INVESTIGATING ASPECTS OF AGGREAGTE PROPERTIES

THAT INFLUENCE ASPHALT MIXTURE PERFORMANCE

by
Clint Miller
Kamilla L Vasconcelos
Dallas N Little
and
Amit Bhasin
Research Report For DTFH61-06-C-00021
Texas A & M University, College Station
and
The University of Texas at Austin, Austin
June 2011
DISCLAIMER
The contents of this report reect the views of the authors, who are responsible for the facts
and the accuracy of the information presented herein. Mention of trade names or commer-
cial products does not constitute endorsement or recommendations for use.
ACKNOWLEDGMENTS
The authors recognize that support was provided by Federal Highway Administration through
the Aggregates Foundation for Technology, Research and Education and the National Sand
Stone and Gravel Association to the International Center for Aggregate Research.
v
ABSTRACT
The physical and physio-chemical properties of aggregates inuence different aspects
of the performance of asphalt mixtures. Some of these properties are inherent to the nature
and source of the aggregate (e.g. mineral composition) while other properties are, at least to
some extent, inuenced by the processes used to produce the asphalt mixture (e.g. mixing
and compaction temperature). This research was conducted in two parts.
The rst part of this research was to evaluate the role of asphalt mixture production
temperatures on the performance of Warm Mix Asphalt (WMA). Results from the dynamic
mechanical analysis of ne aggregate matrix (FAM or ne aggregate-asphalt mortar) spec-
imens indicate that for a given material combination, shear modulus and fatigue cracking
resistance of the FAM typically decreased when the specimens were produced at a rela-
tively lower mixing and compaction temperature compared to standard hot mix. Results
from tests conducted using the micro calorimeter demonstrate that for the non-porous ag-
gregates used in this study, lower aggregate pretreatment temperatures (within the range
of 90
o
C to 150
o
C) did not signicantly impact the adhesive bond strength with asphalt
binders.
The second part of this research was to evaluate the physio-chemical properties of com-
mon minerals found in aggregates that inuence their interaction with asphalt binders.
Twenty-two minerals that commonly comprise the surfaces of aggregates were carefully
selected and tested using the Universal Sorption Device (USD) to determine their surface
free energy components. The researchers believe this to be the most extensive catalog
of mineral surface properties ever compiled. This catalog can serve as a reference for
properties that can be used to explain specic interactions between minerals and materials
interacting with these minerals including but not limited to bitumen and water.
The dimensionless energy ratio of adhesive bond strength between aggregate (mineral)
and bitumen in dry condition to the bond strength in the presence of water was calculated
for two typical asphalt binders. Results demonstrate a wide variation in this energy ra-
tio based on the mineral considered. An important nding from this study was that certain
minerals developed a thermodynamically favored bond with bitumen compared to the com-
peting bond with water. Previous testing on aggregates and computation of energy ratios
always revealed that aggregate surfaces thermodynamically favor a bond with water com-
pared to bitumen. However, aggregates are not generally purely comprised of one mineral
type, and the large majority of the minerals tested demonstrated a potential to strip. This
nding requires more evaluation.
vi
TABLE OF CONTENTS
List of Figures ix
List of Tables xi
Chapter 1. Introduction 1
1.1 Background and Objectives . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Report Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Chapter 2. Background and Literature Review 3
2.1 Aggregate Properties Related to Strength and Stability . . . . . . . . . . . . 3
2.2 Aggregate Properties Relevant to Adhesion . . . . . . . . . . . . . . . . . 6
2.2.1 Inuence of aggregate shape . . . . . . . . . . . . . . . . . . . . . 6
2.2.2 Inuence of physio-chemical properties . . . . . . . . . . . . . . . 7
2.3 Impact of Construction Operations on Aggregate Properties Relevant to
Adhesion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.3.1 Moisture on Aggregate Surfaces During Production . . . . . . . . . 9
2.3.2 Aggregate Storage and Contamination . . . . . . . . . . . . . . . . 11
2.4 Test Methods to Measure Aggregate Properties Relevant to Adhesion . . . . 12
2.4.1 Universal Sorption Device . . . . . . . . . . . . . . . . . . . . . . 13
2.4.2 Wilhelmy Plate Method . . . . . . . . . . . . . . . . . . . . . . . . 14
2.4.3 Micro-calorimeter . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.4.4 Aggregate Imaging System (AIMS) . . . . . . . . . . . . . . . . . 15
2.5 Test Methods to Measure Performance of Asphalt Composites . . . . . . . 15
2.6 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Chapter 3. Inuence of Mixture Production Temperature on Adhesive Prop-
erties of Aggregates 19
3.1 Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
3.2 Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
3.3 Inuence of Production Temperature on Adhesion and Surface Properties
of Aggregates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
3.3.1 Overview of the test method . . . . . . . . . . . . . . . . . . . . . 21
vii
3.3.2 Sample preparation . . . . . . . . . . . . . . . . . . . . . . . . . . 23
3.3.3 Test and analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
3.3.4 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
3.3.5 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
3.4 Inuence of Production Temperatures on Performance of FAM . . . . . . . 31
3.4.1 Sample preparation . . . . . . . . . . . . . . . . . . . . . . . . . . 31
3.4.2 Test and analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
3.4.3 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
3.4.4 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
Chapter 4. Physio-Chemical and Adhesive Properties of Common Minerals
in Aggregates 39
4.1 Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
4.2 Factors That Inuence Surface Free Energy of Aggregates . . . . . . . . . 39
4.2.1 Non-polar active sites . . . . . . . . . . . . . . . . . . . . . . . . 39
4.2.2 Polar active sites . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
4.2.3 Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
4.3 Materials and Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
4.3.1 Elemental analysis of the minerals . . . . . . . . . . . . . . . . . . 42
4.3.2 Pretreatment of minerals for surface energy testing . . . . . . . . . 43
4.3.3 Testing with the universal sorption device . . . . . . . . . . . . . . 43
4.4 Results from Surface Energy Testing . . . . . . . . . . . . . . . . . . . . . 45
4.4.1 Carbonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
4.4.2 Sulfates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
4.4.3 Phyllosilicates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
4.4.4 Feldspars . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
4.4.5 Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
4.4.6 Nesosilicates and Inosilicates . . . . . . . . . . . . . . . . . . . . 50
4.5 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
Chapter 5. Concluding Remarks 63
5.1 Inuence of Mixture Production Temperature . . . . . . . . . . . . . . . . 63
5.2 Physio-chemical and adhesive properties of mineral aggregates . . . . . . . 64
References 67
viii
LIST OF FIGURES
Figure 2.1. Typical temperature prole in a drum mix plant during hot mix
asphalt production. . . . . . . . . . . . . . . . . . . . . . . . . . 10
Figure 3.1. Schematic illustrating the working principle of the differential
micro-calorimeter (Bhasin 2006) with a reaction cell containing
ne aggregates and an empty reference cell; the syringes on cells
are lled with the liquid used to immerse the aggregate sample. . . 23
Figure 3.2. The micro-calorimeter (left) is shown with a typical vial contain-
ing an aggregate sample (right); the asphalt binder is in solution
form in the syringe ready to be injected into the vial with the ag-
gregate to measure the heat of immersion. . . . . . . . . . . . . . 25
Figure 3.3. Typical heat ow measured using the micro-calorimeter when a
solid (aggregate) is immersed in a probe liquid. . . . . . . . . . . 25
Figure 3.4. Inuence of aggregate treatment temperature on the total energy
of immersion with asphalt binders. . . . . . . . . . . . . . . . . . 28
Figure 3.5. Inuence of aggregate treatment temperature on the heat of im-
mersion for aggregate RK. . . . . . . . . . . . . . . . . . . . . . 28
Figure 3.6. Inuence of aggregate treatment temperature on the heat of im-
mersion for aggregate RL. . . . . . . . . . . . . . . . . . . . . . 29
Figure 3.7. Inuence of aggregate treatment temperature on the heat of im-
mersion for aggregate RD. . . . . . . . . . . . . . . . . . . . . . 29
Figure 3.8. Inuence of aggregate treatment temperature on computed adhe-
sive bond strength with different asphalt binders. . . . . . . . . . . 30
Figure 3.9. A typical plot used to identify the number of load cycles to failure;
note that curve with the number of load cycles multiplied by the
normalized reduction in shear modulus has a well dened peak
that is identied with failure. . . . . . . . . . . . . . . . . . . . . 33
Figure 3.10. Inuence of mixing and compaction temperature on the shear
modulus of dry specimens (average shown with +/- one standard
deviation). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
ix
Figure 3.11. Inuence of mixing and compaction temperature on the fracture
resistance of dry specimens (average shown with +/- one standard
deviation). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
Figure 3.12. Inuence of moisture conditioning on linear viscoelastic property
of different FAM specimens. . . . . . . . . . . . . . . . . . . . . 36
Figure 3.13. Inuence of moisture conditioning on fracture resistance of dif-
ferent FAM specimens. . . . . . . . . . . . . . . . . . . . . . . . 36
Figure 4.1. Summary of total, polar and non-polar components of surface en-
ergies for minerals (arranged by group and in the order discussed
above). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
Figure 4.2. Laboratory performance (tensile modulus) of mixtures compared
to ER2 * SSA (ER2 is a parameter based on surface free energies
of asphalt binder and aggregate and SSA is the specic surface
area of the aggregate). (After Little and Bhasin, 2006). . . . . . . 53
Figure 4.3. Laboratory performance (plastic deformation) of mixtures com-
pared to ER2 * SSA parameter (ER2 is a parameter based on sur-
face free energies of asphalt binder and aggregate and SSA is the
specic surface area of the aggregate) (After Little and Bhasin,
2006). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
Figure 4.4. Energy ratio representing inherent resistance to moisture induced
damage for mineral-asphalt binder pairs presented from lowest
to highest and for asphalts AAB and AAD (higher energy ratio
indicates better resistance to moisture damage). . . . . . . . . . . 55
Figure 4.5. Comparison of fatigue lives of moisture conditioned asphalt mix-
tures to dry asphalt mixtures for bitumen AAB and AAD. . . . . . 56
Figure 4.6. Surface energy trends within a mineral group and identication of
minerals that preferred a bond with bitumen rather than water. . . 56
Figure 4.7. Base surface energy versus moles of organic carbon on mineral
surfaces. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
x
LIST OF TABLES
Table 4.1. List of Minerals for Surface Energy Measurements . . . . . . . . 59
Table 4.2. List of Minerals for Surface Energy Measurements . . . . . . . . 60
Table 4.3. Summary of Surface Energy Measurements of Minerals (ergs/cm
2
)
61
xi
CHAPTER 1. INTRODUCTION
1.1 BACKGROUND AND OBJECTIVES
The physical and physio-chemical properties of aggregates inuence different aspects of
the performance of asphalt mixtures. Some of these properties are inherent to the nature
and source of the aggregate (e.g. mineral composition) while other properties are, at least
to some extent, inuenced by the processes used to produce the aggregate or the asphalt
mixture (e.g. mixing and compaction temperature). The importance of characterizing the
physical, chemical and thermodynamic properties of the aggregates that inuence the per-
formance of the asphalt mixtures cannot be underestimated.
The broader objective of this project was to understand the importance of inherent
physio-chemical properties of the aggregate and factors related to aggregate and mixture
production that inuence mixture performance. More specically, this research evaluated
the following:
1. The role of asphalt mixture production temperatures on the performance of WMA.
2. The physio-chemical properties of common minerals found in aggregates and the
inuence of these properties on the ability of the mineral to bond with asphalt binders.
1.2 REPORT STRUCTURE
Chapter 2 of this report presents a comprehensive literature review on the aggregate prop-
erties that inuence the strength and stability of asphalt mixtures as well as aggregate prop-
erties that inuence its adhesion to asphalt binders and resistance to moisture induced dam-
age. This chapter also presents a discussion on the impact of production processes that
inuence these aggregate properties, a summary of test methods that are available to char-
acterize the aggregate properties relevant to adhesion, and a summary of test methods that
are used to characterize the performance of asphalt mixtures.
Chapter 3 presents the ndings from the tests conducted to evaluate the inuence of
mixture production temperatures on the performance of asphalt mixtures. The rst part
of this chapter evaluates the inuence of mixture production temperatures on the physio-
chemical or surface properties of aggregates relevant to adhesion. The second part of this
chapter evaluates the inuence of mixture production temperatures on the cracking and
1
moisture damage resistance of ne aggregate matrix (FAM or asphalt binder - sand com-
posites) using a dynamic mechanical analyzer. The ne aggregates used in the FAM speci-
mens correspond to the ne aggregate from different full-graded mixtures.
Chapter 4 presents the ndings from the tests conducted to evaluate the surface free en-
ergy of pure minerals commonly found in aggregates. Twenty two pure minerals were in-
cluded in this study and their surface properties were cataloged. This chapter also presents
analysis that demonstrates the inherent resistance to moisture induced damage offered by
different minerals. Finally, Chapter 5 presents concluding remarks and a summary of nd-
ings from this study.
2
CHAPTER 2. BACKGROUND AND LITERATURE REVIEW
It is important to assimilate knowledge regarding the inuence of aggregate properties that
have a signicant impact on asphalt mix performance as well as the test and analytical
methods that can be used to determine these properties. A detailed review of applicable
literature was conducted to assemble information from domestic and international agencies
that have explored the inuence of inherent aggregate characteristics (surface energy, shape
characteristics) on mixture performance.
2.1 AGGREGATE PROPERTIES RELATED TO STRENGTH AND STABILITY
The physical and chemical properties of aggregates are known to inuence the performance
of asphalt mixes. For example, many studies emphasize the role of aggregate shape in
controlling the performance of asphalt mixtures, especially resistance to fatigue cracking
and rutting (Masad et al., 2005). These studies conducted experiments that focused on the
inuence of ne aggregate, coarse aggregate, or the combined effect of ne and coarse
aggregate on the mechanical properties and performance of asphalt mixtures.
Campen and Smith (1948) found that when crushed ne aggregates were used instead
of natural rounded aggregates, the stability of dense-graded HMA mixtures increased from
30 to 190 percent. They measured stability using the bearing-index test. Ishai and Gellber
(1982) used the packing volume concept developed by Tons and Goetz (1968) to quantify
the geometric irregularities of a wide range of aggregate sizes. The HMA mixtures con-
taining different aggregates types were evaluated by Ishai and Gellber (1982) for Marshall
stability and ow, resilient modulus, and split tension strength. The results showed that
there was a signicant increase in stability with an increase in the geometric irregularities
of the aggregates. No correlation was found between geometric irregularities and resilient
modulus or indirect tensile strength of the HMA mixtures.
Kalcheff and Tunnicliff (1982) evaluated the affect of ne aggregate shape on HMA
properties. HMA mixtures were tested using Marshall stability, repeated-load triaxial com-
pression, static indirect tensile strength, and repeated-load indirect tensile resistance tests.
They found that the use of manufactured sand instead of natural sand improved the mix-
tures resistance to permanent deformation from repeated loads, tensile strength, and tensile
fatigue resistance. Winford (1991) reached the same conclusion by relating mechanical
properties of HMA, such as those obtained from the static conned creep test, to the type
3
of ne aggregate in the mix.
Herrin and Goetz (1954) reported that when the amount of crushed gravel in the coarse
aggregate increased, the triaxial compressive strength of the dense-graded HMA was not
signicantly inuenced. However, the strength of the open-graded HMA mixture increased
signicantly when the percentage of angular coarse aggregates was increased. Field (1958)
found a considerable increase in HMA Marshall stability due to an increase in the percent-
age of crushed coarse particles. The inuence of crushed gravel coarse aggregate on the
properties of dense-graded HMA mixtures was also investigated by Kandhal and Wenger
(1975). They found that the Marshall stability of a dense-graded mix decreased with an
increase in uncrushed gravel particles. However, the differences among the mixes were not
signicant. They also noted that there was no signicant difference in the tensile strength
of HMA mixtures containing crushed and uncrushed coarse aggregates.
Sanders and Dukatz (1992) reported on the inuence of coarse aggregate angularity on
permanent deformation of four interstate sections of HMA pavements in Indiana. One of
the four sections developed permanent rutting within two years of service. They found that
HMA mixtures used in the base course and the surface course of the rutted section had
lower amounts of angular coarse aggregate compared to the other three sections.
Kandhal et al. (1998) pointed out that only a few studies had been conducted to examine
the inuence of at and elongated coarse aggregate particles on HMA strength compared
to the number of studies that addressed coarse aggregate angularity. The presence of ex-
cessive at and elongated aggregate particles is undesirable in HMA mixture because such
particles tend to break down (especially in open-graded mixtures) during production and
construction, thus affecting the durability of HMA mixtures.
A study by Li and Kett (1967) found that the dimension ratio (width to thickness or
length to width) had no effect on Marshall or Hveem stability as long as the dimension
ratios were less than 3:1. The permissible percentage of at and/or elongated particles (di-
mension ratio exceeding 3:1), that did not adversely affect the mix stability was determined
to be 30 percent or as much as 40 percent. Stephens and Sinha (1978) reported that HMA
mixes containing 30 percent or more at particles (longest axis to shortest axis is more
than or equal to three) maintained higher void contents compared to some other blends
with lower percentages of at particles. These mixes were compacted with equivalent ef-
forts using a kneading compactor.
Some studies focused on comparing the relative inuence of ne aggregate and coarse
aggregate shape properties on the mechanical properties and performance of HMA. Lefebure
4
(1957) utilized the Marshall test to measure the stability of HMA mixtures containing a
crushed cubical coarse aggregate or crushed aggregates with at and long particles com-
