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Thermal Degradation of Antistripping Agents
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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INTRODUCTION
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).
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.
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
I
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t AJl~halt with I
tl
Alphall without .I
Additive Additive 1
~ . i~'~:!~z~;s ~;i!~if:)~iiiii~!iii!i~iiiii~ill~i::
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.
..... 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
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
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
,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
~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
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
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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
10
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
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
(.3
~ * C~CULAEDV~J.UES•IH
0.6
Z
0.4
i 0.2
1.0 ~ ,
(.)
I--
Z
Z
0
0.2
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
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-
13
~:
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
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~
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)
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).
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-
factants." Surfactant Sci. Series 4, E. Jungermann, ed., Marcel Dekker, New York,
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.
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