THERMAL DEGRADATION OF ANTISTRIPPING AGENTS

AND E N H A N C E D P E R F O R M A N C E BY C U R I N G
By Hyon H. Yoon, ~ Arthur R. Tarrer, 2 and Vinay P. Wagh3

ABSTRACT: The heat stability of antistripping (AS) additives held in hot asphalt
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cement is investigated by observing the changes in additive concentration and

additive performance with holding time at 162.8~ The effect of mix curing by
hot storage 149~ on stripping resistance is also investigated. The diffusitivity of
an additive in hot-asphalt cement is measured to determine the rate of additive
migration to the aggregate surface during curing. The concentrations of all com-
mercial AS additives tested are observed to decrease significantlywhen heated in
asphalt at 162.8~ with a corresponding loss in effectiveness. It is also found that
mixture curing by hot storage remarkably improved stripping resistance. This is
believed to be due to improved adhesion of asphalt to the aggregate surface.
Additive migration rate to the aggregate surface is shown to be higher than apparent
curing rate. This implies that the enhanced stripping resistance observed with curing
is not due to additive migration. Asphalt hardening occurring during mixture curing
is shown to have only a second-order effect on stripping resistance.

INTRODUCTION

Stripping of asphalt cement from p a v e m e n t aggregates has long been

recognized as a m a j o r cause of failure in asphaltic concrete pavements. The
cause of stripping is attributed to water o r moisture penetrating the asphalt-
aggregate matrix. Stripping results in a loss of integrity of the asphaltic
concrete and subsequent failures, requiring early and costly maintenance.
A n u m b e r of methods have been d e v e l o p e d for reducing stripping damage
in asphaltic concrete pavements. Of these methods, the addition of a chem-
ical antistripping (AS) additive has become the most widely practiced method
for maintaining p a v e m e n t durability, because of its relatively low cost and
ease of implementation. Lime is the most widely used A S additive. A large
n u m b e r of other A S additives, which are normally surfactants, are com-
mercially available today. According to the 1984 survey of state highway
agencies by Tunnicliff and R o o t (1984), m o r e than 100 chemical A S additives
are used in the United States.
A S additives are used to improve the resistance of the asphalt p a v e m e n t
to stripping damage. Most A S additives are mixtures of p r o p r i e t a r y chemical
compounds, and detailed characterizations of these c o m p o u n d mixtures are
usually not available; however, most of the active compounds are typically
amines or chemical c o m p o u n d s derived from a m m o n i a (Mathews 1962;
H u b e r and T h o m p s o n 1955). Usually these compounds act as cationic sur-
factants that reduce interracial tension at the asphalt-aggregate interface.
Many A S additives are known to be susceptible to heat, and thus, with
storage in hot asphalt cement, the effectiveness of these additives can be
severely reduced (Mathews 1962; H u b e r and T h o m p s o n 1955; Dybalski
1982). Dybalski p o i n t e d out that some fatty diamines, which are used as
1Chem. Engrg. Dept., Auburn Univ., Auburn, AL 36849.
2Chem. Engrg. Dept., Auburn Univ., Auburn, AL.
3Chem. Engrg. Dept., Auburn Univ., Auburn, AL.
Note. Discussion open until July 1, 1993. To extend the closing date one month,
a written request must be flied with the ASCE Manager of Journals. The manuscript
for this paper was submitted for review and possible publication on July 25, 1989.
This paper is part of the Journal of Materials in Civil Engineering, Vol. 5, No. 1,
Februaw, 1993. 9 ISSN 0899-1561/93/0001-0001/$1.00 + $.15 per page. Paper
No. 27020.

J. Mater. Civ. Eng. 1993.5:1-18.

 AS additives, thermally degrade to amides at 100~ and above. In addition,
in this temperature range (100~ many of the AS additives can interact
chemically or physically with compounds in the asphalt to form inactive
complexes (Huber and Thompson 1955), which cannot act as surfactants.
Tunnicliff and Root (1984) have observed, however, no significant loss in
AS additive effectiveness with storage at high temperatures 162.8~ In
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order to clarify the importance of heat stability to AS additive performance,