bined with natural sand or crushed sand. His study concluded that ne aggregate was the
most critical component of the HMA mixture. Its quantity and characteristics controlled, to
a large extent, the Marshall stability. Wedding and Gaynor (1961) evaluated the inuence
of crushed coarse and ne aggregate on the Marshall stability of dense-graded HMA mix-
tures. Using crushed coarse aggregates caused a signicant increase in stability compared
to uncrushed coarse aggregates. The use of crushed ne aggregates increased the stability
of mixes containing uncrushed coarse aggregates. However, the use of crushed ne ag-
gregates had a minimal effect on HMA stability when the mixes contained crushed coarse
aggregates.
Foster (1970) measured the resistance of dense-graded HMA mixtures to trafc by
using test sections. He concluded that HMA mixtures containing crushed coarse aggregate
showed no better performance than a mix containing uncrushed aggregates. The study
attributed this nding to the crushed ne aggregate, which controlled the capacity of the
mix to resist stresses induced by trafc.
The inuence of shape, size, and surface texture of aggregate on stiffness and fatigue
response of HMA mixture was investigated and summarized by Monismith (1970). He
indicated that aggregate characteristics affect both stiffness and fatigue response of HMA
mixtures. Monismith (1970) recommended utilizing rough-textured materials with dense
gradation for thick pavements in order to increase mix stiffness and fatigue life; whereas,
it might be acceptable to utilize smooth-textured aggregates in thin pavements since they
produce less stiff mixtures resulting in increased fatigue life. Barksdale et al. (1992) eval-
uated the effect of aggregate on rutting and fatigue of HMA mixtures. Aggregate shape
was measured using image analysis techniques and the packing test developed by Ishai and
Gellber (1982) . They found that aggregate shape properties obtained from the packing test
were statistically related to the rutting behavior of selected HMA mixtures. A comprehen-
sive study by Kandhal et al. (1991) evaluated the factors that contribute to asphalt pavement
performance. They found that mixtures with less than 20 percent natural sand in the ne
aggregate had better performance than mixtures with more than 20 percent natural sand.
They also recommended using coarse aggregate having at least 85 percent of particles with
two or more fractured faces for heavy-duty wearing and binder courses.
A study conducted at the Texas Transportation Institute related an imaging index of
aggregate texture (fractal dimension) to the creep behavior of asphalt mixes (Yeggoni et al.,
5
1996). In this study, seven different aggregate blends of the same gradation but with varying
amounts of crushed coarse aggregate particles were prepared.
2.2 AGGREGATE PROPERTIES RELEVANT TO ADHESION
Geometric, chemical and thermodynamic properties of the aggregate surfaces are impor-
tant in determining the nature and durability of the bond with bitumen in dry condition
and in the presence of water. Loss of bond between the aggregate and the bitumen can
occur in two modes. The rst mode is adhesive failure between the aggregate and the bi-
tumen, and the second mode is cohesive failure of a weak boundary layer that is formed
at the bitumen-aggregate interface. Several theories in the literature explain adhesive fail-
ure based on mechanisms related to mechanical bonding, thermodynamic interactions or
physical bonding, and chemical bonding. It is unlikely that any of these mechanisms or
theories can exclusively explain the quality of the bond between an aggregate surface and
bitumen. The relative inuence of these mechanisms on the performance of any combina-
tion of asphalt and aggregate depends on the physical and chemical characteristics of both
the aggregate and the binder.
2.2.1 Inuence of aggregate shape
Aggregate shape characteristics inuence mechanical adhesion between the aggregate and
binder. Pocius (1997) described that three factors that contribute to mechanical adhesion:
physical lock and key, redistribution of stresses, and increased surface area. An important
aspect of resistance to moisture damage is the bond strength per unit area within the binder
and at the binder-aggregate interface. As the level of aggregate texture and angularity in-
creases, aggregate surface area increases, and the result is an increased total bond energy in
the mix. Tarrer and Wagh (1991) emphasize the importance of surface texture in mechan-
ical bonding of the bitumen and aggregate. They characterized macroscopic roughness of
aggregates in terms of its surface texture. Surface texture of aggregates at the microscopic
level can be signicantly different from the surface texture at the macroscopic level. A
measure of the surface texture of aggregates at the microscopic level is the specic surface
areas of the aggregates. Bhasin and Little (2006) demonstrate that aggregates have a very
broad range of specic surface areas that varies from 0.1 to 10 m
2
/gm for the same size
fraction (passing 4.7 mm sieve and retained on 2.36 mm sieve). Specic surface areas of
aggregates were measured during the process of estimating their surface free energies using
6
the universal sorption device.
Hicks (1991) built upon the work by McBain and Hopkins and reported that it is gen-
erally accepted that aggregates with a porous, slightly rough surface promote adhesion by
providing a mechanical interlocking effect (McBain and Hopkins, 1929, 1925). A possible
adverse effect of angularity on moisture damage is an increased probability of puncturing
the asphalt lm and allowing intrusion of water to the asphalt-aggregate surface.
The relationship between aggregate shape properties and HMA performance under wet
conditions was described by Masad et al. (2004). Researchers tested and analyzed HMA
mixtures with limestone, siliceous gravel, and granite aggregates. The granite aggregate ex-
hibited the highest levels of texture and angularity, followed by limestone, and then gravel
(Masad et al., 2004). The performance testing results indicated that the granite mix was
superior to the limestone mix under wet conditions. Researchers theorized that the granite
retained a superior level of bonding in the presence of water compared to the limestone
aggregate because of its higher texture and angularity.
2.2.2 Inuence of physio-chemical properties
Thermodynamic properties such as surface free energies of the aggregate and bitumen are
used to explain the adhesion between these materials and the propensity of water to displace
bitumen from the bitumen-aggregate interface (Majidzadra and Brovold, 1968; Kanitpong,
2004). Curtis et al. (1993) determined the Gibbs free energy of aggregates from adsorption
isotherms. Cheng (2002) demonstrated the use of Wilhelmy plate method and the Universal
Sorption Device (USD) to measure surface free energies of aggregate and bitumen. He
uses the surface free energies of these materials to calculate their interfacial bond strength
in wet and dry conditions based on thermodynamic relationships. Kim et al. (2004) and
Bhasin et al. (2006) demonstrate the correlation of these thermodynamic parameters to the
moisture sensitivity of an asphalt mix.
The chemical bonding theory suggests that the adhesion between the aggregate and
bitumen is due to the formation of weak chemical bonds between various polar functional
groups in the bitumen with the active minerals on the aggregate surface. Petersen (1984)
reported eight different types of functional groups that are typically found in bitumen and
can chemically interact and form bonds with the aggregate surface. Examples of weak
acid type functional groups are carboxylic acids and anhydrides, and examples of weak
base type functional groups are sulfoxides and pyridines. Jamieson et al. (1995a) report
that, chemical sites on aggregate surfaces associated with high afnity for bitumen include
7
elements such as aluminum, iron, magnesium and calcium. Elements associated with low
bonding afnity include sodium and potassium. Little et al. (2002) reported the formation
of calciumor sodiumsalts when carboxylic acid fromthe bitumen chemically interacts with
the available calcium or sodium on the aggregate surface. While sodium salts are readily
soluble in water and accelerate moisture damage, calcium salts are relatively insoluble and
therefore are more resistant to water induced damage. The utility of active llers such
as hydrated lime and liquid anti-strip additives to retard moisture induced damage is also
explained based on such chemical interactions. Details of specic interactions between
various types of aggregates and bitumen functional groups are available in the literature.
In another study, a micro-calorimeter was used to quantify the effect of chemical and
physical interactions between model compounds (that represent bitumen functional groups)
and active minerals (Ensley and Scholz, 1972; Ensley, 1973). Evidence in the literature
supports the hypothesis that the amount of insoluble material produced at the interface, and
hence the resistance of the bond to moisture damage, depends on the amounts of chemical
reactants present on the aggregate surface and the bitumen (Institute, 2001). Methods such
as quantitative X Ray diffraction can be used to quantitatively determine the percentage
of active minerals on aggregate surfaces. This can be combined with the knowledge of
specic interactions between active minerals and functional groups from bitumen to predict
the behavior of bonding between the aggregate and the bitumen.
Another mode of loss of the aggregate-bitumen bonding is the failure in cohesion of
a weak boundary layer. Phenomenological observation indicates that when absorption of
bitumen on a porous aggregate occurs, the bitumen on the outside becomes hard and brittle
(Jeon and Curtis, 1990). This forms a weak boundary layer that makes the bond between the
bitumen and aggregate susceptible to premature damage. Podoll and Becker (1991) used
Surface Analysis by Laser Ionization (SALI) to examine water bonded surface of bitumen
and aggregate pairs. This technique essentially produces an elemental depth prole through
mass spectrometry. Calculation of relative abundances of various elements on the stripped
and unstripped areas indicates that the locations of failure of some bitumen-aggregate pairs
occurs on the aggregate side. Weak boundary layers of this nature may be intrinsic to the
aggregate used, or can be developed by dissolution of surface complexes (Jeon and Curtis,
1990) or the mineral itself in the presence of water. The latter is dependent upon the pH
of the contacting water. Cohesive failure due to dissolution of surface layers in carbonates
occur at pH levels lower than 6, while dissolution of silica minerals occurs at pH values
grater than about 8 (Jamieson et al., 1995b).
8
2.3 IMPACT OF CONSTRUCTION OPERATIONS ON AGGREGATE PROPER-
TIES RELEVANT TO ADHESION
2.3.1 Moisture on Aggregate Surfaces During Production
A number of factors during the production of asphalt mixtures inuence the quality of the
adhesive bond between the aggregate and the asphalt binder. The mechanical forces during
mix production change the physical and chemical characteristics of the aggregate. The
physical changes are evident in aggregate abrasion and breakage that can change aggregate
shape characteristics and gradation. These changes, although not signicant, affect the
mechanical bond between aggregates and the binder.
The temperature prole and the operation of a drum mix plant affects the aggregate
moisture content. A typical temperature prole along the depth of the drum is shown in
Figure 2.1. Aggregate movement along the drum is caused by gravity and the lifting ights
as the drumrotates. The owof aggregates is retarded in the middle of the drumto allowfor
better heat transfer from the exhaust gases so that the drying and heating of the aggregate
can take place. This can be accomplished by inserting a ring inside the drum, installing
reverse-angle ights to intercept aggregates, reducing the drum diameter in the middle, or
lowering the slope of the drum (HMA Handbook, 1991).
Although the temperature inside the drum decreases downstream, the aggregate tem-
perature does not follow the same prole. When aggregate is introduced into the drum,
its temperature increases as it moves downstream until it reaches a point before the drum
midpoint. After this point, the aggregate temperature remains almost constant as water
evaporates. The amount of time for which aggregate temperature remains constant de-
pends on moisture content and aggregate porosity. More porous aggregates may require
more time to remove moisture. Once most of the moisture has been removed from the ag-
gregate, its temperature begins to rise again. The moisture content of the mix at discharge
is almost always less than 0.5 percent.
Aggregate moisture content can have signicant effect on aggregate coating and perfor-
mance. At the point where asphalt is introduced in the drum, the small amount of moisture
remaining on the surface of the aggregate causes the volume of the binder to expand by
foaming and helps to coat the aggregate. Therefore, when the average moisture content
of the incoming aggregate is very low, incomplete coating of the aggregate may occur.
On the other hand, excessive moisture content in the aggregate would lead to performance
problems as the trapped moisture will damage the adhesive binder-aggregate bond lead-
9
Figure 2.1. Typical temperature prole in a drum mix plant during hot mix asphalt
production.
ing to moisture related damage that can be manifested in loss of binder, disintegration of
aggregate, and premature fatigue cracking and rutting.
Parker and West (1992) evaluated the impact of residual moisture in aggregates on the
stripping potential of asphalt mixtures. The moisture content of the aggregates just prior to
mixing with the asphalt binder in a drum mix plant depends on the ambient temperature and
the moisture content of the stock piles. Parker and West reported that aggregates may not
be effectively dried by the rapid heating in drum dryers. They also reported that siliceous
aggregates were more sensitive to the presence of residual moisture compared to limestone
aggregates. In another study, Fwa and Ong (1994) reported that smaller aggregate par-
ticles had more moisture content expressed as a percentage of the dry aggregate weight
as compared to larger aggregate particles. This was attributed to the larger surface areas
per unit mass of the smaller aggregate particles. However, these authors also reported that
the time required for fully saturated aggregate particles to oven dry at 110C was longer
for larger aggregate particles compared to smaller aggregate particles. The authors also
cite Lottmans (1961) observation that moisture in deep pores of large aggregates may not
completely vaporize if the aggregates are not heated for sufcient duration of time.
10
Typically, a very small amount of surface adsorbed water or residual moisture is re-
quired to reduce the surface free energy of the aggregate surface (Adamson and Gast,
1997). For example, Legrand (1998) reports that as the temperature for preconditioning
certain types of silica is decreased, the percentage of silanol groups on the surface increases
and the total surface free energy decreases. Reduced surface free energy of the aggregate
translates into reduced adhesive bond strength with the asphalt binder.
In summary, existing literature demonstrates that the temperature and duration for which
aggregates are heated prior to mixing with the asphalt binder are important factors that dic-
tate the durability of asphalt mixtures. This is especially an important consideration for
warm asphalt mixtures that are produced at temperatures that are typically 20 to 30C
lower than conventional mixtures. Although the workability of asphalt binders at lower
temperatures is achieved with the use of specialized additives, the qualitative and quan-
titative impact of residual moisture on aggregate surface on the durability of the asphalt
mixture remains to be addressed.
2.3.2 Aggregate Storage and Contamination
Aggregate storage is another factor that inuences aggregate surface properties. Solid sur-
faces with high surface energies, such as aggregates, rarely have clean surfaces in their
native environments (Adamson and Gast, 1997). Freshly crushed aggregate surfaces in a
quarry are rapidly contaminated upon coming into contact with the atmosphere. Dust parti-
cles, organic materials, and water from atmospheric humidity adhere to the freshly crushed
surfaces. Adsorption of impurities on the aggregate surfaces continues while the aggregates
are stored in stock piles before being used in the hot mix. Even a single layer of organic
molecules can contaminate and alter the surface properties of the aggregates. Sources of
such contaminants include exhaust from plant mix operations in the vicinity of the stock
piles and atmospheric water. The presence of dust and organic substance on aggregate sur-
face affect its surface energy, and consequently the efciency of binder coating and mix
performance.
Based on the testing of a limited number of aggregates, Little and Bhasin (2006) re-
ported that in most cases surface energy properties of freshly crushed aggregates did not
vary signicantly from that of aged aggregates. However, a more detailed investigation of
the affect of aging on the surface properties of aggregates is required.
Johnson and Freeman (2002) report the presence of dust on aggregates as one of the
causes for its poor adhesion to asphalt binder. Tarrer and Wagh (1991) report that the pres-
11
ence of excessive dust and clay coatings on the aggregate surface inhibits its adhesion with
the asphalt binder and also provides a pathway for the water to get to the binder-aggregate
interface. Kandhal (1992) report that dust coated aggregates promote hydraulic scouring
and deterioration in the asphalt mixture. This report also cites examples of cases where
removal of dust from aggregate surface by cleaning improved the adhesion characteristics
of the coarse aggregate.
In summary, existing literature demonstrates that the contamination of aggregates due
to presence of dust on the aggregate surface and/or aging of the aggregate may affect the
quality of its adhesion with asphalt binder. However, very little information is available
that quanties the impact of these factors on the adhesion with asphalt binder. This must
be considered for future work on aggregate properties.
2.4 TEST METHODS TO MEASURE AGGREGATE PROPERTIES RELEVANT
TO ADHESION
Adhesion is the tendency of dissimilar molecules to maintain intimate contact. Adhesion
involving geologic materials is controlled by the interfacial characteristics of rocks and
minerals, specically the surface energy of natural minerals and rocks. Surface energy is a
thermodynamic construct dened as the work necessary to form a unit area of surface by a
process of division (Parks, 1990; Shuttleworth, 1950). Conceptually surface energy can be
considered as the amount of energy lost when the molecular bonds that are normally lled
inside a solid remain unlled as a result of being at the edge of the solid (van Oss et al.,
1988a).
Surface energy of natural substances can be divided into a polar and non-polar com-
ponent. The non-polar (also referred to as the van der Waals or dispersive component) is
present in all molecules to varying degrees. These forces are produced by dipole-dipole in-
teractions and induced dipole interactions. Van der Waals interactions are generally weaker
than electrostatic interactions; however their inuence extends over longer distances (van
Oss et al., 2001). Polar or non-dispersive forces are found where electron donor/electron
acceptor interactions take place and are further divided into electron donor (Lewis base
like), and electron acceptor (Lewis acid like) components (van Oss et al., 1988b,a, 2001).
The polar or Lewis acid-base interactions are mainly hydrogen donor and hydrogen accep-
tor reactions (Fowkes, 1966). However, it is useful to dene polar more broadly for all
electron acceptor-donor interactions.
Using Good-van Oss Theory (vOGT) the total surface energy can be found by combin-
12
ing these elements as follows:

