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SHRP 91 510
SHRP 91 510
SHRP 91 510
Strategic
SHRP-A/UWP-91-510 Contract A-002A Product Code 1001, 1007 Program Manager: Edward T. Harrigan Project Manager: Jack S. Youtcheff Program Area Secretary: Juliet Narsiah March 1991 Reprinted November key words: adhesion aging asphalt chemical mode failure models fatigue cracking imermolecular metals moisture damage oxidation pavement performance permanent deformation polarity rutting thermal cracking virgin asphalt
1993
Strategic Highway Research Program National Research Council 2101 Constitution Avenue N.W. Washington, DC 20418
(202) 334-3774 This manual represents the views of the author only, and is not necessarily reflective of the views of the National Research Council, the views of SHRP, or SHRP's sponsor. The results reported here are not necessarily in agreement with the results of other SHRP research activities. They are reported to stimulate review and discussion within the research community.
50/NAP/1193
Acknowledgments
The research described herein was supported by the Strategic Highway Research Program (SHRP). SHRP is a unit of the National Research Council that was authorized by section 128 of the Surface Transportation and Uniform Relocation Assistance Act of 1987. This project was conducted by the Western Research Institute in cooperation with the Pennsylvania Transportation Institute, the Texas Transportation Institute, and SRI International. Raymond E. Robertson was the principal investigator. The support and encouragement of Dr. Edward T. Harrigan, SHRP Asphalt Program Manager, and Dr. Jack Youtcheff, SHRP Technical Contract Manager, are gratefully acknowledged. The experimental work cited herein was conducted by Dr. J. F. Branthaver, Dr. K. Ensley, Dr. J. Duvall, H. Plancher, P. M. Harnsberger, S. C. Preece, F. A. Reid, J. Tauer, M. Aldrich, A. Gwin, M. Catalfomo, G. Miyake, and J. Wolf. Their support in the preparation of this report is gratefully acknowledged. The review of this manuscript by Dr. J. Claine Petersen, former principal investigator for A-002A; Dr. Jan F. Branthaver at WRI; and Dr. David Anderson at PTI, co-principal investigator for A-002A; and Dr. Edward T. Harrigan and Dr. Jack Youtcheff of SHRP is hereby acknowledged.
nl
Contents
1.0 Introduction ................................................... 1.1 Objectives of the SHRP Asphalt Program ........................ 1.2 Purpose of Report ......................................... 2.0 Chemistry .................................................... 2.1 Molecular Level ........................................... 2.1.1 Typical Species in Virgin Asphalt ........................ 2.1.2 Oxidation to Form New Molecules ....................... 2.1.3 Metals ............................................ 2.1.4 Polarity ........................................... 2.2 Intermolecular Level ...................................... 2.3 Chemical Mode of Asphalt .................................. 3.0 Speculation on Relationship of Chemistry to Pavement Performance ................................................ 3.1 General Comments ....................................... 3.2 Aging ................................................. 3.3 Speculation on the Relationship of Composition to Various Failure Models ................................. 3.3.1 Rutting and Permanent Deformation ..................... 3.3.2 Thermal and Fatigue Cracking ......................... 3.3.3 Adhesion and Moisture Damage ........................ ....................................................
1 1 2 3 3 3 5 9 9 10 17 20 20 21 23 24 25 26 29
4.0 Summary
List of Structures
1 2 3 4 5 6 7 8 9
Molecular Fragment Molecular Fragment Molecular Fragmem Molecular Fragment Molecular Fragmem Molecular Fragmem Molecular Fragmem Molecular Fragmem Molecular Fragmem Fragmem
of an Aliphatic
Hydrocarbon
4 4 4 4 5 5 6 6 6 7 7 7 7 8 8
....................................
of a Carboxylic Acid .............................. of a Sodium Carboxylate of a Calcium Carboxylate of a Carboxylic Anhydride of a Phenol of a Homolog of a Homolog ........................... .......................... .........................
10 Molecular
11 Molecular Fragment 12 Molecular Fragment 13 Molecular Fragment 14 Molecular Fragment 15 Molecular Fragment
vii
..................................