a study was done in which the rate of additive disappearance due to either
degradation or interaction with asphaltic components was measured directly,
and then correlated with the additive performance as measured by a boiling-
water test. The boiling-water test was performed to determine the stripping
propensity of a mix. If the asphalt separated from the aggregate surface
during this test, it was characterized as having stripped, and the asphalt-
a.ggregate bond was concluded to have been weak and to have a high strip-
ping propensity.
Storage of hot asphalt-aggregate mixes increases the flexibility of oper-
ation of the mixing plant. For this reason, the effects of hot storage on
asphaltic concrete have been studied by a number of investigators (Zdeb
and Brown 1974; Kandhal and Wengler 1974). Most of these studies have
been concerned with the effect on hardening of the asphalt coating, migra-
tion of asphalt, and segregation of the mix. Little attention has been given
to the chemical effect of hot storage on stripping resistance. However, hot-
mix storage, which is called "high-temperature curing," was thought to
improve stripping resistance, as a result of more efficient migration of an-
tistripping additives to the aggregate surface (Dybalski 1982) and/or an
increase in adhesion between the asphalt and aggregate surface due to the
formation of a "solid" layer of asphalt on aggregate surface (O'Connor
1984).
Because of the chemical makeup of asphalt and AS additives, irreversible
chemical interactions are suspected to occur at the aggregate surface during
hot-mix storage (or curing). The reaction mechanisms would be similar to
those by which coke forms on solid catalysts in petroleum-refining processes.
Catalyst deactivation by coking has been observed to occur even at low
temperatures (100~ under hydrogen deficient conditions.
The presence of an AS additive at the aggregate surface should promote
adhesion because of either improved "wettability" between the aggregate
and the asphalt or because the AS, which tends to concentrate at the in-
terface, has a propensity to induce coupling between the asphalt and ag-
gregate. For the aforementioned reasons, a study was done to examine the
response of AS additive performance to high-temperature curing. To better
understand the role of additive migration during curing, the diffusivity of
an AS additive in a hot-asphalt cement was also measured.

EXPERIMENTAL
Materials

Asphalts
Two different AC-20 asphalt cements and an AC-30 asphalt cement were
used in this study. These asphalts, which were produced by different man-
ufacturers, were supplied by the Alabama Highway Department. The as-
phalt cements were labeled AC-20-1 (supplied by Amoco), AC-20-2 (sup-
plied by Chevron), and AC-30-1 (supplied by Hunt Oil).

J. Mater. Civ. Eng. 1993.5:1-18.

 Aggregates
An Alabama granite, for which stripping problems had been experienced,
was used throughout the study. This aggregate was crushed and screened
to 0.00925 m - - N o . 4 mesh size.

Antistripping Additives
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Five different antistripping additives were used in this study. All the
additives were commercial antistripping additives, marketed by three dif-
ferent manufacturers. In each case, the additive was mixed with asphalt
cement by first placing the additive in a glass beaker and then pouring asphalt
cement, heated at 135~ into the beaker. The mixture was then stirred
vigorously with a spatula for 30 s. The mixture was placed back in the oven
at 135~ for 5 rain, followed by vigorous stirring for l min to assure complete
mixing.

Procedures

Boiling-Water Test
After soaking in distilled water for 24 hours and towel drying, 100 g of
water-saturated aggregate was placed in a stainless-steel bowl and held in
an oven maintained at 149~ for one hour of preheating time. Next, asphalt
cement that had been heated at 135~ for 10 minutes was poured onto the
preheated aggregate in the ratio of 5.5 g of asphalt to 100 g of aggregate.
The asphalt and aggregate were mixed for 2 rain using a hot spatula and
placed in an oven maintained at 149~ for 10 rain. After it was cooled to
room temperature, the completely coated aggregate was placed into boiling
water (250 ml in a 400 ml beaker) on a hot plate. The water was maintained
at a slow boil for 10 rain; during this time the immersed aggregate was
stirred using a glass rod for 10 s at intervals of 4 rain and 8 rain of boiling.
The mixture was then held in the water while it was allowed to cool to room
temperature. After cooling to room temperature, the water was drained
from the beaker, and the mixture was placed on a paper towel and allowed
to dry.
The resultant amount of stripping was determined by visual observation
and reported in terms of the observed percentage of asphalt coating retained
on the aggregate. A rating board was developed having 10 intervals from
0% to 100% of retained coating, in order to standardize as much as possible
the visual evaluation.

Infrared Spectra of Antistripping Additives

Each antistripping additive used was characterized by fingerprinting its
infrared spectra using a Perkin-Elmer (Model 983) infrared spectropho-
tometer. All spectra were taken using capillary films of the additives. Each
additive sample was placed directly between two KBr windows, which were
then squeezed together and mounted in the spectrophotometer for analysis.

Ultraviolet Spectroscopic Analysis

AS additive concentrations in asphalt cements were measured quantita-
tively using a Gilford ultraviolet and visible spectrophotometer (Model 250).
UV spectra in the region of 240-340 wavelength were obtained by scanning
with a split 1-cm path length quartz cuvette to determine characteristic
absorption bands of the AS additives. A pair of 1-cm path length silica
cuvettes was used in measuring the absorbance of the samples at the char-

J. Mater. Civ. Eng. 1993.5:1-18.

 acteristic absorption band. The accuracy of the UV spectroscopic analysis
(extraction and measurement) was 92%.
The asphalt sample (about 2.0 g) containing an additive was dissolved in
a solution (20 ml) of 20 weight percent n-butyl alcohol and 80 weight percent
hexane using a sonicator. The solution was then placed in a 125-ml sepa-
ratory funnel and mixed with 20 ml of extraction solution consisting of 27
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volume percent concentrated hydrochloric acid and 73 volume percent dis-

tilled water saturated with sodium chloride. After vigorous mixing for 3
min, the sample was left undisturbed in the separatory funnel to allow the
layers to separate. Warming was necessary for complete separation of the
layers, especially for samples that contained high concentrations of the
additive. The bottom layer, the aqueous phase, was then used to make the
ultraviolet absorbance measurements at the characteristic wavelength. A
reference solution was prepared by following the same procedure but using
an asphalt sample containing no additive.
Using different samples containing known additive amounts, standard
analytical AS additive concentration versus absorbance curves were pre-
pared, and subsequently, were used in determining the additive concentra-
tions of unknown asphalt samples.

