RHEOLOGY OF ASPHALT

J. W. Romberg and R. N. Traxler

From The Texas Company, Port Neches, Texas
Received Nov. 11, 19.~6

INTRODUCTION
The flow properties of asphalts vary widely. Values of viscosity at
25°C. (77°F.) range from about 103 poises for the fluid petroleum residua
to 109 poises and higher for hard asphalts. The type of flow varies from
that of an essentially simple liquid (Newtonian flow) to highly complex
(non-Newtonian) flow. Most asphalts are deformed continuously even
by the smallest applied shearing stresses and thus do not exhibit measur-
able yield values. Exceptions to this are certain asphalts very high in wax
content. When subjected to stress many asphalts undergo an elastic
deformation in addition to the usually more predominate permanent flow.
An accurate, complete and rapid evaluation of these different flow prop-
erties is the goal of rheological measurements of asphalts.

VISCOSITY
Viscosity, 7, is defined as the ratio of shearing stress, F, to rate of
shear, S:
.= F / S , poises, (1)
where F = shearing stress, dynes/sq, cm., S = rate of shear, reciprocal
seconds.
The energy, W, expended in one second for unit volume (6) is re-
lated to viscosity, 7, as follows:
W = ~S2 = FS. (2)
A complex material is one for which the viscosity varies with the rate
of shear. Another way of saying this is that the plot of rate of shear, S,
vs. shearing stress, F, is not linear. However, it has been shown (21) that,
for many asphalts, in the range of rate of shear and shearing stress em-
ployed in the rotary viseometer (20), the plot of log S vs. log F is essen-
tially a straight line.
One of the purposes of using absolute viscosity units is to make pos-
sible the comparison of all materials on the same basis. In order to com-
pare the viscosities of two complex materials, it is necessary to select
arbitrarily some standard conditions under which the viscosities are
33
34 J. W. ROMBERG AND R, N. T R A X L E R

obtained. The methods which have been used are discussed in the fol-
lowing pages.
Using the rotary viscometer (20) the viscosities of complex materials
have been compared at a particular rate of shear. Since it is impossible
to measure both hard and fluid materials under the same conditions, it
is necessary to select some intermediate rate of shear. A value of 0.1
reciprocal second has been used in most of the work done at this labora-
tory. Since neither the very hard nor the very fluid materials can be
measured at this rate, all asphalts are measured at two or more con-
venient rates of shear and a plot of log shearing stress vs. log rate of shear
is extrapolated to 0.1 reciprocal second. However, this method has
several disadvantages. Extrapolation in itself tends to magnify any errors
in measurement. In addition, a more serious obstacle to the success of
this method has become apparent which is best illustrated by the follow-
ing example. On Fig. 1, are plotted log rate of shear vs. log shearing stress
for a series of air-blown Gulf Coast II asphalts. On the log-log plot essen-
tially straight lines are obtained in the region in which the determinations
are made. It has been the practice to extend these lines when necessary
until they cross the ordinate representing 0.1 reciprocal second (10-1
see.-1). From the value of shearing stress at this line the viscosity is
calculated.
As asphalts are air blown and become harder, the degree of complex
flow becomes greater and the plot of log S against log F becomes steeper.
It will be noted from Fig. 1 that, if a rate of shear of 100 reciprocal
seconds had been selected instead of 0.1, the calculated viscosity (7
= F / S ) of Asphalt 1C (146°F., ring and ball) would have been lower
than that for Asphalt 1B (125°F., ring and ball). Although, in the several
series of asphalts listed in this paper, no such reversal in magnitude of
viscosity has been obtained at 0.1 reciprocal seconds, the effect is apparent
in the disproportionately low values of viscosity for the highly complex,
hard materials.
The explanation of this reversal in magnitude of calculated viscosity
for two succeeding samples in a series and for the unexpectedly low values
of viscosity for the hard, complex asphalts probably lies in the fact that
the extrapolated lines do not represent the actual behavior of the ma-
terials since the plot of log S against log F may be curved over a long dis-
tance. For hard asphalts this curvature may be accentuated by slippage,
or by a rise in the temperature of the sample caused by the excessive
amount of energy that must be dissipated in shearing at high rates. This
latter subject is discussed in greater detail below.
With the falling coaxial cylinder viscometer (19) asphalts are compared
at a particular shearing stress. For certain purposes, such as evaluating
age hardening, where the same shearing stress (same load) can be used
 RHEOLOGY OF ASPHALT 35

on each sample, this method is useful. However, the same shearing stress
cannot be used for materials of widely different viscosities. To make
measurements at several different shearing stresses and extrapolate to
some common value would be subject to the same disadvantages discussed
above for the use of a particular rate of shear.