8 8 9 9
...............................................
Vll" 1""
List of Figures
1A 1B 2 3 4 5 Randomized Organized Molecules Molecules
.........
" "
" *
..............
10
10
Three Dimensional
Molecular
Matrix ..............................
11 14
S.E.C. Chromatograms
........................................
Effects of Temperature on Aging Kinetics of an Asphalt Sensitive to Molecular Structuring ....................................... Performance ................................................
17 21
ix
F,_C_ZVE
S_Y
The
chemistry
of levels
petroleum is discussed
asphalt
at
the and
molecular a combination
and of
intermolecular
herein
interpretation
and
speculation
placed
on
how
chemical
data
may
explain
performance historical
in
At are
the at
molecular least
level of
hundreds
thousands
of
unique
molecular
species
that
exist
within
any
particular
asphalt.
Asphalts
are
known
to
be
comprised
of
molecular
species
that
vary this
widely portion
in of
and is
molecular to explain
weight. behavioral
The
major
objective
of of
characteristics
asphalts the
in
terms
of
chemistry.
Polarity Polar
is
very
major tend to
contributor associate
to
performance
characteristics.
materials
strongly
into
a matrix
which
is
dispersed
in
less
polar
and
non-polar
materials.
In
general,
the
mechanical
or
structural
properties
of
asphalt
are
related
to
the
intermolecular
structuring
among
polar
components. numerous
These different
polar chemical
interactions species.
may The
arise exact
by
involvement of the
of
any
of
nature
chemical
specie
is
less
important
than
the
overall
assemblage
of
set
of
polar
materials
to
form
a matrix
within
the
non-polar
continuous
medium.
The
matrix
gives
elastic
character
to
the
asphalt
while
the
continuous
non-
polar
phase
gives structuring
viscous leads
component to brittle
to
asphalt. which
It
is tends
speculated to crack
that
excessive
cements
while
too
little
structuring
leads
to
materials
which
deform
under
stress.
Oxidation
adds
to
the
age
hardening
and
brittleness
of
asphalt
cement
by
contributing
additional
polar
materials
to
the
structured
zones
within
the
binder.
At
very
low
temperature
it
appears
that
the
xi
also
tend
to
organize at
into low
a very
rigid It
material type of
shrinks shrinkage
temperature.
speculated temperature
that
is
largely
responsible
cracking.
second
major
objective types of
is to research with
methods employed
into to
test
methods.
Numerous among
differentiate which
asphalts
an in
identifying that
distinguish by
among their
asphalts performance
fashion
distinguished
characteristics.
The are to
expected develop
of this selection
work, of
technical that
and
economic, in of a
will
fashion road of
thereby
alleviating the
current
conunon users
failure.
both
petroleum to is give
worked
with and
SHRP to
contractor a
both what
program
maintain
practically
implementable
each
sector.
As
with
any
new will
questions for
arise
as
to of
how new
implementation
test
methods
become
extraordinarily there is no
complex, more
another absolutely
objective
assure
complexity therefore,
necessary. and a
Problems so
be method
minimized will
that
each
new
enter
program
state has
highway
user
laboratories.
round
robin
effort,
fact,
already
xii
begun.
Finally,
this
work
is
supported
by
public
funding
and
the
results domain.
that
are
implemented
into
new
test
methodology
will
be
public
xiii
1.0
INTRODUCTION
i.i
of
the
SHRP
Asphalt area
asphalt
research
ultimately
must
develop
specifications
for
binders
and
asphalt-aggregate
mixtures
that
relate
to
the
performance
of
both
binders
and
mixtures
in
pavements.
To
accomplish
this
the
fundamental
material
properties
must
be
known
first.
Then
fundamental
properties
are
to
be
used
to
develop
The a
current quality
for for
vacuum
crude
tower
operations,
hence
there
is
little
or
no
distinction
among
asphalts
other
than
set
of
viscosities
at
two
elevated
temperatures
and
a mix
plant
oxidation
susceptibility.