Metal Analysis
Some AS additives contain metals (e.g., Carstab BA2000), and most other
liquids can be complexed with a tracer metal such as copper (Yoon 1987).
The AS additive concentration in an asphalt cement can thus be determined
by measuring the tracer metal content in the asphalt sample. Copper metal
analyses, for diffusion studies, were done using an atomic absorption (AA)
spectrophotometer (a Varian model AA-475). A calibration curve for the
amount of metal (using standard solutions) versus absorption was first de-
veloped. The asphalt samples were slowly ashed (Petersen et al. 1974) in
preparation for performing the AA analyses to minimize metal evaporation
losses.

Heat-Stability Test
Each asphalt sample was sealed in a metal container and placed into an
oven (with an air atmosphere) maintained at specified temperatures for
different periods of time. Initially, each sample contained a specific amount
of AS additive. The samples were analyzed by measuring the residual con-
centration of the additive and observing the asphalt's performance using
the boiling-water test.

Mixture Curing
A mixture of an aggregate and asphalt cement was prepared following
the same procedure as that used for the boiling-water test. The mixture was
cured by placing it in an oven maintained at 149~ in either an ambient or
nitrogen atmosphere. When specified, a nitrogen atmosphere was used.
After curing, the mixture was tested using the boiling-water test.

Diffusivity Measurement
A special glass-tube diffusion cell, a schematic of which is shown in Fig.
1, was designed for measuring the diffusivity of an AS additive. The cell
consisted of 10 glass tubes (Pyrex, 2 cm inside diameter, and 1 cm in length)
connected together with silicone rubberbands. Initially, the cell was sepa-
rated into two equal-size parts, each of which was capped at one end with

J. Mater. Civ. Eng. 1993.5:1-18.

 Illlcone |lllcon! Glas t Tabe:
em ID
9 length

I
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I i I I I I .... | I" I I 1 I I I I_.J

t AJl~halt with I
tl
Alphall without .I
Additive Additive 1

~ . i~'~:!~z~;s ~;i!~if:)~iiiii~!iii!i~iiiii~ill~i::

FIG. 1. Schematic of Glass-Tube Diffusion Cell

a silicone rubber stopper. One-half of the cell was filled with an asphalt
containing no additive, while the other was filled with an asphalt containing
an AS additive. These two parts were connected using a silicone rubberband
so as to provide close contact between the asphalt in the two halves. The
connected cell was then placed horizontally in an oven and held at a specified
temperature for a given period of time (e.g., six hours). The cell was quickly
cooled to room temperature by immersing it in ice water. It was then sep-
arated into its 10 separate parts by cutting the silicone bands. The concen-
tration of the AS additive in each section (each glass tube) was measured
to determine the additive concentration gradient along the cell. It was as-
sumed that the entire system was at the oven temperature during the dif-
fusion process.

Adsorptivity Measurement
Granite was further crushed and then separated by screening into a 40-
60 mesh-size range and washed with distilled water. The powdered granite
was then dried by heating it in an oven at 162~ for 24 hours and cooling
it in a vacuum desiccator. An asphalt sample (10 g of AC 20), which con-
tained a specified amount of an AS additive (<1 weight percent), was
dissolved in toluene (50 ml). The dried granite powder (10 g) was added to
the asphalt solution in a 250-ml round flask with a ground glass stopper.
The mixture was continually shaken in a water bath at 20~ except during
sampling. The asphalt-toluene solution was sampled periodically after de-
cantation. The AS additive in the sample was extracted using an aqueous
HC1 solution. This was then analyzed by UV spectrometry to determine its
AS additive concentration.