~02

,o , ,// ,¢/
/

I
,7 --
/
/
/
/

,,,~e e) /
lo'i / I
/ ,..o/
~' ' ~"I

SHEARING STRESS, F, DYNES/GM 2

FIG, 1
Variation of the Rate of Shear of Asphalts with the Applied Shearing Stress at 25°C.

These difficulties in comparing viscosities of complex materials ap-

parently can be overcome by making the comparison at a particular power
input per unit volume of sample. This requires calculation of the viscosity
at a constant value of the product of the shearing stress times the rate
of shear, F X S (6). The product FS is the power input at the mean
radius at which F and S are calculated. In a rotary viscometer this is not
 36 J. ~r. I~OMBERG AND R. N. TRAXLER

~OB

I I + I

I~.
oO

oO . °

.qo

o~o ~ ~ ~ ~ O O O O

~e
8

OQOQ~
 RHEOLOGY OF ASPHALT ~7

H,

0 ,
~o ~ boo

0 O © C
38 J.W. ROMBERG AND R. N. TRAXLER

quite equal to the total power input divided by the total volume of sample.
Since the values of both F and S within the sample vary, the total power
input must be obtained by integration.
A power input of 1000 ergs (one kiloerg)/sec./cc, has been selected
as a convenient value at which to evaluate the viscosities of asphalts.
i0 IC

109
VALLEY /
SPHALTS j ~'-

.: 'oS //
,. ,...,
'/ J

.o f
f
f

• AT I000 ERGS SEG-IGI~3

r. /
o AT 0.1 SEG"l

105
/ 130 170 210 250 290
SOFTENING POINT, RS,B , "F

FIG. 2
Ring and Ball Softening Point-ViscosityRelation for Two Series of Asphalts

This power input is represented on Fig. 1 by the diagonal line marked

F S -- 1000. Very little extrapolation is required to reach this line from
any of the rheological data normally obtained on asphalts. The rheoo
logical data are obtained at two or more rates of shear and log S vs.
log F plotted. A straight line is drawn through the plotted points and, if
 RHEOLOGY OF A S P H A L T 39

necessary, extrapolated until the line F S = 1000 is crossed. The vis-

cosity is equal to F divided b y S at F S = 1000.
In Table I, viscosities calculated at both 0.1 reciprocal second and at
1000 ergs sec. -1 cm. -a are listed for several different asphalts. T h e values

lollI

\\
i0Ic

loft

o ~ ~ERGS SEC
-! GM-3
z
- ,0 a

?,
=o

,07

I06
278.PK(5"C) 298.1*K(25°C) 523.1=K(50"C)
TEMPERATURE
FIG. 3
Log Absolu?¢ Temperature--Log-Log Viscosity Relation for
Air-Blown East Texas Asphalt, 2C

of viscosity calculated at 1000 ergs sec. -1 cm. -a appear to give a b e t t e r

indication of the consistency of the hard, complex materials. T h e differ-
ence in the results obtained by the two methods is illustrated in Fig. 2,
in which log viscosity at 25°C. is plotted against softening point, ring and
40 J. W, ROMBERG AND R. N. TRAXLER

bail, for two series of asphalts. All except the hardest of the air-blown
San Joaquin Valley asphalts are essentially simple liquids, and vis-
cosities obtained by the two methods differ but little. However, for the
air-blown Gulf Coast II asphalts which show considerable complex flow,
the viscosities calculated by the two methods differ considerably.
Since most air-blown asphalts show increased complex flow as the
temperature is lowered, somewhat different values of susceptibility will
be obtained depending on whether viscosities are calculated at S -- 0.1
sec. -1 or F S --- 1000 ergs sec. -~ cm. -3. This is illustrated in Fig. 3, in
which the log-log viscosity (calculated by each of the two methods) is
plotted against the log of absolute temperature for air-blown East Texas
Asphalt 2C. The line drawn through the points at F S = 1000 is somewhat
steeper (more susceptible) and fits the data better than the line drawn
through the values at S = 0.1 sec. -~.