Total
=
LW
+2

(2.1)
In equation 2.1,
Total
is the total surface energy,
LW
is the Lifshitzvan der Waals or
dispersive component,
+
is the Lewis acid component, and

is the Lewis base compo-

nent (van Oss et al., 1988b,a).
Bhasin and Little (2006) and Hefer et al. (2006) used the Universal Sorption Device and
the Wilhelmy plate device to determine the surface free energy components of aggregates
and asphalt binders, respectively. They demonstrated a good correlation between parame-
ters derived from these surface energy measurements to eld and laboratory performance
of asphalt mixtures.
2.4.1 Universal Sorption Device
The universal sorption device (USD) is used to determine the surface energy components
of the aggregates. Tests with non-polar probe vapors such as nHexane are also used to
determine the specic surface areas of different aggregates (Bhasin, 2006). Most vapor
sorption methods described in the literature (Bilinski and Holysz, 1999; Chen and Dural,
2002) use very nely divided solids and a sample mass of about 1gmor less. These methods
cannot be effectively employed to measure surface free energies of aggregates on account
of their heterogeneity and difculties in obtaining a representative aggregate sample. One
of the capabilities of the USD is its ability to test larger sample sizes of about 25 grams
which enables testing of representative aggregate samples. The aggregate size fraction
typically used in this device is between ASTM #4 and ASTM #8 sieves. Since surface
energy of an aggregate is an intrinsic material property it is independent of its geometry
and it is not required to test every size fraction of the same aggregate. This is true unless
the size fraction is extremely ne where the general crystal structure of the surface is altered
affecting its surface properties. Such nes are more likely to be considered as part of the
bitumen mastic rather than an aggregate bound by the bitumen. It must also be noted that
the size fraction tested with the USD have the same mineralogy as the coarse and ne
aggregates used in a typical full graded asphalt mixture. In some cases, the aggregate used
in an asphalt mixture may be a blend of aggregates representing two different sources. In
such cases, samples representing each source are tested separately.
13
2.4.2 Wilhelmy Plate Method
The Wilhelmy plate method is used to determine the surface free energy components of the
asphalt binder. Although this method does not measure aggregate properties, the surface
energy components of the binder are required as an input in order to quantify its work of
adhesion with an aggregate in dry condition and the release of free energy when water
displaces the binder from a binder-aggregate interface (Cheng, 2002; Hefer et al., 2006).
Therefore, it is important to measure the surface free energy of typical asphalt binders for
further analysis. Bhasin et al. (2007) used the Wilhelmy plate device to demonstrate the
impact of modication processes such as aging of asphalt binder, addition of liquid anti
strip agent, and addition of polymers on the work of adhesion using different aggregates.
2.4.3 Micro-calorimeter
The micro-calorimeter can be used to measure the total energy of a solid-liquid or a liquid-
liquid interaction in the form of enthalpy of immersion. Ensley et al. (1984) determined
the heat of immersion of different aggregates in different asphalt binders using a micro-
calorimeter. He related the measured heat of immersion to the rutting performance and
moisture sensitivity of asphalt mixes. Bhasin and Little (2006) employed the micro-calorimeter
using different approaches to determine properties of aggregates relevant to adhesion with
asphalt binders. They used the micro-calorimeter to measure the enthalpy of immersion of
aggregates in different pure homogenous probe liquids in order to compute the total sur-
face energy components of the former. Similarly, the enthalpy of immersion of aggregates
in water (at room temperature) and asphalt binder (at mixing temperature) was used as a
measure of hydrophilicity of the aggregate and the total energy of adhesion between the
aggregate and the binder, respectively. The enthalpy of immersion of aggregates in asphalt
binder can also be measured at room temperature by using the asphalt binder in a suitable
solvent. One of the advantages of using a micro-calorimeter is that it is a relatively faster
technique compared to the USD. However, the specic surface area of the aggregates must
be known a-priori in order to provide a general interpretation of the test results. Another
advantage of the micro-calorimeter is that the aggregate surface can be pre treated to rep-
resent a variety of different conditions prior to the test. This is in contrast to the USD that
requires the test to be conducted always from a clean dry aggregate surface conditioned
under vacuum. This advantage of the micro-calorimeter allows it to be used for surface
characterization of aggregates used in the production of warm asphalt mixtures.
14
2.4.4 Aggregate Imaging System (AIMS)
Masad et al. (2005) report the use of an Aggregate Imaging System (AIMS) to rapidly
measure the shape, form, and texture characteristics of aggregates. This system is equipped
with top lighting, back lighting, and autofocus microscope. These are necessary elements
of the system to capture black and white images, and gray scales images at different mag-
nications for the analysis of all shape characteristics. The system is computer-controlled
to achieve motion in the x, y, and z directions as well as magnication. Masad et al. (2005)
developed a system for classication of aggregates based on their shape characteristics.
The AIMS was used in the preliminary portions of this study to determine the shape char-
acteristics of the aggregates.
2.5 TEST METHODS TO MEASURE PERFORMANCE OF ASPHALT COMPOS-
ITES
The test methods reviewed in the previous section are useful to determine properties of
aggregates that inuence its adhesion with the asphalt binder. Mechanical tests and perfor-
mance modeling of ne aggregate matrix or whole asphalt mixture is necessary in order to
quantify the impact of change in these properties on the performance of the asphalt mixture.
The ne aggregate matrix (FAM) represents the portion of the asphalt mixture that
comprises of the asphalt binder, nes (material passing #200 sieve), and ne aggregates
(material passing #16 sieve). The FAM is an important and critical component of the
asphalt mixture that holds the coarse aggregate matrix together. Material distresses such as
fatigue cracking can be considered to be largely concentrated in the FAM. The shape and
gradation of coarse aggregates inuence the overall performance of an asphalt mixture.
Since the focus of this study was to evaluate the inuence of production temperatures on
the mechanical properties and performance of the mix, it is helpful to focus on the inuence
of aggregate mineralogy by using FAM and ltering out the effect of shape and gradation
from coarse aggregates. The only requirement for this approach is that the ne aggregates
passing #16 sieve are selected to represent the mineralogy of the coarse aggregate in the
asphalt mixture.
The Dynamic Mechanical Analyzer (DMA) has been used in several studies to charac-
terize the aggregate-asphalt resistance to fatigue and moisture damage (Kim et al., 2004;
Branco et al., 2008; Masad et al., 2006). The DMA apparatus applies a cyclic, torsional
stress-controlled or strain-controlled load to a cylindrical sample of the FAM until failure
15
occurs. Specimens for DMA testing were prepared using ne aggregates (passing #16) and
asphalt binder in proportions that were representative of the original asphalt mixture.
Masad et al. (2008) used a comprehensive methodology to evaluate of the resistance
of DMA specimens to fracture under dry and wet conditions based on crack growth using
Paris law. They expressed Paris law in terms of the J integral of the dissipated pseudo-strain
energy as follows:
d r
dN
= A[J
R
]
n
(2.2)
where, r is the average crack radius in the specimen, and J
R
is the J-integral, which is the
pseudo-strain energy release rate per unit crack area dened below.
J
R
=
W
R
N
(c.s.a)
N
(2.3)
where, W
R
is the dissipated pseudo-strain energy (DPSE) per unit volume of the intact
material or the volume of the material that is capable of dissipating energy, c.s.a is the
crack surface area, which is equal to 2r
2
for a circular crack with radius r. By integrating
equation 2.2 the authors expressed the crack size as a function of loading cycles as follows:
r (N) =