J. Mater. Civ. Eng. 1993.5:1-18.

 RESULTS AND ANALYSIS
Heat Stability
An infrared analysis was performed for all five amine based AS additives
tested (Table 1). These spectra had major functional bands of primary and
secondary amines and organic nitrogen compounds. This implied that the
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additives contained primarily amines or amine derivatives. Additives 2, 4,

and 5 contained mostly primary amines.
Generally, amines are known to be capable of reacting with some of the
components present in asphalt cement. For example, amines can react with
carboxylic acids and anhydrides to form amides (Linfield 1969). Amides,
unlike amines, are not effective AS additives (Mathews 1962).
Some additives such as fatty diamines and amidodiamine salts including
quaternary ammonium compounds are likely to decompose in hot asphalt
(Mathews 1962; Huber and Thompson 1955; Dybalski 1982). In addition,
active components in the additives can become coupled with other com-
ponents within the additives and/or with some components of asphalt (Hell-
geth et al. 1984). Any of the aforementioned reactions and also thermal
degradation can result in the additive losing its polarity. Thus these reactions
result in a loss in additive effectiveness. It should be noted also that additives
that contain primary amines have relatively high vapor pressures and may
vaporize at elevated storage temperatures, and this would result also in a
loss of additive effectiveness.
Fig. 2 shows the change in concentration of an AS additive (1) mixed in
different asphalts while it was held at 162.8~ The additive concentration
in the asphalts was measured using the UV method described earlier. The
amount of additive loss was significant and depended upon the type of
asphalt in which it was incorporated. Apparently, a significant amount of
additive loss occurred due to the reaction between the additive and asphalt
components and/or due to thermal degradation and/or by evaporation. The

TABLE 1. Compositional Properties of Antistripping Additives

Major Functional Infrared Bands (cm -1)
Additive Deformation Stretch Wag Wag
number NH2 ~ CN b NH= = NH d Other
(1) (2) (3) (4) (5) (6)
1,650 1,050 870 (weak) 720 (weak) 3,270, second
amine, amide
1,650 1,070-1,120 820-840 730 (weak) 3,280, second
aminer
1,630 1,070-1,120! 830 (trace) 720 3,300, amide
(weak)
1,650 1,070-1,120 830 725 (weak) 3,280, second
amine
1,630 1,070-1,120 820-840 730 (weak) 3,280, second
amine
atypical for primary amines.
bTypicalfor organic nitrogen compounds.
CTypicalfor primary amines.
dTypicalfor secondary amines.
~ amine.

J. Mater. Civ. Eng. 1993.5:1-18.

 0.5

..... AC-20-I
0.4
..... AC[2012
z"
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~0.3
z
o
z
o
c.)O. 2
bJ

~0.1

0.0 i : i i L I ~ i i i i I i i i g f j i i t i

0 t2 24 48
HEATING TIME AT 162.8 ~ HOURS
FIG. 2. Variation in Additive Concentration with Heating in Different Asphalts

rate of additive loss was higher when mixed in AC-30-1 than when mixed
in either AC-20-1 or AC-20-2. AC-30-1 thus appeared to react with the
additive at a faster rate than did any of the other asphalts tested. With AC-
30-1, the amount of additive loss after being held for 48 hours at 162.8~
was about 65% by weight of the initial amount of additive added into the
asphalt. A reaction temperature of 162.8~ was selected, because this is the
temperature at which an asphalt (AC-20) is normally stored.
In the preparation of some of the additives, either more amine is added
to a fatty acid or some other similar type hydrocarbon than that stoichio-
metrically required to form the desired active compound. When excess
amines are present, an additive solution is said to contain free amines. These
amines may react with acidic components of the asphalt and/or with un-
reacted fatty acids in the original additive solution to form ammonium salts
that are effective surfactants. This may occur at a faster rate than the rates
of evaporation or thermal degradation or reactions that cause a loss in
surfactant activity. For this reason, the concentration of additive 2 (as de-
tected using the UV method) increased during the earlier period of hot
storage, as shown in Fig. 3. However, after the free amine in additive 2 had
been consumed, there was a loss in its concentration and effectiveness.
Specifically, the concentration of additive 2 increased during the initial six
hours of hot storage; however, after this time its concentration decreased
steadily, and after 48 hours of storage at 162.8~ in asphalt AC-20-1, its
concentration was only 44% of its initial concentration.
Fig. 4 illustrates the dependency of the rate of additive loss on hot-storage
temperature. Apparently, the rate of additive loss was accelerated as the
storage temperature was increased [(149-162.8~ A significant amount
of evaporation, presumably that of the additive, was observed visually to
occur during the hot storage of asphalt and additive mixtures when the
additive contained large amounts of primary amines (additives 2, 4, 5).
For each observed decrease in measured AS additive concentration, there

J. Mater. Civ. Eng. 1993.5:1-18.

 ol.0
C.)

C)

~'0.8
I--
,<
cF
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I--
Z
(~0.6
Z
O
C.)
bJ
> 0.4
F-
* * * * , Additive No. 2, C = 1.C~
s aAaAA Additive No. 1, C = 0.5~
,(

~02
Z
O
O
<
o.o I I i'" I I I I I ~ I I I 'i' I e S I I e I I I I

0 12 24 36 48
HEATING TIME AT 162.8 ~ HOURS

FIG. 3. Variation in Additive Concentration in AC-20-1 with Heating at 162.8~

100

e 80
z"
_o

~- 60
Z
IM
r
Z
O ADDITIVE NO. 1
~2 40
hJ ***** Heotlng ot 149. "C
_> A=AAZ, Heotlng ot 162.8 ~
F--