Thermodynamic Considerations
The energy required to produce any deformation of matter appears
in three forms which are (1) kinetic energy, (2) potential energy, and
(3) thermal energy. In the evaluation of the theological properties of
asphalts, kinetic energy effects are usually negligible. The potential en-
ergy is that required to overcome the elastic resistance of the material
and appears in the early part of the measurement. When equilibrium
conditions are reached, essentially all of the energy is being converted to
thermal energy (heat).
If the power input and the size of sample are such that the energy
dissipated as heat in shearing cannot be conducted away quickly, an
appreciable rise in temperature of the sample will occur. For a material
as susceptible to temperature as asphalt, even a slight change in tempera-
ture will affect the viscosity determination.
Calculations have been made of the power input required to cause a
maximum temperature rise of 0.056°C. (0.1°F.) in the sample. It was
found that a power input of about 20,000 ergs sec. -1 cm. -3 would be re-
quired to give this temperature rise for an instrument having a rotor
length of 2.54 cm., rotor diameter of 3.81 cm. and stator diameter of 2.54
cm. On the basis of these calculations a power input of 1000 ergs sec. -1
cm.-3 appears to be a safe value at which to compare the viscosities of
complex materials.
COMPI~EX FLOW
An equation for the evaluation of complex flow has been described
elsewhere (21). This relation may be written:
M = F / S ~, (3)
 RHEOLOGY OF ASPHALT 41

where F --- shearing stress, dynes/sq, cm., S = rate of shear, reciprocal

sec., c = slope of log F vs. log S plot, M = value of F when S = 1.
For a simple liquid, the constant c is unity, M is the viscosity in
poises and Eq. (3) is the same as Eq. (1). For complex materials, the
value of c is a measure of the deviation from simple flow. For materials,
such as certain asphalts, which have lower viscosities for increasing values
of rate of shear, c is less than one.
Values of the degree of complex flow, c, at 25°C. (77°F.) for various
residua and asphalts are given in Table I. The complex flow of the
residua at 5°C. (41°F.) and of the 50 penetration (25°C., 100 g., 5 sec.)
asphalts at 5°C. (41°F.) and 50°C. (122°F.) are also given in Table I.
These values of c vary from 0.40 to 1.00.

ELASTICITY

Elasticity has been defined (1) as "that property of a body by virtue

of which it tends to recover its original size and shape after deformation".
Many of the uses of asphalt depend upon its ability to be deformed with-
out rupture and to recover from small deformations. Following deforma-
tion of some solids, such as steel and vulcanized rubber, elastic recovery is
practically complete and instantaneous (under certain conditions). How-
ever, for viscoelastic materials, such as most asphalts, recovery is only
partial and takes place over a period of time. Because permanent and con-
tinuous deformation occurs in asphalts under stress, it is usually impos-
sible to evaluate the elastic modulus by direct tensile or torsion measure-
ments. Several other methods discussed below have been used for evalu-
ating the elasticity of viscoelastic materials.

Vibrational (Dynamic) Methods

If a viscoelastic material is subjected to alternating stresses, the de-
formation is essentially elastic if the frequency is high compared with the
relaxation time (7). Other vibrational methods involve measurements of
the fundamental frequency of a rod or sheet of the material from which
the elastic modulus can be calculated (5, 9).
The velocity of sound waves in a liquid is a function of its density
and compressibility (reciprocal of bulk modulus of elasticity). From the
bulk modulus and Poisson's ratio the shear modulus of elasticity has been
calculated (15).

Thermodynamical Methods
The work required to produce an elastic deformation is stored as po-
tential energy and is expended on recovery. In viscous flow, work is dis-
sipated as heat. Thus, ff the relative amounts of work which go to heat
42 J. W. ROMBERG AND R. N. TRAXLER

and to potential energy are measured, the relative amounts of viscous

and elastic deformation are known. The losses of energy to heat have
been measured by the damping effect upon a torsional vibration (8).