2n+1
n+1
n+1
2n+1

A
(4M)
n
1
2n+1

N=0

W
R
N
n
n+1
dN

n+1
2n+1
(2.4)
where, M is the number of cracks in a specimen. Based on the work of Schapery and Lyt-
ton, n was approximated as 1/m for strain-controlled testing where m is the exponent of
time in the power law equation for the relaxation modulus. Lytton et al. (2001) developed
a form for A as a function of viscoelastic properties, bond energy, and tensile strength.
These properties were computed based on surface energy measurements and DMA tests.
Masad et al. (2006) and Little and Bhasin (2006) demonstrated a good correlation between
moisture sensitivity of various asphalt mixtures observed in the eld and the results ob-
tained using this approach with the DMA. Little and Bhasin (2006) also conducted tests on
dry and moisture conditioned specimen using the DMA in order to evaluate the moisture
sensitivity of the FAM.
Mixture performance can be characterized using a similar approach with the modi-
cation that the tests will be conducted on asphalt mixtures instead of the FAM. Another
methodology to characterize mixture performance in terms of plastic deformation is based
16
on applying creep and recovery tests at relatively high temperatures. The results from
this test when analyzed using a viscoelastic-viscoplastic model provide information on the
recoverable and irrecoverable components of the mixture deformation and the damage ac-
cumulated in each of these components (Dessouky, 2005; Saadeh, 2005).
2.6 SUMMARY
In summary, this chapter presented a review of the various aggregate properties and their
signicance in terms of dictating the strength, stability and moisture resistance of asphalt
mixtures. The chapter also presented a brief discussion on the various aspects of asphalt
mixture production that can inuence these aggregate properties as well a few methods to
determine the aggregate properties and mixture performance. The scope of this study was to
(i) evaluate the inuence of mixture production temperature on the adhesive characteristics
of aggregates and (ii) evaluate the adhesive characteristics of common minerals found in
aggregates. These two objectives are addressed in the following two chapters of this report.
17
CHAPTER 3. INFLUENCE OF MIXTURE PRODUCTION
TEMPERATURE ON ADHESIVE PROPERTIES OF
AGGREGATES
3.1 BACKGROUND
The production of hot mix asphalt (HMA) typically requires heating the asphalt binder
and aggregate to temperatures in the range of 140C to 160C. These high production
temperatures are required to generally achieve the required workability with the asphalt
binder and also to ensure that the aggregate surface is dry and forms a durable bond with
the asphalt binder. Therefore, selection of the mixing and compaction temperatures is
crucial to ensure proper aggregate coating, matrix stability during production and transport,
ease of placement, acceptable compaction, and ultimately acceptable performance of the
pavement.
Several new techniques have been developed to reduce the temperatures used for mix-
ing and compaction of hot mix asphalt (HMA). The asphalt mix produced at lower than
conventional mixing and compaction temperature using any of these techniques is referred
to as warm mix asphalt (WMA). Development of the WMA technology was initiated by the
German Bitumen Forum in 1997 in response to the Kyoto agreement. WMA is produced
at temperatures that are up to 40C lower than the typical HMA production temperatures.
Lower production temperatures reduce emissions, fumes and odors, and hardening of the
binder during construction. Lower production temperatures also offer benets such as en-
ergy savings, ability to open sites early and pave during cooler periods.
Some of the techniques currently being explored to produce WMA are: (i) creating a
foaming action within the asphalt binder at the time of mixing (e.g. WAM-Foam), (ii)
use of emulsion to reduce binder viscosity (e.g. Evotherm), (iii) use of mineral additives
to release water during the mixing process so that binder viscosity is reduced (e.g. Aspha-
Min and Advera), (iv) use of organic additives to reduce binder viscosity (e.g. Sasobit
and Asphaltan B), and (v) use of a combination of dry and wet aggregates during mix-
ing to release water and reduce binder viscosity (low energy asphalt). Irrespective of the
technique used to produce a WMA, a major concern while producing asphalt mixtures at
reduced mixing and compaction temperatures is inadequate drying of the aggregate surface
and its impact on the long term durability of the asphalt mixture.
19
Hurley and Prowell (2005a; 2005b; 2006) report that in some cases lower compaction
temperatures used to produce WMA increased the potential for moisture damage. They
speculated that incomplete drying of the aggregate at lower temperatures could have re-
sulted in the reduced durability of the asphalt mixture. Several researchers have evaluated
the performance of WMA produced using different techniques under laboratory conditions
(Hurley and Prowell, 2005a,b, 2006; Barthel et al., 2004; Sousa Filho et al., 2006; Wasi-
uddin et al., 2007). Most of these studies compare the performance of WMA to a similar
HMA. The ndings from these studies enumerate potential durability and performance re-
lated issues that are associated with the use of different WMA technologies. However, it is
also noted that such issues have not been reported from recent eld sections using WMA
mixes. This may be either due to the fact that such test sections are relatively few and recent
or that the laboratory tests do not accurately reect the degradation processes in the eld or
both.
There is a need to individually address each attribute that makes the WMA different
from a HMA. These include: i) efciency of the technique or additive that is used to im-
prove binder and mixture workability, ii) impact of residual moisture within or on the sur-
face of aggregate on the performance and durability of the mix, and iii) long term impact
of the additive that remains as a part of the mix (after paving and compaction) on its per-
formance and durability.
The main objective of this study was to isolate and evaluate the impact of reduced mix-
ing temperatures on the residual moisture retained on aggregate surfaces. Residual moisture
retained on the aggregate surface can reduce the bond strength between the asphalt binder
and the aggregate as well as the wettability of the asphalt binder to the aggregate. Wetta-
bility and the bond strength between the binder and the aggregate are strongly correlated
to the performance and durability of the composite (FAM or asphalt mixture). A micro
calorimeter was used to measure the total energy of adhesion between the asphalt binder
and aggregates pretreated at different temperatures. The test method was devised such that
the measured total energy of adhesion was only affected by the pretreatment temperatures
of the aggregate.
In addition to the results from the micro calorimeter, mechanical tests were conducted
on Fine Aggregate Matrix (FAM) specimens produced at different mixing and compaction
temperatures. As discussed in section 2.5, the performance and durability of an asphalt
mixture is strongly related to the performance and durability of its FAM (Kim et al., 2004;
Arambula et al., 2007). FAM specimens were produced at three different mixing and com-
20
paction temperatures for different asphalt binder-aggregate combinations. The mechanical
behavior of the FAM was evaluated using a Dynamic Mechanical Analyzer (DMA). A ze-
olite based additive was used to produce FAM specimens at reduced temperatures. The
choice of zeolite rather than other additives was based on the following rationale. One
group of specimens was prepared at reduced mixing and compaction temperatures using
hydrated zeolite particles as ller. Addition of hydrated zeolite particles causes micro
foaming which in turn improves workability of the binder and allows for the production
of FAM specimens at reduced temperatures. However, during mixing and compaction the
zeolite particles dehydrate and are retained in the specimen as a ller. A second group of
specimens was prepared at conventional mixing and production temperatures. In this case
dehydrated zeolite particles were added as a ller to the mix. Use of dehydrated zeolite will
not cause foaming and consequently will not affect the workability of the mix at conven-
tional mixing and production temperatures. Therefore this approach allows one to produce
and compare two groups of mixtures that are identical in composition but are produced at
conventional and reduced mixing and production temperatures. Such comparisons are not
possible with the wax based or emulsion based additives.
3.2 MATERIALS
Three aggregates with different mineralogies were selected from the Strategic Highway
Research Program (SHRP) Materials Reference Library (MRL): Basalt (RK), Gravel (RL),
and Limestone (RD) (Robl et al., 1991). Two asphalt binders, AAB and AAD, were also
selected from the SHRP MRL. Binder AAB is a PG 58-22 grade from Wyoming and AAD
is a PG 58-28 grade California Coastal product (Jones, 1993). The selection of softer grade
asphalt binders renders the mechanical performance of the mixture more sensitive to the
aggregate properties at test temperatures (around 25C).
3.3 INFLUENCE OF PRODUCTION TEMPERATURE ON ADHESION AND SUR-
FACE PROPERTIES OF AGGREGATES
3.3.1 Overview of the test method
A differential isothermal micro calorimeter (OmniCal Inc., USA) was used to measure the
inuence of aggregate treatment temperature (used to represent production temperature)
on the adhesive properties of the aggregate. This was done using two different methods
of measurement. First the total energy of adhesion (TEA) between an asphalt binder solu-
21
tion and aggregate specimens treated at different temperatures were measured directly. The
TEA represents the total energy given out as heat when the liquid (binder) adheres to the
surface of the solid (aggreagte). Second, the surface free energy components of the aggre-
gate specimens treated at different temperatures were measured by using heat of immersion
(HoI) with three different probe liquids. The HoI is similar to the TEA, except that the total
heat is measured for aggregate-liquid pairs where in the liquid is a pure probe liquid with
known surface tension characteristics. The surface energy values calculated using the HoI
were then used to estimate the adhesive bond strength of aggregates treated at different
temperatures with typical asphalt binders.
The total energy of adhesion or heat of immersion is inuenced by the specic surface
area (SSA) of the aggregates (the higher the SSA, the higher the energy released), and the
surface energy of the materials involved in the adhesion process. The SSA of the aggregates
in question was determined using a nitrogen adsorption method with BET equations (Gregg
and Sing, 1967).
The following is a brief description of the procedure to measure the TEA or HOI using
the micro-calorimeter. The solid or aggregate sample is placed in a 16 ml glass vial in
the reaction cell of the micro-calorimeter. Details of the solid sample are presented in
the following subsection. The glass vial has an open top polypropylene (PP) cap sealed
with a PTFE (poly-tetraouroethylene) line silicone septa. A similar empty glass vial is
placed in the reference cell of the micro-calorimeter. Syringes with 21 gauge needles lled
with a probe liquid are placed over the silicone septa of the reaction and reference vials.
A temperature controlled aluminum jacket encloses the vials and the syringes within the
micro-calorimeter. A series of thermocouples interconnecting the reaction and reference
cell measures the differential heat ow between the two cells within an accuracy of 10
watts. After the cells reach thermal equilibrium, syringes with the probe liquid (or asphalt
solution) are punctured through the silicone septa and the liquid is injected in both cells
simultaneously. Immersion of the aggregate in the liquid causes heat ow between the
reaction cell and the reference cell, which is recorded by the data acquisition computer and
accompanying software. Thermal equilibrium between the reaction and the reference cell is
restored after the reaction is fully complete. Integration of the heat ow curve between the
two equilibrium states (before and after injection) yields the enthalpy of immersion. Note
that the term reaction does not necessarily imply a chemical reaction where two materials
react to form a third material. In this report, the term reaction is also used to denote the
physio-chemical surface interactions between the clean aggregate surface and the liquid.
22
Figure 3.1 illustrates a schematic of the device used in this study (Bhasin, 2006). A more
detailed description of the materials used and test procedure followed for each of the three
different tests is described in the following sections.
Figure 3.1. Schematic illustrating the working principle of the differential
micro-calorimeter (Bhasin 2006) with a reaction cell containing ne aggregates and
an empty reference cell; the syringes on cells are lled with the liquid used to
immerse the aggregate sample.
3.3.2 Sample preparation
Aggregates passing ASTM sieve #100 and retained on ASTM sieve #200 were used for
this test. The aggregates were washed with distilled water to remove dust particles from
surfaces, and dried overnight in an oven. Two vials were used for each test, one empty
(reference) and the other with 8 g 0.01 g of the aggregate (sample). Both vials were
subjected to the same conditioning procedure. The aggregates were treated at four differ-
ent temperatures (90C, 110C, 130C, and 150C). The heat treatment was carried out by
placing the sample and the reference vials on top of an electronically controlled heating
surface. The vials were heated with open caps for a period of three hours at the speci-
ed temperature. Immediately after removal from the heater, the vials were closed using a
poly-propylene cap with air tight silicone septa. The vials were then allowed to cool down
to room temperature. This procedure allowed the aggregate sample in the vial to retain
its surface characteristics, which were representative of different mixing temperatures. In
23
addition to the four treatment temperatures, samples of each aggregate type were prepared
at 150C under vacuum for three hours as well as at room temperature (referred to as no
heat). High temperature and vacuum were used together in an attempt to create an ideal dry
aggregate surface. Additional details on the sample preparation procedure can be found in
(Vasconcelos et al., 2008).
In order to measure the TEA, stock solutions for different asphalt binders were prepared
using 1.5 g of asphalt dissolved in 11 mL of HPLC grade toluene. Previous studies con-
ducted at the Western Research Institute indicate that asphalt binder in a toluene solution
does not compromise the physio-chemical characteristics of the bitumen. Also, the bitu-
men molecules in a toluene solution have similar kinetics to those of molecules in liquid
bitumen at elevated temperatures (Western Research Institute, 2001). Figure 3.2 illustrates
the micro-calroimeter and a typical asphalt binder in the syringe that is injected into the
vial containing an aggregate sample (shown outside of the microcalorimeter).
The HoI of aggregates was measured using three different probe liquids: chloroform,
benzene, and heptane. All three liquids were HPLC grade. The HoI was used to estimate
the surface free energy of the aggregates.
3.3.3 Test and analysis
The micro calorimeter was used with its proprietary data acquisition and analysis software
to record heat ow during the test and to compute the total heat of immersion. The vial
with the aggregate sample was placed in the reaction cell and the empty vial was placed
in the reference cell of the micro calorimeter. Four syringes of 2 ml capacity each were
used to draw the asphalt solution or probe liquid. Two of these syringes were positioned
on top of the reaction vial and two on top of the reference vial (Figure 3.2). Heat ow
between the sample and reference cell was recorded using the software that accompanied
the micro calorimeter. The cells were allowed to reach thermal equilibrium. Equilibrium
was conrmed as the point when the heat ow ceased to change over time. After reaching
thermal equilibrium, the asphalt binder solution was injected into the vials.
The asphalt binder molecules preferentially adhere to the aggregate surface reducing
the total energy of the system and producing heat. The heat ow from the reaction cell was
recorded over time and the system was allowed to return to thermal equilibrium. The area
under the heat ow curve over time was integrated to obtain the measured TEA or HoI,
H
meas
(Figure 3.3). The magnitude of the TEA is proportional to the bond strength be-
tween the binder and the aggregate surface. In the case of the probe liquid, the magnitude
24
Figure 3.2. The micro-calorimeter (left) is shown with a typical vial containing an
aggregate sample (right); the asphalt binder is in solution form in the syringe ready
to be injected into the vial with the aggregate to measure the heat of immersion.
Figure 3.3. Typical heat ow measured using the micro-calorimeter when a solid
(aggregate) is immersed in a probe liquid.
25
of the HoI is proportional to the work of adhesion between the aggregate and the probe
liquid. A correction in the integrated value is necessary due to the difference in free vol-
umes inside the reaction and reference cells, H
v
. The corrected enthalpy of immersion
is determined as follows:
H
imm
=H
meas
H
v
=H
meas
H
vap
v
s
p
0
RT
(3.1)
where, v
s
is the volume occupied by aggregates in the vacuum sealed reaction cell, p
0
is the
saturation vapor pressure of toluene (or probe liquid in the case of HoI) at the test temper-
ature, R is the universal gas constant, T is the test temperature, and H
vap
is the change in
enthalpy due to vaporization or heat of vaporization per mole of toluene or probe liquids.
A minimum of three replicates were tested for each combination of three aggregates and
six treatment conditions with the two asphalt binders and probe liquids.
For the interaction between asphalt binders and aggregates, H
imm
divided by the total
surface area, A
sur f ace
, of the aggregates is the TEA or total energy of immersion per unit
surface area of the aggregate. The total surface area of the aggregates was determined as
the product of the specic surface area and the mass of the aggregate sample in the cell.
The specic surface area was measured using the multi-point BET method with nitrogen
as adsorbate, and with an outgas temperature of 150C. The specic surface areas for RK,
RL, and RD were: 11.292; 3.803; and 0.906 m
2
/g, respectively. It must be noted that the
rank order as well as the order of magnitude for the specic surface area of therse three
aggregates is the same as reported in previous studies on these aggregates (Robl et al.,
1991).
For interaction between the three probe liquids and the aggregates, the following method
was used to estimate the surface free energy of the aggregate. Equation 3.2 relates the heat
of immersion, H
imm
, to the three surface energy components of the aggregate and probe
liquid, and the total surface area of the aggregate, A
sur f ace
.
H
imm
= 2A
sur f ace