CI
< 20

i p i i i I i i J ~ i I i i i i ~ I i i i i r

0 12 24 36 4-8
HEATING TIME, HOURS

FIG. 4. Variation of Additive Concentration in AC-20-1 Due to Heating at Different

Temperature

was a decrease in a p p a r e n t additive effectiveness, as m e a s u r e d by the boiling

water test (Figs. 5 and 6). There was some eventual loss in effectiveness
with hot storage for all the additives tested. H o w e v e r , for additive 3, the
rate of decrease in its effectiveness was much lower than those of the o t h e r

J. Mater. Civ. Eng. 1993.5:1-18.

 Z
100 * * * * * 1.1~l ADDITIVE NO. 2
,...,J OOCX:O 0.5== ADDITIVE NO. 3
o o o c ~ 0.5~ ADDITIVE NO. 1
0 ^ ^ ^ ^ A 0.5~ ADDITIVE NO. 4
rn
lZ
i,i 80
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,r:-
Cb
I,.LJ
Z 60

LLI

(,3 40
Z
F-

0
(.P
t-.-- 20
Z
L~
(.3
IZ:

0 12 24 ,36 48
ADDITIVE HOLDINO TIME IN ASPHALT AT 162.8 ~ HR

FIG. 5. Heat Stability of Antistripping Additives in AC-20-1 as Determined by

Boiling-Water Test

~z 1 0 0
.,,_1
ADDITIVE NO, 1

~'**** AC-20-1
,~~.~,,~~, A C - 2 0 - 2
ba:
J 80-
E
<

z 60

IJ
c~

~
Z
40

~
Z
20
L.ul
C~
I,i
Ck
0 i i 1 ] i ] i i i i i I i i t i i I F I I I =

0 12 24 .36 48
ADDITIVE HOLDING TIME IN ASPHALT AT 1 6 2 . 8 ~ HOURS

FIG. 6. Heat Stability of an Antistripping Additive in Two Different Asphalts as

Determined by Boiling-Water Test

J. Mater. Civ. Eng. 1993.5:1-18.

 additives, and after 48 hours at 162.8~ it had decreased only by about
10%.
Fig. 7 shows the response of the performance to changes in its storage
temperature of additive 2. At both 162.8~ and 176.7~ its effectiveness
deteriorated rapidly; whereas at 149~ it maintained its effectiveness for a
relatively longer period of storage (48 hours).
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Curing of Asphalt-Aggregate Mixes

While performing the boiling-water tests, it was observed that reheating
an asphalt-aggregate mixture usually resulted in a increase in its stripping
resistance. Mixtures of different asphalts and aggregates were cured by
holding the mixes at a fixed temperature for a set period of time, Fig. 8
shows the response in stripping resistance (i.e., the boiling-water-test result)
of these different mixes to changes in curing time. A curing temperature of
149~ was used because this is the temperature at which asphalts and ag-
gregates are normally mixed (Tunnicliff and Root 1984). Even when no AS
additive was present in the asphalt, the percent asphalt retained after boiling
(i.e., the boiling-water-test result) increased steadily with curing at 149~
However, when an AS additive was present, the response in improved
stripping resistance to curing was considerably more. In general then, de-
pending on the presence and the type of AS additive used, after several
hours of curing at 149~ the stripping resistance of each asphalt-aggregate
mixture tested was improved significantly.
The observed improvement in stripping resistance with curing as a resutt
of hardening of the asphalt cement was then evaluated. To this end, an
asphalt-aggregate mixture was cured in a nitrogen atmosphere at 149~ (Fig.
9). The response in stripping resistance to curing in a nitrogen atmosphere
was about the same as that observed in an ambient atmosphere. A similar

zo 100
d
5CO
cx
W 80
<

C21
W
z 60
<
F--
W
Qs 1

oZ 40
-*~** 149. ~
c, o o e o 162.8 ~
.<
~-~,~.~, 176.7 ~
O

~-
Z
20
W
C)
r'e"
W
13_
i i I ~ i L i a I i u i u i I i u i i i

12 24 36 48
ASPHALT HOLDING TIME, HOURS

FIG. 7. Heat Stability of Antistripping Additive in AC-20-1 at Different Tempera-

tures as Determined by Boiling-Water Test

10

J. Mater. Civ. Eng. 1993.5:1-18.

 1O0 ~1

5m
rr 80
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a
iJ
z 60
t..d

o
z
40-
I.-..
,,<
O
cO

20-
Z A~z,. O.5~ ADDITIVE NO. 5
ooooo CONTROL, AC-20--1
cO

EL
0 i i i i i i i I i i i t i i i I i z i , 1 i ,
0 8 4 2
MIXTURE CURING TIME AT 149 ~ HOURS