Elastic Fore- and After-Effects

In viscosity measurements, an increasing ratio of shearing stress to

rate of shear at the start of the determination is said to be caused by an
elastic fore-effect. Nutting's equation (13, 14), which is discussed below,
might be considered a method of evaluating this elastic fore-effect.
Elastic after-effect (recoil) has been measured (2, 4, 11, 16), but
quantitative analyses by this method are complicated b y the fact that
recovery and relaxation are both occuring at the same time. In addition,
for such materials as asphalt, recovery may take place over a long period
of time.
Relaxation of stress after deformation offers another means of measur-
ing elasticity. Maxwell (12) in his classical treatment was perhaps the
first to offer an equation for deformation of materials intermediate be-
tween viscous fluids and elastic solids. When such a material is sheared,
it tends to recover part of the deformation. If after deformation the ma-
terial is not allowed to recover (recoil), the stress required to maintain
the initial deformation decreases because of relaxation or creep. B y
making certain assumptions Maxwell obtained the equation:
F = GDe-~lr (4)

where F = shearing stress, dynes/sq, cm., G = modulus of elasticity in

shear, dynes/sq, em., D = strain in shear, t = time, seconds, e -- Na-
perian base, 2.718 . . . . , T = an integration constant with the dimensions
of time in seconds, called the "relaxation time". The relaxation time, T,
is numerically equal to t when the shearing stress has fallen to 1/e of its
original value.

Relaxation One-Half Time

After a study of the methods which have been employed for evaluat-
ing elastic properties of viscoelastic materials, the simplest procedure
appeared to be the evaluation of relaxation. To measure relaxation it is
necessary to follow the decrease in shearing stress with time after shearing
is stopped. This was made possible with the rotary viscometer (20) in
which viscosity and complex flow are evaluated, by employing an indi-
cating balance to measure the torque.
It was found that asphalts, like many other materials (10, 17), do
not follow Maxwell's equation. This is illustrated in Fig. 4. It was also
 RHEOLOGY OF A S P H A L T 43

found that the observed values for relaxation time not only varied widely
with temperature, but were dependent upon the shearing stress and size
of sample. In view of the fact that the relaxation time is not an absolute
value and for expediency in routine measurements, a simpler term for
relaxation has been used, i.e., the time required for the shearing stress to
decrease to one-half its original value. This is called the relaxation one-

7X104

6 X 104

5XIO 4 ~ %.

e~ 4 X 104 ~"
o~ '~ "\

. 3XIO4
==
~) EXPERiM

m 2X104
,.---....

Io 4i
0 50 I00 150 200 250
11ME, SECONDS

Fro. 4
Relaxation Curve for Air-BlownGulf Coast II Asphalt 1C at 25°C.

half time and like the Maxwell relaxation time may be used to evaluate
relative elasticity of asphalts for certain specified conditions of tempera-
ture, shearing stress, and size of sample.
For comparison of elastic effects of different asphalts the relaxation
one-half time is evaluated at a power input of 1000 ergs/sec./cc, using
the same procedure as for determining viscosity. Values of the relaxation
one-half time for several different asphalts are given in Table I.
44 J. W. ROMBERG AND R. N. T R A X L E R

STRESS-STRAIN-TIME RELATION

I t would simplify the theological evaluation of viscoelastic materials

such as asphalts if the deformation could be represented by a single
equation. Nutting (13, 14) has proposed such a law of deformation for
semi-solid materials relating stress, strain, and time. Several investiga-
tors (3, 18), notably Scott Blair, have used this relation for a wide variety
of materials. A few experiments have been made by the authors in order
to investigate the possibility of using this equation for evaluating the
theological properties of asphalts.
Nutting's proposed relation represents strain as a function of time
and stress as expressed by the following equation:

D = a t ~ F ~, (5)

where D = strain in shear, t = time, seconds, F -- stress, dynes/sq, cm.,

a, n , m = constants.
If this relation is valid, the constants a, n, and m should evaluate
the deformation properties of a material. The constant a is a measure
of intensity while n and m are measures of degree. Thus, for a perfectly
elastic deformation n = 0, m = 1, and a is the reciprocal of the elastic
modulus. For a perfectly viscous deformation, n = 1, m = 1, and a is
the fluidity. For intermediate materials a m a y be considered a measure
of softness; however, its dimensions depend on the values of n and m.
There is some difficulty in visualizing which properties n and m meas-
ure. The constant, n, being the exponent of time, is a measure of how
strain changes with time for a particular stress. The constant n is equal
to 1 if the rate of strain is constant; n is greater t h a n I if the rate of strain
is increasing with time; and n is less than 1 if the rate of strain is de--
creasing with time. Changes in rate of strain are caused by elasticity as
well as by thixotropy, work hardening, etc. Without making other meas-
urements, there appears to be no way of telling whether a value of n of
less than 1 indicates elasticity, work hardening, or a combination of the
two. The constant m, since it is the exponent of stress, is a measure of
how strain at a particular time is affected by the stress.
Theoretically, Nutting's equation could be used to analyze data ob-
tained in the constant rate of~ shear rotary viscometer. However, from
available data it is apparent that, even at best, Nutting's equation can
hold only for the initial deformation in the constant r a t e of shear vis-
cometer. Over a period of years, results obtained with the rotary vis-
cometer have shown t h a t F becomes constant (equilibrium is attained),
or m a y go through a maximum for very complex materials. Under such
conditions Nutting's equation cannot hold. For this reason a constant
shearing stress apparatus was constructed.
 RHEOLOGY OF ASPHALT 45

In this apparatus the rotor and stator of the regular rotary viscometer
were used. The outer cylinder was held stationary in a chuck, and thus
became the stator instead of rotor. The inner cylinder was driven b y
weights suspended on a thread which ran over a pulley and around a d r u m
attached to the vertical shaft. The angular deflection of the inner cylinder
was indicated on a graduated scale.
Three asphalts were studied at 25°C. in the constant shearing stress
viscometer using three different weights. E a c h determination was made
on a freshly prepared sample, and each measurement was started one
hour after pouring. Most determinations were made in duplicate or
triplicate.
TABLE II
Stress-Strain-Time Relation

Asphalt.. 9 10 11
Process. Steam Air Blown Air Blown
Residuum Source. Gulf Coast I I I Gulf Coast I I Gulf Coast II*

Physical Tests
Softening Point, Ring & Ball, °C. 50.0 65.6 81.7
°F. (122) (150) (179)
Ductility at 25°C., 5 cm./min., cm. 200+ 8 2
Penetration at 25°C., 100 g., 5 sec. 53 53 48
Rheological Data at 25°C.
Viscosity, Megapoises, S=0.1 3.0 5.7 9.4
Viscosity, Megapoises,'FS = 1000 3.1 22 94
Complex Flow, c 1.00-- 0.50 0.35 -
Relaxation One-Half Time, sec. 14- 20 66
Value of Parameters in Stress-Strain-
Time Equation
at 1.49 X 10 -5 2.9 X 10-e 1.85 X 10 -6
n 0.926 0.566 0.408
m 0.970 1.100 1.059
Standard Error of Estimate, % 10 16 20

* Asphalt 11 was prepared from a lower viscosity residuum than Asphalt 10.

The parameters a', n, and m of Eq. (5) were evaluated* for each
asphalt by the m e t h o d of least squares. For this purpose the angular
deformation in degrees,* D r, was used instead of strain, D, inasmuch as
the rotation is proportional to strain, and hence, only the numerical value
of the constant a in the N u t t i n g equation is affected. The calculated
values of the parameters are summarized in Table I I . Also included are
the values for the s t a n d a r d error of estimate.
F r o m these data, it will be noted t h a t values of m vary only slightly
* When angular deformation in degrees, D', is used in place of strain, constant a will
be designated as a'.
46 J. W. ROMBERG AND R. N. TRAXLER

from 1.00. This means that at any particular time the deformation is
essentially proportional to the shearing stress.
Assuming that variations in values of n are caused b y differences in
elasticity alone, asphalt 9 shows the least elasticity, asphalt 10 is inter-
mediate and asphalt 11 shows the most elasticity. This lists the three
asphalts in the same order as the relaxation one-half times given in
Table II.
Values of a' would indicate that asphalt 9 is the softest of the three
asphalts with asphalt 10 slightly softer than asphalt 11. Other rheological
data as well as physical tests given in Table II classify asphalt 10 as being
considerably softer than asphalt 11.
Considering the reproducibility of check data, the standard error of
estimate of 10% for asphalt 9 is not considered excessively high. How-
TABLE I I I
Standard Error of Estimate for Constant Shearing Stress