Total
l
2

LW
l

LW
a
2

+
l

a
2

l

+
a

(3.2)
In equation 3.2, the superscripts LW, +, and denote the non-polar, acid and base
components of surface free energy, respectively and the subscripts l and a denote the probe
liquid and aggregate, respectively. Since the specic surface areas of the aggregate were
measured using the nitrogen adsorption BET method, and the surface energy components
of the three liquids are known, the only unknowns in equation 3.2 are the three surface free
26
energy components of the aggregate. Consequently, heats of immersion with the three dif-
ferent probe liquids were used to generate a systemof three linear equations (using equation
3.2) in order to determine the three surface free energy components of the aggregate.
3.3.4 Results
The two asphalt binders (AAB and AAD) were combined with the three aggregates (RK,
RL and RD) treated using six different conditions: at ambient conditions with no heat
treatment, heated and dried at 90C, 110C, 130C, and 150C in air, and heated and dried
at 150C under vacuum. For the aggregates that were heated and dried in air, The TEA
was measured using three or more replicates for each of the aforementioned 36 combina-
tions. In addition, three probe liquids were used to determine the surface free energy of
aggregates as a function of the treatment temperature. Figure 3.4 illustrates the inuence
of aggregate treatment temperature on the total energy of adhesion for the combinations of
different asphalt binders and aggregates. Figures 3.5, 3.6, and 3.7 illustrate the inuence
of aggregate treatment temperature on the heat of immersion of these aggregates in differ-
ent probe liquids. The surface free energies of the aggregates were calculated using the
measured HoI with different probe liquids with equation 3.2. These surface energy values
were then used with the surface energy values for two different asphalt binders in order
to estimate the inuence of aggregate treatment temperature on its adhesive bond strength
with the asphalt binder (Figure 3.8).
3.3.5 Discussion
One of the objectives of this study was to isolate the impact of reduced mixing temper-
atures on the residual moisture on aggregate surfaces and concomitant changes in the
binder-aggregate bond strength. This was achieved in two ways: (i) by determining the
TEA between asphalt binders and aggregates pretreated at different temperatures and (ii)
by measuring the surface energy components of pre-treated aggregates and using these to
compute the adhesive bond energy with asphalt binder. Results based on the direct mea-
surement of TEA and the computed energy of adhesion were similar and the following
discussion pertains to both.
Results indicate that the TEA between the asphalt binder and the aggregate either de-
creases slightly or is not signicantly affected by the treatment temperature of the aggregate
within the temperature range of 90C to 150C (which is of interest for the production of
27
Figure 3.4. Inuence of aggregate treatment temperature on the total energy of
immersion with asphalt binders.
Figure 3.5. Inuence of aggregate treatment temperature on the heat of immersion
for aggregate RK.
WMA). The TEA between the asphalt binder and aggregate was also determined for aggre-
gates that were not subjected to any heat treatment. In this case, the TEA was signicantly
28
Figure 3.6. Inuence of aggregate treatment temperature on the heat of immersion
for aggregate RL.
Figure 3.7. Inuence of aggregate treatment temperature on the heat of immersion
for aggregate RD.
lower compared to aggregates treated between 90C to 150C. This was as expected, since
aggregates that are not heated retain substantial amounts of surface adsorbed moisture and
result in reduced adhesion with the asphalt binder.
29
Figure 3.8. Inuence of aggregate treatment temperature on computed adhesive
bond strength with different asphalt binders.
The conclusion would then, in summary, be that the TEA is substantially different for
aggregates that are not heated before mixing with asphalt binder and aggregates that are
heated before mixing with asphalt binder. However, the difference in TEA (for aggregates
mixed with asphalt binder) when the aggregates are heated to between 90C and 150C
before mixing with asphalt binder is not signicant. A signicant increase in the TEA
was observed for the limestone aggregate when the aggregate were treated at 150C under
vacuum as compared to when it was treated at the same temperature without vacuum. This
increase was not substantial for the other predominantly siliceous aggregates.
The results from this study were compared to the ndings from other similar studies
on different types of silicate minerals. Ligner et al. (1989) presented the variation in the
dispersive components of the surface energies for different silicates (amorphous and crys-
talline) as a function of thermal treatment. A decrease in the dispersive component of the
aggregate surface energy will reduce its bond strength with any given asphalt binder. Con-
sequently this should result in a lower TEA when measured using the micro calorimeter.
The results reported by Ligner et al. (1989) for crystalline and amorphous silicates suggest
that the TEA (at least for the siliceous aggregates) should not change signicantly for the
temperature range used in this study (90 to 150C). This was consistent with the results
30
based on the TEA measured using the micro calorimeter.
3.4 INFLUENCE OF PRODUCTION TEMPERATURES ON PERFORMANCE OF
FAM
3.4.1 Sample preparation
The mixture design for the Fine Aggregate Matrix (FAM) followed the method described
in Zollinger (2005). Fine aggregate particles smaller than 1.18 mm in size (passing ASTM
sieve #16) were used in the mixture design. The ne aggregates were separated into differ-
ent size fractions and recombined to match the gradation of a typical dense graded mixture.
The ne aggregates were oven dried for four hours at the selected mixing temperature prior
to use. The aggregates were then mixed with the asphalt binder and aged for a period of
two hours at the selected compaction temperature. Each combination of asphalt binder and
aggregate was prepared at three different mixing and compaction temperatures.
The rst mix was prepared using a mixing and compaction temperature representative
of conventional hot mix asphalt (according to ASTM D 2493). The other two mixtures
were prepared at 20C and 40C below conventional mixing and compaction temperatures.
These two mixtures are representative of WMA. Zeolite was added at the rate of 0.3% by
weight of the total mixture during the preparation of each of the three mixtures. As de-
scribed previously, the most important difference was that for the conventional hot mix,
the zeolite was dehydrated by heating it to the same temperature as the aggregate prior to
mixing. Since dehydrated zeolite does not release water during mixing it can be treated as
a mineral ller that is incorporated within the FAM. For the mixes prepared at reduced tem-
peratures, hydrated zeolite stored at room temperature was added to the aggregates along
with the asphalt binder during mixing. In this case, hydrated zeolite particles come into
contact with the binder, at relatively higher temperature. This causes the zeolite particles
to release their moisture and the binder to foam simultaneously improving the workability
of the mixture.
After mixing and short term aging, the dehydrated zeolite particles can be considered
to remain in the mix as mineral ller. The Superpave Gyratory Compactor (SGC) was
used to compact the mix and fabricate samples approximately 80 mm height in a 150 mm
diameter mold. The compaction was set to stop at 87% of the maximum specic gravity
(Gmm). The ends of the 150 mm diameter sample were sawed to achieve a target height
of 50 mm. Following this, approximately 15 specimens each of 12 mm diameter were
31
obtained by coring the 150 mm diameter SGC specimen. The bulk specic gravity of the
DMA specimens was determined and the average air void content of the samples was 15%
(+/- 1.5%). The specimens were then glued using epoxy to metal holders for testing with
the DMA.
3.4.2 Test and analysis
All tests using the DMA were conducted in the controlled-strain mode. A torsion load was
applied following a sinusoidal wave form at a constant frequency (10 Hz) and temperature
(24C) for all the tests. The test was performed in two steps: (i) a low strain amplitude
(0.0065%) was applied to obtain the linear viscoelastic complex modulus of the material;
and (ii) a high strain amplitude (0.15%) was applied to induce damage in the specimens.
The progression of damage during the cyclic loading process was monitored to determine
the fatigue damage resistance of the FAM. Both steps were conducted on at least four
replicate specimens for each of the eighteen mixtures, and at least four more replicates were
tested following moisture conditioning. Moisture conditioning was carried out by partially
saturating the specimens (65 - 80%) using a vacuum pump, and leaving the specimens
under water at room temperature for a period of 12 hours.
At high strain amplitudes, the apparent or measured shear modulus of the specimen
gradually decreases as the number of load cycles increases until the specimen fails. The
results from the DMA were analyzed to obtain three different measures of performance
for the FAM: (i) the undamaged viscoelastic properties of the FAM quantied based on its
shear modulus (G*) measured at 1200 cycles at a low strain amplitude, and (ii) the fatigue
damage resistance of the FAM determined based on a dissipated strain energy parameter.
Dissipated energy was used as a measure of fatigue life as it typically has much lower
variability compared to the number of load cycles to failure (Branco, 2008; Branco et al.,
2008). This was also conrmed based on the data from this study. In addition, the mois-
ture damage resistance of the FAM was quantied by comparing the above parameters for
moisture conditioned specimens to the same parameters for unconditioned specimens. The
following dissipated strain energy parameter was used to characterize the fatigue cracking
resistance of the FAM specimens.
W =
1
2

2
0

VE
G

N f

(3.3)
where, G

VE
is the complex shear modulus of the FAM specimen in its initial state deter-
32
mined using the low strain amplitude (0.0065%), G

N f
is the shear modulus just before
specimen failure when subjected to the cyclic test at the high strain amplitude (0.15%),
and
0
is the target constant strain amplitude during the fatigue test (0.15% in this case).
The number of load cycles to failure were identied from a plot of NG

1
/G

N
where N is
the number of load cycles, G

1
is the complex shear modulus at the beginning of the test
and G

N
is the complex shear modulus at the N
th
cycles. The number of load cycles at the
maximum value of NG

1
/G

N
was considered as N
f
(Figure 3.9). In addition to W from
equation 3.3, other dissipated energy parameters may also be used to characterize fatigue
damage in the FAM specimens. Masad et al. (2007) present the use of other parameters
such as the crack growth index to characterize the fatigue cracking life of FAM specimens.
In the context of this study, the material properties required to compute the crack growth
index could not be readily determined for specimens produced at the different tempera-
tures. Furthermore, since the objective of this study was to evaluate the impact of mixing
and compaction temperature on the mechanical behavior of FAM specimens, the parameter
based on equation 3.3 was considered to be adequate to characterize the fatigue cracking
resistance for comparative purposes.
Figure 3.9. A typical plot used to identify the number of load cycles to failure; note
that curve with the number of load cycles multiplied by the normalized reduction in
shear modulus has a well dened peak that is identied with failure.
To determine the moisture damage resistance of the mixtures, the specimens were par-
33
tially vacuum saturated (65-80%) and left under water for a period of 12 hours at room
temperature. After removal from water, the specimens were tested again the same strain
amplitude, temperature, and frequency as the unconditioned specimens. The shear modu-
lus at low strain amplitude and the dissipated energy parameter, W, at high strain amplitude
were determined as before. For each material combination, the values of the shear modulus,
G

, and dissipated energy parameter, W, were normalized with respect to results from the
unconditioned mix prepared at 155C. This facilitated the comparison of both factors (pro-
duction temperature and moisture conditioning) on a common scale. In other words, for
each material combination the normalized values of G

or W indicate the relative change

in the parameter due to the reduction in mixing temperature and/or moisture conditioning
with respect to the unconditioned mix prepared at 155C.
3.4.3 Results
In the rst step of the DMA test, shear modulus of the FAM specimens was determined
by applying 1200 load cycles (2 minutes at 10Hz) in torsion by applying a low strain am-
plitude. Figure 3.10 illustrates the average and standard deviation of the complex shear
modulus of mixtures prepared at different mixing temperatures; results were obtained on
three or more replicates for each material. In the second step of the DMA test, fatigue
cracking resistance of the FAM specimens was determined by applying cyclic loading at
a higher strain amplitude until failure occurred. The dissipated energy parameter W was
computed for all replicates of the 18 mixtures using equation 3.3. Figure 3.11 illustrates the
results for the average and the one standard deviation of the dissipated energy parameter,
W. A higher value of this parameter indicates better fatigue cracking resistance. Figures
3.12 and 3.13 illustrate the impact of mixing temperature and moisture conditioning on G

and W, normalized for each of the six different material combinations.

3.4.4 Discussion
The mechanical properties of the unconditioned FAM specimens, as determined using the
DMA, either decreased with a decrease in the mixing temperature or did not change signi-
cantly (Figures 3.10 and 3.11). This is most likely due to the differences in the effectiveness
of the warm mix additive to enable mixing and compaction at reduced temperatures. An-
other, although less likely, factor that can contribute to these differences is the increase in
residual moisture on the aggregate surface resulting in poor bonding with the asphalt. The
34
Figure 3.10. Inuence of mixing and compaction temperature on the shear modulus
of dry specimens (average shown with +/- one standard deviation).
Figure 3.11. Inuence of mixing and compaction temperature on the fracture
resistance of dry specimens (average shown with +/- one standard deviation).
inuence of this factor was isolated and discussed in section 3.3.5. Finally, the interaction
of the binder with the WMA additive, in this case the zeolite particles, is the least likely
factor for the differences in the mechanical properties shown in Figures 3.10 through 3.13.
35
Figure 3.12. Inuence of moisture conditioning on linear viscoelastic property of
different FAM specimens.
Figure 3.13. Inuence of moisture conditioning on fracture resistance of different
FAM specimens.
This is because the zeolite particles were added to all mixtures, WMA as well as those
produced at conventional mixing and compaction temperatures. It must be noted that the
aforementioned statement does not imply that additive does not interact with the binder. In
other words, for the experiment design used in this study, such interactions were normalized
36
by using a dehydrated form of the additive in the control mix.
Another aspect that must be noted from these results is that, for most combinations
of materials and mixing temperatures, moisture conditioning resulted in a reduced value
of G

