.3%), note the down frequency of failure by adhesion in
the groups of Cu/Ni = 0.25 and Cu/Ni = 0.33, while groups of Cu/Ni = 1 and Cu/Ni = 2 the
frequency of adhesion failure is higher.

Cohesion failure

Figure 3. Test result of cohesion failure strength

Below are the frequencies of failure by cohesion

Figure 4. Percentage of samples that failed by cohesion.

Failure strength obtained for the case of the cohesion, also present higher values in the
modified Asphalts which in the original asphalt (unmodified) (Cely, 2015), i.e. that the
modification also improves the cohesion. In the modified asphalt there is strengths fail
cohesion than those obtained in the failure by adhesion.
Improving the adhesion is therefore recommended to decrease the frequency by this
failure mode, since the failure by cohesion have higher values then the performance of the
asphalt will improve.

FREE SURFACE ENERGY RESULTS

Also there is a study of the free energy of materials, using the sessile drop procedure
(Little & Bhasin, 2006), the measure of angles from three reference liquids over the
substrates, these were ethylene glycol, formamide, and deionized water. Energy
components calculation is showed in the Table 1.

Table 1. Results of surface free energy based on sessile drop

Energy components (ergs/cm2)

Material

Liquids
Water 21,80 25,50 25,50 51,00 72,80
No Modified* 8,95 9,10 0,09 1,84 10,79
Ratio Cu/Ni = 0,25 47,94 6,15 4,56 10,59 58,53
Ratio Cu/Ni = 0,33 37,97 10,92 2,70 10,86 48,83
Ratio Cu/Ni = 1 40,22 11,66 3,97 13,61 53,83
Ratio Cu/Ni = 2 64,47 8,27 11,43 19,44 83,92
Solids
Glass 94,87 32,26 5,77 27,29 122,15
Sandy - Mondoñedo 262,30 1,70 78,14 23,02 285,32
Sandy - Laguna 94,45 0,80 2,79 2,98 97,44
Limestone - Rio Coello 80,56 26,05 3,19 18,22 98,78
No Modified* : From (Cely,2015)

Surface free energy values are comparable with that reported in previous studies (Hefer &
Little, 2004)(Little & Bhasin, 2006) . RI1 and RI2 damage factors were also calculated
(Little & Bhasin, 2006)

(a) (b)

Figure 5. Damage resistance index.

The RI1 (Figure 5a) indicates that modified asphalt has an improvement in resistance to
damage, compared to asphalt without modifying (Cely, 2015), also is possible to see a
best results in the Asphalts Cu/Ni = 0.33 and Cu/Ni = 1 over the sandstone Mondoñedo
and in the limestone of the Coello River, but in the graph RI2 (Figure 5b) asphalt Cu/Ni =
0.33 with the sandstone Mondoñedo have a good result, so this combination will be better.

WETTABILITY OF ASPHALTS
The results of the contact angles of asphalt drops over the substrates are shown in the
Figure 6.

Figure 6. Contact Angles of liquid asphalt. Wettability of asphalt

Over the rocky substrates, the modified asphalt tends to have lower values of contact
angle, than non-modified asphalt, and then it has better wettability. A better wettability
qualitatively indicates greater affinity between the liquid and the substrate.

CONCLUSIONS
Asphalt modified with nanotubes of carbon (CNT), improves performance in adhesion and
cohesion, at the same time show higher rates of resistance to damage by moisture,
compared with the same asphalt without modifying.

Modified asphalt with NTC of Cu/Ni ratio = 0.33, mixing with the aggregate sandstone of
Mondoñedo, report the best responses to stress and resistance to damage.

Strength test in the laboratory and the analysis of the surface free energy, are checked
each other, according to this reports of adhesion, cohesion and power free surface, which
are recommended simultaneously. With the addition of carbon nanotubes, wettability is
also improved in the asphalt

Mix designs by gyratory compactor, check durability and dynamic behavior of asphalts
selected using the procedure presented in this document.
BIBLIOGRAPHY

AASHTO. (1991). AASHTO TP 91-11.pdf. AASHTO.

Caro-Spinel, S., & Alvarez-Lugo, A. E. (2011). Evaluación de la susceptibilidad al daño por

humedad de mezclas asfálticas empleando propiedades termodinámicas. Revista
Facultad de Ingenieria, (58), 95–104.

Cely, N. (2015). Estudio de la adhesión y cohesión de tres tipos de agregados pétreos

utilizados en Bogotá con asfalto 60-70, 93.

Correa, A. (2000). Situación actual de la explotación de canteras en el Distrito Capital.

Ingeniería E Investigación, (46), 45–55.

Hefer, A. W., & Little, D. N. (2004). Adhesion in bitumen-aggregate systems and

quantification of the effects of water on the adhesive bond, 3157434(September),
222–222 p.

IDU. (2000). Unión temporal proyecto ALO: Avenida Longitudinal de Occidente. Informe
final. Bogotá.

INVIAS. (2014). Informe de Gestión, 2013, 1–280.

Jiménez, G. (2012). Mejoramiento del asfalto 60/70 y la mezcla asfáltica MDC-2 con
nanotubos de carbono, obtenidos a partir de metano, vía catalítica. Pontificia
Universidad Javeriana, 118.

Little, D. N., & Bhasin, A. (2006). NCHRP, Using Surface Energy Measurements to Select
Materials for Asphalt Pavement.

Mehrara, A., & Khodaii, A. (2011). Evaluation of Asphalt Mixtures’ Moisture Sensitivity by
Dynamic Creep Test. Journal of Materials in Civil Engineering, 23(2), 212–219.

Moraes, R., Velasquez, R., & Bahia, H. U. (2011). Measuring the Effect of Moisture on
Asphalt-Aggregate Bond with the Bitumen Bond Strength Test. Transportation
Research Record: Journal of the Transportation Research Board, 2209(-1), 70–81.

Reyes, F. (2003). Diseño racional de pavimentos (Primera ed). Bogotá: Escuela

Colombiana de Ingeniería.

Reyes, O., Camacho, J., & Londoño, A. (2013). Caracterización mecánica de mezclas
asfálticas en función del origen y gradación del agregado pétreo. Revista Científica
General José María Cordova, 11 Num. 12(Julio - Diciembre), 215–232.

Rubio, M., & Martínez, J. (2014). NANOTUBOS DE CARBONO PARA EL

MEJORAMIENTO DE LA MEZCLA ASFÁLTICA MDC-2 Y DEL ASFALTO
COLOMBIANO. Pontificia Universidad Javeriana.