Asphalt Process and Re- M e a n Shearing Standard Error

siduum Source Stress of Estimate

dynes/sq.cm. Per c~m~

Steam Refined 5,700 0.940 3
Gulf Coast I I I 11,400 0.914 12
22,800 0.954 2

10 Air Blown 11,400 0.576 17

Gulf Coast II 22,800 0.551 12
57,000 0.567 18

11 Air Blown 22,800 0.378 23

Gulf Coast II 57,000 0.405 15
114,000 0.464 13

ever, standard errors of 16% for asphalt 10 and 20% for asphalt 11 appear
somewhat high and indicate that the form of Nutting's equation does not
satisfactorily fit the data for these two asphalts.
To study further the difference between observed values of strain
and values obtained by Nutting's equation, independent calculations
were made at each shearing stress. Under the conditions of constant
shearing stress, Nutting's equation becomes:
D = Kt", (6)
where D , t, and n have the same meanings as in Eq. (5), K (a constant)
= aPF,~.
By the method of least squares the parameter n was calculated for
each shearing stress. These values are given in Table III, together with
 RHEOLOGY OF ASPHALT 47

the values for the standard error of estimate. The percentage errors by
this method of computation are of the same order of magnitude as the
corresponding results for the same samples given in Table II, calculated
using all the available data. This would indicate that the error is largely
in the strain-time relation rather than the strain-stress relation.
In addition to viscosity, complex flow, and elasticity, there are other
phenomena involving the flow of asphalts. These include the manner in
which the rheological properties vary with temperature, age, prior de-
formation (thixotropy, work hardening, etc.) and pressure. With the ex-
ception of the latter, these phenomena have been discussed in earlier
papers.
Acknowledgment is made to It. E. Schweyer for advice and counsel during the ex-
perimental work and in the preparation of the manuscript.

~:~EFERENCES
1. Am. Soc. Testing Materials, Definition of Terms Relating to Rheological Properties
of Matter (E-24-42), Part I / / , p. ]072 (1944).
2. BROOME,D. C., J. Inst. Petroleum Tech. 25, 509 (1939).
3. BROOME,D. C., Petroleum 5, 122 (1942).
4. COOMBS,C. E., AND TRAXLER,R. N., J. Applied Physics 8, 291 (1937).
5. FROLICK,K., Kunststoffe 30, 10 (1940).
6. GE~Z_~NT,A., J. Applied Physics 12, 530 (1941).
7. Ibid. 13, 210 (1942).
8. Ibid. 14, 204 (1943).
9. GEMANT,A., AND JACKSON,W., Phil. Mag. 23, 960 (1937).
10. HATSCHEK,E., AND JANE, R. S., Kolloid-Z. 39, 300 (1926).
11. LEE, A. R., WARREn, J. B., AND WATERS, D. B., J. Inst. Petroleum Tech. 26, 101
(1940).
12. MAXWELL,J. C., Phil. iVlag. 35, 133 (1868).
13. NUTTING,P. G., J. Franklin Inst. 191, 679 (1921).
14. NUTTING,P. G., Proc. Am. Soc. Testing Materials 21, 1162 (1921).
]5. POCHETTINO,A., Nuovo cimento 8, 77 (1914).
16. SAAL,R. N. J., AND LABOUT,J. W. A., J. Phys. Chem. 44, ]49 (1940).
17. SCIx~WEDOFF,T., J. phys. 8, 341 (1889).
18. SCOTTBLAIR,G. W., A Survey of General and Applied Rheology. Pitman Publishing
Company, New York, 1944.
19. TR•XLEa, R. N., AND SCHWEYER,H. E., Proc. Am. Soc. Testing Materials 36, 518
(1936).
20. TRAXLER,R. N., ROMBERQ,J. W., AND SCHWEYER,H. E., Ind. Eng. Chem., Anal.
Ed. 14, 340 (1942).
21. TRAXLER,R. •., SCHWEYER,H. E., AND ROMBERG,J. W., Ind. Eng. Chem..36, 823
(1944).