and W as compared to the unconditioned specimens. In most cases, the response

of the moisture conditioned specimens prepared at different mixing temperatures followed
the same trend as that of the unconditioned specimens. Another observation was that, for
any given mixing temperature, the FAM prepared using asphalt binder AAD showed better
or similar resistance to moisture induced damage compared to asphalt binder AAB. This
is contradictory to ndings from previous studies that indicate that asphalt binder AAD
has poor resistance to moisture induced damage (Little and Bhasin, 2006). The anomalous
moisture resistance of materials with the binder AAD may be explained as follows. Ad-
dition of divalent cations to the asphalt binder has been shown to result in the formation
of water insoluble salts with carboxylic acids within the mastic. This promotes the migra-
tion of other functional groups such as pyridines, ketones, and sulfoxides to the aggregate
surface in order to form more durable, moisture resistant adhesive bonds. The above mech-
anism has been used to explain the improved moisture damage resistance of certain asphalt
binders with the addition of hydrated lime (Little and Petersen, 2005). Asphalt binders
with more polar and asphaltene content are generally most responsive to the action of the
hydrated lime (Plancher et al., 1976; Petersen, 1984). Since the asphalt binder AAD has
high asphaltene content and polar functional groups (Jones, 1993), and the zeolite that was
used in this study was rich in calcium ions, the authors hypothesize that the high moisture
damage resistance of binder AAD may be due to the mechanisms described above.
37
CHAPTER 4. PHYSIO-CHEMICAL AND ADHESIVE
PROPERTIES OF COMMON MINERALS IN AGGREGATES
4.1 BACKGROUND
As discussed previously, surface energy of bitumen and aggregate can be effectively used
to calculate bond strengths and energy parameters to rank the susceptibility of mixtures
to incur damage due to moisture. Prior to this research a comprehensive study of surface
energy characteristics within and across mineral groups had not been undertaken nor such
data reported. Therefore, the primary purpose and objective of this part of the study was to
assemble and report such data. Although aggregates used in asphalt mixtures are seldom
comprised of a single mineral, understanding the bond strength between bitumen and ag-
gregates or mineral surfaces (dry and in the presence of moisture) is essential to understand
the variability and source of adhesive bond strength between the aggregates and the binder.
Such a database can lead to a better understanding of minerals to avoid in asphalt mixture
combinations.
4.2 FACTORS THAT INFLUENCE SURFACE FREE ENERGY OF AGGREGATES
4.2.1 Non-polar active sites
Chemical surface energy components are located on natural surfaces in sites, commonly
termed active sites. These are the positions where sorption occurs. Combining known
knowledge of individual mineral surface characteristics to surface energy results can cor-
relate type and density of active surface sorption sites on minerals. The sorption sites on
minerals are of varying type (Johnston, 2002). There are two major positions that an active
site of a mineral can be found. These are on the edges and the basal surfaces. Of these two
positions an active site can be either polar or non-polar. Non-polar sites primarily bond with
van der Waals components of adsorbates. Non-polar sites are commonly found on micas,
zeolites, kaolinite, serpentine minerals, smectites, and a variety of other silicate minerals.
Vermiculites and chlorites have non-polar sites to a lesser degree (Johnston, 2002). Micas
and zeolites often have the strongest non-polar sites. non-polar sites are generally found on
the neutral siloxane surface of silicates. These surfaces have no charge and no permanent
dipole moment. Therefore, they are termed hydrophobic. Because of this hydrophobic na-
39
ture water has little or no interaction with neutral siloxane surfaces and they are not able to
form hydrogen bonds. Hydrophobic surfaces occur on 2:1 phyllosilicates where no isomor-
phic substitution has occurred. This is a result of the -2 charge on the oxygen atoms being
completely satised by neighboring silicon atoms (Huheey et al., 1983). Siloxane surfaces
act as very weak Lewis bases but are mostly inert. Their surface energy is therefore domi-
nated by van der Waals forces. For this reason, although water and other polar molecules
have a slight afnity for neutral siloxane surfaces, non-polar organic solutes and non-polar
regions of larger biological molecules such as proteins and enzymes can efciently bond to
this type of surface through van der Waals interactions (Johnston, 2002).
4.2.2 Polar active sites
Polar active sites on surfaces can be broken down into permanently charged sites, condi-
tionally charged sites, exchangeable metal cations, and exposed uncoordinated metal atoms
(Johnston, 1996). Polar sites react with Lewis acid/base components of adsorbates. Polar
sites are generally termed hydrophilic as a result of their charge and dipole moments. Con-
ditionally charged sites are pH dependent. Some examples of pH dependent sites are on
iron oxides such as goethite, aluminum oxides such as gibbsite, manganese oxides such as
birnessite, palygorskite and sepiolite, and a large number of other silicate minerals (John-
ston, 2002). In addition to these kaolinite, serpentine, phyrophyllite, talc, micas, zeolites
such as analcime, carbonates, and even titanium and zirconium minerals have some condi-
tionally charged surfaces.
Conditionally charged sites are primarily a result of inorganic surface hydroxyl groups.
They must always be located on edge sites. The best example of this is gibbsite as explained
by Johnston (2002). Permanent charge sites are often found on aluminosilicates such as
allophane (contains pH dependent sites as well), micas such as biotite, silicate clays such as
montmorillonite (also contain pH dependent sites, and vermiculite, and zeolites. Kaolinite
and serpentinites also contain some permanently charged sites.
Constant charged sites are a result of isomorphic substitution and defects within the
mineral. Isomorphic substitution is a process where one atom or molecule is replaced
by another of similar size. Isomorphous substitution often occurs in either the octahedral
or tetrahedral sheets of 2:1 phyllosilicates. This switch is sometimes accompanied by a
change in charge by the substituted atom. Constant charge sites are characterized by a
permanent negative charge (Johnston, 1996). One example is the substitution of Mg
2+
for Al
3+
in the octahedral sheet of layer silicates. Al
3+
often substitutes for Si
4+
in the
40
tetrahedral sheet. Both of these result in a gain of one electron. Isomorphic substitution
can result in a localized or delocalized charge. Mg
2+
for Al
3+
is thought to be delocalized
over approximately nine oxygen atoms on the siloxane surface whereas Al
3+
for Si
4+
is
more concentrated at around three oxygens (Sposito, 1989).
Closely related to constant charged sites described above are the exchangeable metal
cation sites. In this case, however, the metal cation is not replaced by another cation. In-
stead, the organic solute coordinates directly to the cation occupying the isomorphic substi-
tution site (Isacsson and Sawhney, 1983; Johnston, 1996). One example of this occurrence
is when phenols react with exchangeable alkali and alkaline earth metal cations on these
sites. The degree of metal-organic solute attraction will be a function of the organic solutes
ability to compete for coordination sites around the metal center (Isacsson and Sawhney,
1983). It is also possible for exchangeable and structural transition metals in their oxi-
dized state to interact directly with organic solutes. These metal cations can act as Lewis
acids when they accept electrons from the organic solute (Johnston, 1996; Voudrias and
Reinhard, 1986). An example of this reaction is when Cu
2+
or Al
3+
interact with reduced
aqueous solutes. Cu
2+
and Al
3+
are themselves reduced and a radical organic cation is
produced on the surface. These last two types of polar active sites are common on clay
minerals.
4.2.3 Coatings
All surface energy measurements are based on the surface conditions at the time of mea-
surement(Parks, 1990). Any surface can be altered to change its surface energy (Staszczuk,
1985). An example of this is when large organic molecules sorb to phyllosilicates. The
organic molecule balances the charges of the polar and non-polar sites. The interface es-
sentially becomes part of the interior of a new material comprised of the mineral and the
organic molecule (Neu, 1996). The new edge site has very different characteristics than the
layered silicate had originally. Smaller changes can also affect the surface energy charac-
teristics. If a metal cation is sorbed from an aqueous solution onto the surface of a mineral
it can satisfy a net negative charge imbalance. This reaction causes the negative component
to decrease. Conversely a loss of a metal cation leads to an increase in the electron donor
component of the surface free energy. In addition the presence of water or other aqueous
solution at the surface will increase the positive component.
Water also transports various media making sorbate species available to the material
surface. Conditionally charged surfaces are also strongly affected by the external environ-
41
ment. Acidic solution provides excess hydrogen positive charges to the surface of the min-
eral increasing the electron acceptor component. Basic solutions remove positive charges
from the mineral surface causing the electron donor component to increase. Thus, the ex-
ternal environment can alter the surface energy even when coatings do not bond to the
surface.
4.3 MATERIALS AND METHODS
The method to establish the pure phase minerals surface energies involves using the Uni-
versal sorption device (USD). This device carries the advantage of being a convenient
method that can be used on a routine basis with minimal human biases. All tests were
performed on pure mineral samples that were purchased or obtained. The surfaces of the
pure phase minerals were characterized using an electron microprobe. This characteriza-
tion involves establishing the surface mineralogy and purity of each mineral. Tables 4.1
and 4.2 list the pure minerals used in this study.
4.3.1 Elemental analysis of the minerals
Elemental analyses were performed on the bulk properties of the minerals. Measurements
were achieved by crushing the samples below a number 35 standard sieve and placing them
in an oven for 24 hours at 75C. The samples were then placed in a desiccator and per-
cent nitrogen, sulfur, and carbon was measured with an Elemental Analyzer. Sulphanilic
acid was used to establish the calibration curve at .072, .56, 1.04, 1.6, and 2.6 mg. Sul-
phanilic acid composition was measured at 8.09% nitrogen, 41.61% carbon, and 18.5%
sulfur. Montana soil standards reference material (SRM) 2711 was used for quality control
every 25 samples.
Blanks were placed after each Montana soil standard to allow venting of residual ma-
terial from the standard and the previous samples. All samples were analyzed in quadru-
plicate unless otherwise noted. Detection limits were set at 0.01 N%, 0.018% C, and 0.01
S% based on the calibration curve used for these analyses, however personal experience
on this device has shown that these detection limits are conservative. The minerals were
washed with distilled (DO) and reverse osmosis (RO) water prior to crushing to remove
large particles on the surface. Aggregates were also washed with DO and RO water prior
to crushing. After crushing, the aggregates were separated and three batches were made
for all except RD-7 Limestone. Batch number one was placed in consecutive hydrochloric
42
acid solutions until effervescence ceased. Batch one was performed in quadruplicate and
placed in the oven. Batch two was placed in consecutive hydrochloric acid solutions in
quadruplicate and not placed in the oven. Batch three was not placed in acid solutions or in
the oven. This was done to quantify organic carbon and carbonate carbon in the samples.
No nitrogen was measured above detection limits in any of the samples. Both carbon and
sulfur were present above detection limits in most samples. Carbon to nitrogen ratios are
listed for comparison. The detailed results from the elemental analysis of the minerals used
in this study can be found (Miller, 2009).
4.3.2 Pretreatment of minerals for surface energy testing
Samples of the minerals were crushed with a stainless steel impact mortar to be passed
through a #4 (4.74 mm) ASTM standard sieve and retained by a #8 (2.36 mm) ASTM
standard sieve. This method was chosen as opposed to saws and pressed powders to mimic
natural erosion by breaking along cleavage or fracturing. After the samples were crushed
they were be washed with reverse osmosis water to remove large particles and then with
distilled water. The minerals were then placed in an oven (Fisher Isotemp 200 series) at
75-80C for at least one day. The samples were then allowed to cool for one hour and then
were carried to the USD. They were not placed in a desiccator to cool so that they would
continue to closely model minerals in the environment.
4.3.3 Testing with the universal sorption device
Theoretical background
As discussed in the previous sections, the USD indirectly measures the surface free energy
of solid surfaces based on the work of adhesion of a solvent vapor onto the solid. The
USD uses adsorption isotherms to calculate the specic surface area of the solid, and the
spreading pressure of the vapor over the solid. Hexane vapor is used to calculate the specic
surface area of the mineral using the relationship:
A =

n
m
N
0
M

(4.1)
where A is the specic surface area, N
0
is Avogadros number, M is the molecular weight
of the probe vapor (86.16 for hexane), is the projected area of a single molecule, and
n
m
is the monolayer capacity of the solid surface (Gregg and Sing, 1967). Bhasin and
43
Little (2006) used the liquid density formula to estimate the projected area of a hexane
molecular as 39
2
. However, Bhasin found that using 56.2
2
, which was a value found in
the literature, t Micrometrics N
2
specic surface area measurements of aggregates more
tightly (McClellan and Harnsberger, 1967). The estimated 56.2
2
hexane molecule will
hereafter be referred to as the standard hexane molecule.
The monolayer capacity is the number of molecules required to cover the solid surface
in a single layer and is calculated as:
n
m
=
1
I +S
(4.2)
where S is the slope and I is the intercept of the best t line between P/n(P
0
P) and P/P
0
;
and where P is the partial vapor pressure, P
0
is the maximum saturation vapor pressure, and
n is equal to the mass of vapor adsorbed per unit mass of the mineral. From the isotherm
the equilibrium spreading pressure of the reference vapor over the solid is calculated using:

e
=
RT
MA
p
n

0
n
P
dp (4.3)
where
e
is the equilibrium spreading pressure, R is the universal gas constant, T is the test
temperature, M is the molecular weight of the probe vapor, n is the mass of vapor adsorbed
per unit mass of the mineral at the vapor pressure P, and A is the specic surface area of the
mineral. The spreading pressure is related to the work of adhesion through the equation:
W
SN
=
e
+2
Total
v
(4.4)
where W
SN
is the work of adhesion between the reference vapor and the solid,
e
is mean
equilibrium spreading pressure of the reference vapor over the solid, and
Total
v
is the total
surface energy of the reference vapor. Finally, using the Good - van Oss theory the work of
adhesion can be related to surface energy using the equation:
W
SN
= 2