FIG. 8. Effect of Mixture Curing at 149~ on Additive Performance as Determined

by Boiling-Water Test

100.00

5
EEl

80.00
<

C2~
~ 60.00

~
z 40.00
,<
O
CO

Z
20.00
L,LI
O
n,"
hJ
EL
0.00 i i i i I i i i I i i i i i r i i i I i 1 1 i i i i i ~
0:00 4.00 8,00 1 .00
MIXTURE CURING TIME AT 149 ~ HOURS
FIG. 9. Effect of Mixture Curing at 149~ in Different Atmospheres on Additive
Performance as Determined by Boiling-Water Test

observation was made by O'Connor (1984). It did not appear then that the
observed improvement in stripping resistance was due to oxidation.
It has been suggested by several investigators (Dybalski 1982; O'Connor
1984; Petersen et al. 1974) that mixture curing would improve stripping
11

J. Mater. Civ. Eng. 1993.5:1-18.

 1.0

G 0.8 ~ ~ur - = Hours

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(.3
~ * C~CULAEDV~J.UES•IH
0.6

Z
0.4

i 0.2

0,0 ~rl i i i i i i , ['1'1 i i i i i i i i i i i i

-5 -3 -1 1 3 5
DISTANCE (X), CM

FIG. 10. Concentration-DistanceCurvefor DiffusionCoefficientof Additive 1 in

AC-20-1at 149~

1.0 ~ ,

d 0.8 ~ ~uE - e HOURS

(.)

~ 0.6 CALCULATED V A L U E S WITH

/'

I--
Z

Z
0

0.2

o.o . . . . I, . . . . I, . . . . I, .... , ' > ~ ,~,

-5.00 -3.00 -1.00 1.00 3.00 5.00
DISTANCE (X), CM

FIG. 11. Concentration-DistanceCurvefor DiffusionCoefficientof Additive1 in

AC-20-2at 149~

resistance, because of m o r e efficient migration of the A S additive to the

aggregate surface (Dybalski 1982) and/or possibly because of an increase in
adhesional strength due to the formation of a "solid" or an " i m m o b i l i z e d "
asphalt layer on the aggregate surface (Petersen et al. 1974). Conversely,
12

J. Mater. Civ. Eng. 1993.5:1-18.

 Dybalski (1982) stated that excess migration of AS additive with mixture
curing could adversely effect active performance by forming a layer around
the aggregate surface of weakly bonded compounds.
In order to evaluate the degree to which additive migration occurs during
mixture curing, the diffusivities of an AS additive in two different asphalt
cements were determined, Additive 1 was used, which contained 2 weight
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percent copper. Since the additive molecular structure itself contained cop-
per (a metal complex), the additive concentration was determined by mea-
suring the copper concentration in the asphalt. The copper concentration
was measured using A A spectroscopy. Figs. 10 and 11 show the AS additive
concentration distribution across the diffusion cell after six hours at 149~
for additive 1 in AC-20-1 and AC-20-2 respectively.
Initially, one-half of the diffusion cell was filled with the asphalt containing
no additive, and the other half of the cell was filled with asphalt having an
AS additive with a concentration of Co. The initial conditions of the ex-
periment thus were

C = Co, x<O, t=O .................................. (1)

C=O, x>O, t=O ................................... (2)

where C = the concentration of the additive in the asphalt; and x = the

position along the diffusion cell with x = 0 being located at the initial
interface between the part of the diffusion cell that contained additive and
that which contained no additive.
Assume that the diffusion coefficient, D, is constant and the concentration
changes do not reach the ends of the diffusion cell during the time of the
experiment; that is mathematically

C = Co, x = -% t>O ............................... (3)

C = 0, x = +% t>0 ................................. (4)

For the boundary conditions given by (3) and (4), the concentration gradient
in the diffusion cell follows the expression (Crank 1975)

C 1 x
Co - 2 erfc 2Dt .............................................. (5)

where erfc denotes the error function complement, solutions of which can
be obtained from standard mathematical tables.
The diffusion coefficient, D, was estimated by comparing the experi-
mental values for C/Co at different locations, x, with values for C/Co cal-

TABLE 2. Diffusion Coefficient of Additive 1 in AC-20-1 at Different Temperatures

Diffusivity
Temperature (~ [cm=/s ( • 106)]
(1) (Z)
121.1 0.46
135 0.72
149 0.95
162.8 1.27

13

J. Mater. Civ. Eng. 1993.5:1-18.

 mzO~I00
-~

~:
hJ
80-
I,,--
LL
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<

0
I,i
z 60.

W
n.-

o
z 40.
F.-
<
O
O

F-
Z
20-
W o o o o o 0 . 2 ~ ADDITIVE NO. 1
'f-,-) aa~,~,t~ G O N T R O L , A C - 2 0 - 1
rY
W * 1.1 x 10 . 5 G N O . 1 / g AGGREGATE
13-
0 i i i i I I i i i I i i i i I i i i i I i i i i
0.0 2.5 5.0 7.5 10.0 12.5
MIXTURE CURING TIME AT 149 ~ HOURS
FiG. 12. Effect of Mixture Curing at 149~ with and without Aggregate Pretreat-
ment with Additive