LW
s

LW
v
+2

+
s

v
+2

s

+
v
(4.5)
where W
SN
is the work of adhesion between the reference vapor and the solid being tested
and other terms are as described before where subscript v refers to the probe vapor and
subscript s refers to the solid (aggregate or mineral). Using three probe vapors with known
characteristics (n-hexane, methyl propyl ketone, and water), a system of equations can
44
be created in order to solve for the three unknowns in equation 4.5. For a more detailed
description of the USD device and its usage the reader is referred to Bhasin and Little (6).
Testing
After the samples were oven dried approximately 20 to 25 grams of a mineral sample was
placed in the sample cage, and the sample column was closed. The sample and sample
column were then brought to vacuum (< 0.05 mbars) and hot degassed at 60C for at least
two hours. Next, the Rubotherm magnetic suspension balance was run continuously (auto
balance) until the readings remained stable within 0.001g. When the analytical balance
remained consistently stable n-hexane was introduced into the sample chamber. Hexane
has no electron acceptor or electron donor components; therefore it only exerts van der
Waals forces onto the mineral sample. For this reason, hexane can be used to calculate the
van der Waals component for the mineral surface energy. The sample was then exposed to
ten equal increments of partial vapor pressure from vacuum to saturation vapor pressure.
After each increment the adsorbed mass was recorded to plot the adsorption isotherm after
it reached equilibrium. The process was repeated using methyl propyl ketone (MPK) and
water as the reference vapors. For each mineral, the adsorption isotherms using the three
reference vapors were used to compute the surface free energy components of the mineral
sample as well its specic surface area following the procedure described above.
4.4 RESULTS FROM SURFACE ENERGY TESTING
4.4.1 Carbonates
Five carbonates were analyzed on the USD: Calcite (CaCO
3
), Cerussite (PbCO
3
), Siderite
(FeCO
3
), Rhodochrosite (MnCO
3
), and Dolomite (CaMg(CO
3
)
2
). The carbonate series
was most useful for comparing surface hardness and softness. This was accomplished by
comparing the surface chemistry of the various cations. The SSA of the carbonates ranged
from .06 to .28 cm
2
/g based on the standard hexane molecule. Methylpropylketone was
very low and did not vary much across the carbonate series.
Calcite and Dolomite
Calcite surface energy was primarily non-polar with a fractional polarity of .25. The total
surface energy was 46.54 ergs/cm
2
. Dolomite surface energy was also non-polar with a
fractional polarity of .25. Dolomite and calcite differed considerably on the van der Waals
component, however with 34.94 and 60.29 ergs/cm
2
respectively. The polar surface energy
45
of calcite was 11.6 ergs/cm2 while dolomite was approximately double at 20.28 ergs/cm
2
.
Rhodochrosite, Cerussite, and Siderite
The polar surface energy increased from cerussite, rhodochrosite, to siderite. This increase
corresponded with the hard/soft acid base concept. The van der Waals energy was 35.07,
40.33, and 61.39 ergs/cm
2
for cerussite, rhodochrosite, and siderite. Cerussite was limited
in sample quantity. For this reason an error analysis could not be performed. The coefcient
of variation for the total surface energy of rhodochrosite was 5.81%and 16.21%for siderite.
Siderite was the only sample to have a fractional polarity greater than .50.
4.4.2 Sulfates
Gypsum was acquired for analysis. In order to improve any heterogeneity the bassanite and
hot gypsum were prepared from the gypsum sample. After the gypsum was fractured with
the impact mortar between a number 4 and 8 sieve 1/3 of the sample was placed in the oven
at 75C for two weeks. When gypsum (CaSO
4
2H
2
O) is heated to 70C it loses 1.5 waters
and becomes Bassanite (commonly known as hemihydrates CaSO
4
0.5H
2
O).
The rest of the sample was placed in a plastic bag and stored. Half of the remaining
sample was placed in vacuum and hot degassed in the same manner at the other minerals
while the rest was allowed to get to vacuum but not hot degassed. The bassanite measured
the highest SSA with all the reference vapor calculations. Hot gypsum measured higher
SSAfor MPKand both waters indicating higher afnity for polar molecules. The difference
was most profound with water. Bassanite SSA for 5 and 10 square angstrom water was
approximately 30 times higher than hot gypsum and 40 times higher than gypsum. Gypsum
measured higher SSA for both hexane molecular sizes.
Bassanite
The bassanite sample showed a large increase in polar surface energy (59.90 ergs/cm
2
). The
van der Waals component was slightly lower than gypsum and hot gypsum. Fewer sample
runs were performed on bassanite than the other two sulfates based on time constraints on
the universal sorption device. This caused an increase in standard error. The coefcient of
variation for the standard hexane molecule was 29.19% for the total surface energy.
Gypsum and Hot Gypsum
As discussed in the chemistry section the gypsum sample was homogeneous and the sample
size was over 500 grams. The coefcient of variation for the standard hexane molecule was
46
1.81% for non-polar and 8.9% for polar surface energy. The 95% condence interval for
the total surface energy was 56.45 to 62.84 ergs/cm
2
. Hot gypsum measured similar results
to gypsum. The main differences were increased afnity to polar probe vapors. The polar
surface energy of hot gypsum was 21.49 while the polar surface energy for gypsum was
18.52 ergs/cm
2
. The fractional polarity was 3% higher.
4.4.3 Phyllosilicates
Four phyllosilicates were analyzed on the sorption device: biotite, muscovite, kaolinite,
and montmorillonite. Two of the minerals were clays (kaolinite, and montmorillonite).
These samples were separated from all the other minerals based on their specic surface
areas. SSAmeasurements with the standard hexane molecule were two orders of magnitude
higher than the other mineral specimens. Kaolinite SSA was 10.53, and montmorillonite
SSA was 23.30. These agreed well with literature values.
Muscovite & Biotite
Muscovite and biotite are 2:1 phyllosilicates with of the tetrahedral sites occupied by
Al
3+
instead of Si
4+
. This charge increase is balanced by monovalent potassium in the
interlayer. The main difference between biotite and muscovite is that biotite is trioctahedral
and muscovite is dioctahedral. This means that the hydroxides in the octahedral sheet are
balanced by a divalent cation in trioctahedral sheets and a trivalent cation in dioctahedral
sheets. This is the reason that biotite is more dense than muscovite (3.09 and 2.82).
The total surface energy for muscovite and biotite were 82.07 and 67.41 ergs/cm
2
.
The non-polar component was roughly equal with biotite begin slightly higher (47.55 and
52.51), but muscovite had a larger polar component (34.52 to 14.90). The acid component
of biotite was the second lowest of the mineral set (.01). This increased the error of this
measurement due to its proximity to the detection limit. The coefcient of variation for the
acid component of biotite was 181.49%.
Kaolinite
It was also necessary to place the kaolinite on the special holder inside the sorption device
because of the friable nature of kaolinite. The total surface energy of kaolinite was 70.51
ergs/cm
2
. The magnitude was mainly due to the polar component, 40.02 ergs/cm
2
. This
gave a fractional polarity of .57. Thus, the polar component of kaolinite was similar to
montmorillonite, but the non-polar component was much less. The acid component was
47
higher than the acid component for montmorillonite, but both were higher than the mineral
average.
Montmorillonite
The montmorillonite mineral sample had a non-polar surface energy of 42.85 ergs/cm
2
.
This was higher than kaolinite but lower than the two micas. The polar component was
22.45 ergs/cm
2
. This was lower than kaolinite and muscovite. The montmorillonite was
homogeneous, but very friable. For this reason the sample had to be placed in a specially
designed holder cage inside the USD in order to catch the sample if any broke off during
adsorption of the probe vapors. The error for the sample reected the homogeneity. The
coefcient of variation of the total surface energy was 10.66% and the 95% condence
interval was 51.65 to 78.94 ergs/cm
2
.
4.4.4 Feldspars
Four feldspar samples were sampled: microcline, albite, andesine, and labradorite. Micro-
cline is a Potassium rich Feldspar. Albite, andesine, and labradorite are all members of the
plagioclase Na-Ca series. Albite has the most sodium (90-100%). Andesine and labradorite
are intermediate composition (50-70 & 30-50% respectively). Feldspars are very common
igneous, sedimentary, and metamorphic minerals, and therefore are very important to the
study. The specic surface areas of the feldspars ranged from .10 to .27 cm
2
/g. This range
was higher than the average of the other mineral groups and very similar to the aggregate
specic surface areas. Labradorite had the highest SSA for every reference vapor except
water.
Albite
The albite sample was from a pegmatite and homogeneous. This was displayed in the
tight non-polar surface energy range. The coefcient of variation for the standard hexane
molecule was 3.54%. The 95% condence interval was 48-55.15 ergs/cm
2
with an average
of 51.57. The acid component was the lowest of the feldspars (.22), but the base component
was the second highest second to andesine).
Andesine
The andesine sample measured the highest total surface energy of the feldspars (129.88
ergs/cm
2
). This was mainly due to the polar component measured at 89.24 ergs/cm
2
. The
fractional polarity was also the highest of the feldspars at .69.
48
Labradorite
The chemical composition of labradorite and andesine were very similar (Na.45Ca.50Al1.51Si2.50O
8
and Na.49Ca.45Al1.47Si2.53O
8
respectively both with minor potassium). Thus, any differ-
ence in surface energy might be attributed to other characteristics such as surface coatings
or surface morphology. The total surface energy was measured at 82.92 ergs/cm
2
with
non-polar and polar surface energies of 46.21 and 36.71. Thus, the fractional polarity was
.44. The acid component was much higher than the average for the feldspars (1.81 and .72
ergs/cm
2
). The base component, however was the lowest of the feldspars.
Microcline
The microcline (KAlSi
3
O
8
) was perthitic. Perthitic feldspars are inter grown with sodic
alkali feldspar. Perthitic texture and composition is very common in feldspars. The sample
was pegmatitic which increased the value of the mineral as a homogeneous sample for
measuring the surface energy. Microcline had a large van der Waals component of 44
ergs/cm
2
, and the polar component was only 19.35. This gave a fractional polarity of .31.
The acid component was .46 ergs/cm
2
. This was very close to andesine and albite. The
total surface energy was 63.35 ergs/cm
2
.
4.4.5 Oxides
The oxides measured were quartz (SiO
2
), hematite (Fe
2
O
3
), and ilmenite (FeTiO
3
). Quartz
is also a tectosilicate similar to the feldspars sampled. Specic surface areas for the oxides
ranged from .05 to .1 cm
2
/g for the standard hexane molecule. Using water as the SSA
vapor lowered the measurement slightly. For a 10 square angstrom water molecule the
SSA ranged from .03 to .04 cm
2
/g. Using MPK as the SSA probe vapor lowered the
measurements again to a range of .01 to .02 cm
2
/g.
Hematite
The total surface energy of hematite was measured as 128.81 ergs/cm
2
. This was higher
than the other oxides. The sample had higher polar surface energy than non-polar with
a fractional polarity of .62. The sample was homogeneous but limited in amount. This
caused the condence interval to be larger than desired. There was enough sample to give
an estimate of the magnitudes of the components.
49
Ilmenite
The ilmenite sample was also limited in quantity; however the homogeneity of the sample
(see chemistry section) caused the surface energy measurements to remain tight in range.
The total surface energy 95% condence interval was 49.5-72.2 ergs/cm
2
with a coefcient
of variation of 9.47%. The average total surface energy for the standard hexane molecule
was 60.89. The non-polar surface energy was 39.76 was 21.13 ergs/cm
2
giving a fractional
polarity of .35. This showed that the sample surface energy was controlled by the non-polar
portion.
Quartz
The quartz van der Waals component measured 50.33 ergs/cm
2
for the standard hexane
molecule and 68 ergs/cm
2
for 39
2
hexane molecule. The acid component for quartz
was close to zero. This measurement was close to the detection limit for the sorption
device. This caused the coefcient of variation for the acid component and the total polar
component to be much larger than other minerals. The coefcient of variation for the
acid component was 471%, and the coefcient for the total polar component was 72.81%.
The quartz sample surface energy was controlled by the non-polar component (fractional
polarity of .09). Thus, there were not many unlled bonds on the surface of the sample.
4.4.6 Nesosilicates and Inosilicates
The neso/Inosilicate group had the largest variation in surface energies of any mineral
group. Augite had the highest surface energy at 367.78 ergs/cm
2
. The fractional polar-
ity was .95. The specic surface areas of this group were modest, however with a range
of .03 to .25 cm
2
/g. The van der Waals component increase from olivine, hornblende, to
augite. The fractional polarity of olivine was .30. Heterogeneity increased from olivine,
hornblende, to augite.
A summary of the surface energy results is presented in Table 4.3 and Figure 4.1.
4.5 DISCUSSION
In the context of asphalt mixtures, the surface free energies of mineral aggregates are im-
portant to quantify the moisture damage or stripping potential of different aggregate-binder
combinations. The correlation between the surface properties of these materials and their
tendency to strip in the presence of water is relatively well established in the literature.
50
Figure 4.1. Summary of total, polar and non-polar components of surface energies
for minerals (arranged by group and in the order discussed above).
The three quantities based on the surface energies of asphalt binders and aggregate that are
related to the moisture sensitivity of an asphalt mixture are:
work of adhesion between the asphalt binder and aggregate (W
AB
),
work of debonding or reduction in free energy of the system when water displaces
asphalt binder from a binder-aggregate interface (W
ABW
), and
work of cohesion of the asphalt binder or mastic (W
BB
).
The above three quantities are computed using the surface free energy components of the
individual materials. For an asphalt mixture to be durable and have a relatively low sensi-
tivity to moisture, it is desirable that the work of adhesion, W
AB
, between the asphalt binder
and the aggregate be as high as possible. Furthermore, the greater the magnitude of work
of debonding when water displaces the asphalt binder from the binder-aggregate interface,
W
ABW
, the greater the thermodynamic potential that drives moisture damage will be. There-
fore, it is normally desirable that this quantity be as small as possible. This is because this
term is usually (almost always) a negative quantity, and the more negative it is, the more
likely it is for water to replace bitumen at the interface with mineral or aggregate. Little
and Bhasin (2006) developed an energy ratio (ER) based on the two energy terms W
AB
and W
ABW
and which combines these terms into a single, dimensionless parameter. They
51
later adjusted this ratio to also consider the afnity of the bitumen to develop a cohesive
interaction (W
BB
). The resulting energy ratio (ER
2
) is expressed by:
ER
2
=
W
AB
W
BB
W
ABW
(4.6)
Equation 4.6 denes a parameter that can be used to estimate the moisture sensitivity of
asphalt mixtures based on the hypothesis that moisture sensitivity is directly proportional
to the dry adhesive bond strength, and inversely proportional to the work of debonding or
the reduction in free energy during debonding. Another form of this equation used in the
earlier study was the product of ER
2
and specic surface area of the aggregate. The work
of debonding is determined as follows:
W
ABW
=
AW
+
BW

AB
(4.7)
where,
AW
is the bond strength between the aggregate and water,
BW
is the bond strength
between bitumen and water, and
AB
is the interfacial bond energy between the bitumen and
the aggregate. Figures 4.2 and 4.3 show evidence of the utility of equation 4.6 in predicting
moisture damage based on laboratory experiments (tensile modulus, Figure 4.2, and plas-
tic deformation, Figure 4.3) with twelve different mixtures (twelve combinations of three
aggregates and four bitumens). In the tensile test, Figure 4.2, the ratio of tensile resilient
modulus in the wet (moisture conditioned) state compared to the tensile resilient modulus
in the dry state is plotted on the ordinate versus ER
2
on plotted on the abscissa. In Figure
4.3, repeated compressive loading was continued until the sample accumulated one percent
permanent strain. The ratio of the number of cycles to accumulate one percent strain for
each mixture under wet (moisture conditioned) and dry conditions is plotted on the ordinate
versus the energy ratio (equation 4.6) on the abscissa. In both gures, the dashed lines rep-
resent the 95 percent condence range and demonstrates the strong relationship between
moisture damage, as recorded by these ratios, and ER
2
.
Consider the energy ratio of the form shown in 4.6 for the different minerals with two
substantially different asphalt binders (AAB and AAD). The properties of these binders
were obtained from previous studies (Hefer et al., 2006). The energy ratio was computed
for all combinations of these two binders tested with the minerals. Figure 4.4 shows these
energy ratios for each mineral evaluated as the ERs progress from low to high (most resis-
tant to moisture damage). The ratios are calculated for the two asphalts (AAB and AAD)
with the ER always higher (more moisture resistant) for bitumen AAB, regardless of the
52
Figure 4.2. Laboratory performance (tensile modulus) of mixtures compared to ER2
* SSA (ER2 is a parameter based on surface free energies of asphalt binder and
aggregate and SSA is the specic surface area of the aggregate). (After Little and
Bhasin, 2006).
mineral considered. Since surface area, diffusivity (sorption of bitumen into pores spaces,
etc.) also affect bond strength, the ERs do not necessarily mean superior resistance to mois-
ture damage. However, they should be an excellent indicator of the inherent tenacity of the
bond based on adhesive bond strength.
The efcacy of the data in Figure 4.4 is supported by Figure 4.5, which compares the
wet to dry fatigue ratio for bitumens AAB and AAD for three different aggregates. In a
series of controlled experiments on dense graded asphalt mixtures, it was demonstrated that
a combination of AAD with three different types of aggregates was relatively more suscep-
tible to moisture induced damage as compared to AAB. These results represent the ratio
of fatigue life of moisture conditioned specimens to dry specimens. The fatigue tests were
conducted in direct tension mode by applying cyclic loads with constant stress amplitude
at a frequency of 10Hz. All test specimens were designed and fabricated to have a similar
binder content, air void content, and gradation.
Finally, Figure 4.6 presents the energy ratio data by mineral category and shows by the
number in the text block the number of minerals within the group for which the calculated
53
Figure 4.3. Laboratory performance (plastic deformation) of mixtures compared to
ER2 * SSA parameter (ER2 is a parameter based on surface free energies of asphalt
binder and aggregate and SSA is the specic surface area of the aggregate) (After
Little and Bhasin, 2006).
value of was positive. A positive value of indicates that the bitumen developed a preferred
(thermodynamically stable) adhesive bond with the mineral surface compared to water (one
phyllosilicate, two carbonates, one sulfate and one neo-silicate). More specically, the min-
erals that formed inherently thermodynamically stable bonds with bitumen were olivine
in the neo / ino silicate group, gypsum and hot gypsum in the sulfate group, calcite and
cerussite in the carbonate group, and montmorillonite in the phyllosilicate group. In other
words, these mineral surfaces form a bond with bitumen that is more stable than the bond
with water suggesting that stripping due to water is not thermodynamically favorable for
these combinations. Hundreds of measurements of aggregate and bitumen surface energies
at Texas A&M University indicate that none of the aggregate-bitumen combinations ana-
lyzed thus far were thermodynamically resistant to stripping. This apparent contradiction is
resolved by considering the fact that aggregates used to produce asphalt mixtures comprise
of more than one mineral. It is very likely that the sum effect of all minerals on the ag-
gregate surface will usually result in an aggregate-bitumen bond that is thermodynamically
prone to stripping as evidenced in the previous studies.
54
Figure 4.4. Energy ratio representing inherent resistance to moisture induced
damage for mineral-asphalt binder pairs presented from lowest to highest and for
asphalts AAB and AAD (higher energy ratio indicates better resistance to moisture
damage).
Surface energy results from this study on pure minerals indicate that there is a possi-
bility that localized regions on aggregate surfaces with these minerals may be inherently
resistant to stripping. However, such minerals are very limited in number and the stability
would depend on the mineral as well as the surface chemistry of the binder. It is also inter-
esting to note that no minerals within the oxides and feldspar group were found that were
thermodynamically stable with either one of these two binders. Certainly, these results
deserve more evaluation and consideration.
Although the prime objective of this research was to assess the variability of bond
strength developed between asphalt and the 22 representative minerals selected, a sec-
ondary objective was to understand the complex interrelationship between the three master
variables of surface energy: surface chemistry, surface morphology, and surface coatings.
However, the complex interactions among these master variables and the indirect manner
in which surface energies of solids must be measured prevents a clear path to separating
out the clear impact of these master variables. Nonetheless, several trends were observed.
55
Figure 4.5. Comparison of fatigue lives of moisture conditioned asphalt mixtures to
dry asphalt mixtures for bitumen AAB and AAD.
Figure 4.6. Surface energy trends within a mineral group and identication of
minerals that preferred a bond with bitumen rather than water.
First, organic coatings appear to have the greatest impact aside from the mineral type,
and they have the most impact when the amount becomes great enough to be considered
56
as a separate phase. This is most evident in the comparison of carbonates. The hard/soft
acid/base (HSAB) concept appears to hold true until the amount of organic carbon on the
surface increases signicantly. The siderite sample (4.4 moles of organic carbon) appears
to have enough organic coating to have established a separate phase. None of the other
carbonate samples had as much organic carbon (1.07, 1.95, 0.92, and 1.46 moles). How-
ever, a weak positive trend can also be seen when all of the Lewis Base component surface
energies are plotted against moles of surface organics (Figure 4.7).
Second, organic coatings may increase the Lewis base component. By comparing each
of the individual mineral groups there is no noticeable pattern that arises from the magni-
tude of the organic material on the surface with van der Waals and Lewis Acid. However,
when comparing all of the groups together there appears to an increase in Lewis base sur-
face energy with organic coatings. A weak linear correlation exists among each of the
mineral groups between Lewis basicity and total organic carbon. This might show that
surface coatings always play a role in surface energy, but are additionally affected by other
variables. If a strong correlation was seen then it could be argued that organic coatings are
a dominant control on Lewis Basicity. This, however was not seen.
Third, the universal sorption device specic surface area calculations correlate well
with literature values for similar minerals. Bhasin and Little (Bhasin and Little, 2006)
found that a good correlation exists between aggregate SSA measurements of n-Hexane
adsorption and BET nitrogen adsorption. This research found that results compared well
with published values for similar minerals. This may be evidence that the assumption of
n-Hexane preferentially laying along its long axis is correct.
57
Figure 4.7. Base surface energy versus moles of organic carbon on mineral surfaces.
58
Table 4.1. List of Minerals for Surface Energy Measurements
Minerals Group Formula Comments Acquisition
Andesine Tectosilicate Na(70-
50%)
Ca(30-
50%)
(Al,Si)
AlSi
2
O
8
Dominant feldspar in andesite. Minor
in granite and metamorphic rocks.
TAMU
Collection
Albite Tectosilicate NaAlSi
3
O
8
Found in granite and metamorphic
rocks.
Maine
Augite Inosilicate (Ca,Na)
(Mg,Fe,Al)
(Si,Al)
2
O
6
An important rock-forming mineral in
many igneous rocks, especially in
gabbros and basalts.
TAMU
Collection
Bassanite Sulfate CaSO
4

0.5H
2
O
An active mineral that constitutes
Plaster of Paris.
RNG
Collection
Biotite Phyllosilicate K(Mg,Fe)
3(AlSi
3
O
10
)
(OH)
2
Biotite is a common rock forming
mineral present in most igneous rocks
and both regional and contact.
TAMU
Collection
Calcite Carbonate CaCO
3
Common in sedimentary rocks.
Calcite is also the predominant
mineral in limestone, the predominant
rock that is crushed into aggregate.
Mexico
Cerussite Carbonate PbCO
3
An ore of lead. Tsumeb,
Namibia
Dolomite Carbonate Ca
Mg(CO
3
)
2
A common sedimentary rock-forming
mineral, dolomitic limestone.
RNG
Collection
Gypsum Sulfate CaSO
4

2H
2
O
Common mineral found in arid
landscapes
RNG
Collection
Hematite Iron Oxide Fe
2
O
3
Formed as a secondary weathering
mineral in soils.
RNG
Collection
Ilmenite Iron
Titanium
Oxide
FeTiO
3
Common oxide in igneous
environments
RNG
Collection
Kaolinite Clay Al
2
Si
2
O
5
(OH)
4
Common clay found in variety of soils
and aggregates
RNG
Collection
Labrad-
orite
Tectosilicate Ca(50-
70%)
Na(50-
30%)
(Al,SI)
AlSi
2
O8
Labradorite is a common feldspar. Naim,
Labrador
59
Table 4.2. List of Minerals for Surface Energy Measurements
Minerals Group Formula Comments Acquisition
Microcline Tectosilicate KAlSi
3
O8 Common feldspar found in granites. TAMU
Collection
Montm-
orillonite
Clay (Na,Ca)
(Al, Mg)
6(Si
4
O10)
3(OH)
6
Common clay found in variety of soils
and aggregates.
RNG
Collection
Muscovite Phyllosilicate KAl
2
(AlSi
3
O
10
)
(F,OH)
2
Common silicate in igneous,
sedimentary, and metamorphic
environments.
RNG
Collection
Olivine Nesosilicate (Mg,Fe)
2SiO
4
Found in ultramac igneous rocks and
marbles that formed from
metamorphosed impure limestones.
San
Carlos,
Arizona
Quartz Tectosilicate SiO
2
Most abundant mineral of the crust;
ubiquitous in all environments.
Arkansas
Rhodochrosite Carbonate MnCO
3
Minor ore of manganese. RNG
Collection
Siderite Carbonate FeCO
3
Common mineral found in
sedimentary formations.
Idaho
60
Table 4.3. Summary of Surface Energy Measurements of Minerals (ergs/cm
2
)
Mineral Acid Base Total
Polar
Compo-
nent
van der
Waals
Total
Surface
Energy
Andesine 0.40 3755.04 77.70 40.64 118.34
Albite 0.22 501.69 21.22 51.57 72.79
Augite 8.69 3890.33 367.78 52.67 420.45
Bassanite 0.30 3036.03 59.90 38.27 98.16
Biotite 0.07 809.97 14.90 52.51 67.41
Calcite 0.40 85.16 11.60 34.94 46.54
Cerussite 0.11 113.14 7.04 35.07 42.11
Dolomite 0.18 564.05 20.28 60.29 80.57
Gypsum 1.31 65.47 18.52 41.13 59.65
Gypsum (HD) 1.32 87.66 21.49 42.24 63.73
Hematite 2.85 558.07 79.82 48.99 128.81
Ilmenite 0.35 318.90 21.13 39.76 60.89
Kaolinite 5.01 80.00 40.02 30.48 70.51
Labradorite 1.81 186.54 36.71 46.21 82.92
Microcline 0.46 202.79 19.35 44.00 63.35
Montmorillonite 1.57 80.43 22.45 42.85 65.29
Muscovite 0.55 544.68 34.52 47.55 82.07
Olivine 1.55 57.52 18.87 44.17 63.04
Quartz 0.02 365.00 5.04 50.33 55.37
Rhodocrosite 0.86 145.76 22.33 40.33 62.66
Siderite 1.59 789.63 70.80 61.39 132.18
61
CHAPTER 5. CONCLUDING REMARKS
5.1 INFLUENCE OF MIXTURE PRODUCTION TEMPERATURE
The use of warm mix asphalt has several benets such as energy savings and reduced
emissions. Several research studies have compared the performance of HMA to a similar
WMA produced using different additives and techniques. While these comparisons are
typically made on a holistic basis, there is a need to individually assess the source and
impact of the various factors that differentiate a WMA from a HMA. The objectives of this
study were to evaluate the impact of reducing mixing temperatures on the: i) mechanical
behavior of the ne aggregate matrix (FAM) portion of an asphalt mixture, and ii) residual
moisture on aggregate surfaces and concomitant adhesive bond strength with the asphalt
binder.
In this study, a calcium based synthetic zeolite was used to prepare FAMs produced
over a range of mixing and compaction temperatures. The key ndings from this study are
as follows:
Results based on the dynamic mechanical analysis of the FAM specimens indicate
that for a given material combination, shear modulus and fatigue cracking resis-
tance of the FAM typically decreased when mixing and compaction temperatures
decreased.
Results based on the micro calorimeter demonstrate that for the aggregates with rel-
atively low porosity used in this study, lower aggregate pretreatment temperatures
(within the range of 90
o
C to 150
o
C) did not signicantly impact the total energy of
adhesion. From this, the researchers infer that residual moisture on the aggregate
surfaces at reduced mixing temperatures (within the range of 90
o
C to 150
o
C) did not
signicantly contribute to the observed reduction in the shear modulus and fatigue
cracking resistance at lower mixing temperatures.
A link between the diminished mechanical properties of the FAMs based on DMA
measurements and the reduction in pretreatment temperatures of the aggregate and
the rate of dehydration of the zeolite ller was established. Moisture egress from
zeolite was determined to be slower at lower treatment temperatures. It is speculated
that this could have resulted in the potential for more residual moisture in mixtures
63
prepared at lower temperatures. The higher residual moisture content of the FAMs
prepared at lower temperatures is consistent with inferior mechanical properties.
Based on the historical performance data of the binders used in this study, it appears
that the use of a synthetic zeolite with calcium ions may help improve the moisture
damage resistance of certain asphalt binders.
An important consideration related to the above ndings is that the ndings are limited to
aggregates with low porosity. For porous aggregates, such as certain types of limestone,
lowering the mixing temperature may inuence the moisture absorbed within the aggregate
bulk and consequently contribute to the adverse performance of mixtures. The authors are
conducting further research on the impact of using porous aggregates with WMA.
5.2 PHYSIO-CHEMICALANDADHESIVEPROPERTIES OF MINERALAGGRE-
GATES
The USD can differentiate among surface energy measurements of aggregate and mineral
surfaces, and such measurements can be used to calculate bond strengths between bitu-
men and aggregate and to identify mixtures susceptible to moisture damage. Twenty-two
minerals that commonly comprise the surfaces of aggregates were carefully selected and
tested. The authors believe this to be the most extensive catalog of mineral surface proper-
ties ever compiled. This catalog can serve as a reference for properties that can be used to
explain specic interactions between minerals and materials interacting with these miner-
als including but not limited to bitumen and water. Surface energies vary over the range of
minerals tested; and within a group or category of aggregate, substantial differences in sur-
face energy occur. These differences are probably related to chemical composition, surface
roughness or surface area, and coatings. Due to the complexity of the interactions of the
master variables, the authors could not, independently validate the impact of each master
variable. However, a trend between organic coating and surface energy was identied.
The dimensionless energy ratio of adhesive bond strength between aggregate (mineral)
and bitumen in dry condition to the bond strength in the presence of water demonstrated a
wide variation based on the mineral considered and always favored the bond with bitumen
AAB compared to bitumen AAD and this is veried by laboratory mixture testing. How-
ever, it was surprising that some minerals developed a thermodynamically favored bond
with bitumen compared to the competing bond between aggregate and water. Previous
testing on aggregates and computation of energy ratios always revealed the thermodynamic
64
potential of water to replace bitumen at the aggregate surface. However, aggregates are not
generally purely comprised of one mineral type, and the large majority of the minerals
tested demonstrated a potential to strip. This nding requires more evaluation.
65
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