I O0
J

m
5

w
80
<

w
Z 60
p-
w
n,"

0
Z
40"

0
0

l,-
Z
20"
W ***,* AGGREGATE PRECOATED WITH PHENANTHRENE
0 aa~ CONTROL
n~
w
(3-
0 I I I , | I i i i I * i i i l i i i i I i i i i
0 1 2 5 4 5
MIXTURE CURING TIME AT 149 ~ HOURS
FIG. 13. Acceleration of Curing Effect on Stripping by High-Coking Propensity
Additive, Phenanthrene

culated using (5). The diffusivity of additive 1 at 149~ was estimated to be

9.5 • 10 -5 cm2/s in asphalt AC-20-1 and 7.2 • 10 -5 cm2/s in AC-20-2
(Figs. 10 and 11). Therefore, the diffusion rate of the additive was different
in different asphalts. The diffusion rate of the additive was also observed
14

J. Mater. Civ. Eng. 1993.5:1-18.

 o 3.
x
Ld ADDITIVE NO.1
ASPHALT: A C - 2 0 - I

W
n-
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~2
<

U.l
[13
n-
O

td
_>
5
121
<

0 1 J i J ~ I I } I [ ] I ~ I I f J i J ] J I I J I i

0 1 2 3
ADDITIVE CONCENTRATION IN ASPHALT, w t ~

FIG. 14. Adsorption Equilibrium Curve for Additive 1 on Granite Powder at 20~

to be different at different temperatures (Table 2), as was expected.

The additive migration rate to the aggregate surface was estimated by
assuming a 1-mm asphalt film thickness on a flat aggregate surface. The
diffusing substance was assumed to be initially uniformly distributed and
the concentration at the aggregate surface was assumed to remain at zero;
that is
C= Co, 0<x<L, t=0 ............................. (6)
C = 0, x = 0, x = L, t>0 ......................... (7)
where L = the thickness of the asphalt film. In practice, the latter as-
sumption that C = 0 at the aggregate surface [(7)[ means that all the additive
which reaches the asphalt-aggregate interface is adsorbed onto the aggregate
surface. Assuming the above boundary conditions, the following expression
for the concentration distribution of the additive in the asphalt film at any
time can be derived (Crank 1975):

C 4 ~o 1 exp[_D(2n + 1) 21v2t~ (2n + 1)1v1

C-o - ~ ,= 2n + 1 -L--Zj sin L ...... (8)

Integrating this expression for additive concentration over the film thickness,
an expression for the average concentration of the additive asphalt film at
any time can be derived

Co - ~2
,
= (2n + 1) 2exp
[ -D(2n + 1)--~-j ................. (9)

where C = the average concentration of the additive in the asphalt film.

For thickness of the asphalt film, L, of 1 mm, according to (9), only
about 2 min is required for 90% of the initial amount of the additive to
15

J. Mater. Civ. Eng. 1993.5:1-18.

 migrate to the aggregate surface through the asphalt film at 149~ There-
fore, it was concluded that the additive migration rate is relatively fast and
the additive concentration in the asphalt-aggregate mixture approaches a
near-equilibrium value quickly, probably while the asphalt and aggregates
are being mixed. Thus, it is doubtful that any significant amount of additional
additive migration occurs during mixture curing, unless the additive is not
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initially well distributed in the asphalt. It was also assumed that no additive
absorption by aggregate occurs during mix curing.
It appears then that additive migration during mixture curing did not
contribute significantly to the observed increase in stripping resistance. As
shown in Fig. 12, curing improved stripping resistance both when additive
was applied directly to the aggregate and when the additive was added into
the asphalt prior to mixing the asphalt with the aggregate. Therefore, mix-
ture curing was effective for improving stripping resistance, even when
additive migration was not a factor.
It thus appears that hot-mix storage improved stripping resistance for
some reason other than increased additive migration. Hot-mix storage prob-
ably allowed the asphalt to penetrate better into fine aggregate displacing
any trapped air and forming a stronger mechanical interlock. It might also
allow more coupling reactions to occur between the asphalt and the aggre-
gate surface, and thereby improve the bonding strength between the asphalt
and the aggregate. The presence of an AS additive could enhance adhesion
with curing by reducing the asphalt surface tension and thereby increasing
the wetability between the asphalt and the aggregate surface. This can be
explained based on the theological properties of a mix after curing.
It was thought that the formation of a chemisorbed carbonaceous layer
on the aggregate surface could be the primary cause of the observed curing
effect. If the enhancement of stripping resistance with curing was the result
of such a layer on the aggregate surface, the application of a compound
having a high coking propensity should accelerate the curing effect. For this
reason, the granite aggregate was precoated with phenanthrene, and then
the aggregate was mixed with an asphalt and cured. Phenanthrene is known
to deactivate (poison) coal liquefaction catalysts by coking the catalyst sur-
face. As shown in Fig. 13, this did indeed result in an accelerated curing
effect.
It was mentioned earlier that excessive additive migration to the aggregate
surface during mixture curing could result in the formation of an asphalt
layer that is weakly bonded to the aggregate surface (Dybalski 1982). If this
were true, a lower, rather than a higher stripping resistance should have
been observed to occur with curing. As was shown, the additive migrates
very quickly to the aggregate surface. Also, it was found in measuring the
amount of additive adsorption onto an aggregate surface that an equilibrium
exists between the concentration of additive in the asphalt and the amount
of the additive adsorbed onto the aggregate surface (Fig. 14).

SUMMARY AND CONCLUSIONS

The chemical functionalities contained in the AS additives tested were
found to be primary and secondary amines and other organic nitrogen com-
pounds. These funtionalities were identified using infrared spectroscopy.
All the additives studied were capable of reacting with asphalt components
at temperatures typical of asphalt handling (162.8 ~ The concentration
of those additives tested were shown to decrease when stored in asphalt at
temperatures greater than 149~ Correspondingly, the effectiveness of the
16

J. Mater. Civ. Eng. 1993.5:1-18.

 AS additives tested was found to decrease to some extent after being held
for some time in hot asphalt cement in this temperature range. From Fig.
2, and 4-6, it can be concluded that a positive correlation exists between
the measured decrease in additive effectiveness and measured decrease in
additive concentration with storage in hot asphalt.
The performance of the asphalt-aggregate mixtures studied was observed
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to improve remarkably with storage at about 149QC for several hours (i.e.,
curing). It was found by measuring the diffusivity of an AS additive in
different asphalts that the additive migration rate is relatively fast, and the
additive concentration in the asphalt-aggregate mixture reaches an equilib-
rium quickly. The apparent improvement in stripping resistance of an asphalt
to an aggregate surface during curing did not appear to be due to diffusion
effects, but instead to some other phenomena such as some type of coupling
reactions that occur between the asphalt and the aggregate surface and coke
formation on the aggregate surface. The observed enhanced stripping resist-
ance, resulting from additional curing, appeared to be accelerated by the
presence of an AS additive.

ACKNOWLEDGMENT
This research work was sponsored by the U.S. Department of Trans-
portation, Federal Highway Administration through the State of Alabama
Highway Department. The writers gratefully acknowledge the sponsorship,
assistance, and cooperation of these organizations. The contents of this
report reflect the views of the writers, who are responsible for the facts and
accuracy of the data presented herein. The contents do not necessarily reflect
the official view or policies of the State of Alabama Highway Department
or the Federal Highway Administration. This report does not constitute a
standard, specification, or regulation.

APPENDIX. REFERENCES
Crank, J. (1975). The mathematics of diffusion. Clarendon Press, Oxford, U.K.
Dybalski, J. N. (1982). "Cationic surfactants in asphalt adhesion." Proc. of Assoc.
of Asphalt Paving Tech. (AAPT), 5l, 244-252.
Hellgeth, J. W., Amateis, P. G., and Taylor, L. T. (1984). "The fate of nitrogen
model process solvents in coal liquefaction." Preprint Paper, American Chem.
Soc., 29(5), 99-105.
Huber, C. F., and Thompson, P. F. (1955). "The function and chemistry of asphalt
additives." Proc. of Assoc. of Asphalt Paving Tech. (AAPT), 24, 374-391.
Kandhal, P. S., and Wengler, M. E. (1974). "Storage of bituminous concrete in inert
gas." Highway Res. Record, 468, 61-72.
Linfield, W. M. (1969). Straight-chain alkylammonium compounds in cationic sur-
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9-70.
Mathews, D. H. (1962). "Surface-active agents in bituminous road materials." J.
Appl. Chem,, 12, Feb., 43-51, 56-64.
O'Connor, D. L. (1984). "Action taken by the TDOHPT to identify and reduce the
stripping potential of asphalt mixes." Proc. of Assoc. of Asphalt Paving Tech.
(AAPT), 53, 631-637,
Petersen, J. C., Ensley, E. K., and Barbour, F. A. (1974). "Molecular interactions
of asphalt in the asphalt-aggregate interaction region." Transp. Res. Record, 515,
67-78.
17

J. Mater. Civ. Eng. 1993.5:1-18.

 Tunnicliff, D. G., and Root, R. E. (1984). "Use of antistripping additives in asphaltic
concrete mixtures." NCHRP Report 274, NCHRP, Washington, D.C.
Yoon, H. H. (1987). "Interface phenomena and surfactants in asphalt paving ma-
terials," PhD thesis, Auburn University, Auburn, Ala.
Zdeb, M. S., and Brown, R. A. (1974). "Storage of asphalt concrete." Transp. Res.
Record, 515, 79-88.
Downloaded from ascelibrary.org by Mohammed Junaid Siddiqui on 09/18/14. Copyright ASCE. For personal use only; all rights reserved.

18

J. Mater. Civ. Eng. 1993.5:1-18.