That
is,
all
of
many
asphalts
may
be
classified
as,
for
example,
AC-20,
and
all
will
be
applied
as
if
they
are
single
material.
Yet,
their
performance
characteristics
in
pavements
often
vary
quite
significantly.
The
results
of
using
poorly
classified
asphalts
have
been
rude
and
costly
surprises
in
the
form
of
various
types
of
early
failures
with
increasing
frequency.
It
behooves are
the
user,
therefore, in pavement
to
determine
what and
of
asphalt
binders
reflected
performance
binders
which
have
desirable
performance
properties.
From
practical
viewpoint,
no
doubt
many that
petroleum have
residua
will performance
require
modification
to
prepare
asphalts
desirable
characteristics.
1.2
Purpose
of
Report
The
purpose
of
this
report
is
to
describe
the
current
status
of
the
SHRP
chemical
studies
of
petroleum
asphalt.
It
is
intended
to
be
instructive
to
the
non-chemist
and
further
is
speculative
effort
to
correlate
some
of
the
known
chemical
properties
of
asphalts
with
pavement
performance
characteristics.
It
is
generally
believed
that
performance-
based The
for
binders
will
be
mainly is to
physical develop
property correlations
tests.
composition
studies
between
the
chemical
and
physical
properties.
Further,
the
composition
studies
are
to
define
set
of
practical
analytical
methods
to
describe
composition.
This
then
will
allow
definition
of
acceptable
composition
for
given
performance
which
in
turn
is
instructive
to
the
producer
in
the
manufacture
of
asphalt.
If
any
given
asphalt
has
compositional
deficiency,
the
producer
can
determine
how
to
modify
the
asphalt
and
remedy
the
deficiency.
It
has
become
obvious
that
deficiencies
vary
from
one
asphalt
to
another.
It
is
important
to
note
that
many
chemical
properties distinguish
will the
not
correlate
with
performance that do
so relate.
it
is
a major
goal
to
chemical
properties
References
are
made
to
ongoing
research
which
has
been
reported
to
SHRP, based
but on
in
many
cases SHRP
has research
not
been and
published. have no
Many
statements references.
are
current
literature
2.0
CHEMISTRY
It two the
is
to
divide is
the the
chemistry at
of
asphalt level
into and
parts. second
part
chemistry of
the
chemistry of the
interaction nature
among of
in asphalt. in terms
Much of
physical as an
assembly
blocks)
techniques
both
subsection without of
level
reviewed what
experimental are is
This
illustrate of interaction
types
among
asphalt to some of
with
reference
techniques
currently
program.
2.1
Molecular Extensive
Level research by many on petroleum for composition years. At at the this molecular point, much level of it
has is
been
done
workers
many but
essentially 2.1.1
textbook
material
worth
Species mass of
most
of
the of
variety
boiling are
air-blown carbon. 1
both
aromatic Structures
fragments type).
(aliphatic
type)
H I
H I
H I C/
II
I _c_C_H I H
2 structures
1 commonly
3 are make up
only
representative Structure in
fragments as are a
larger
molecules of of
asphalts. but
shown there or
straight numerous
chain
atoms,
typically chains
combinations
aliphatic
carbon
which
more
branches.
____CH
Structure While the major also mass contain of asphalt one or 4
2 (CH)x-CH3
a large nitrogen,
proportion sulfur,
of oxygen
molecules
and
metals.
Nitrogen,
in
the
form
of
pyridine
is
shown
in
Structure
5.
CH2-(CH2)x"Structure 5
CH 3
Sulfur,
as
benzothiophene,
is
shown
in
Structure
6.
Structure
6 on
the
right
is
shorthand
notation
of
the
one
to
the
left.
These
are
identical
molecular
fragments.
I
--H or
/
Structure 6
Both
sulfur
and
nitrogen it is
may easy
appear to see
in
any
of tens
variety of
of
sites of
within different
molecules.
Hence,
that
thousands
molecular different
species arrangement
may
be of
present elements
in
asphalt
considering a different
that
every It
constitutes
molecule.
also
follows
that species
any would
definition be
of
properties task.
based It is
on much
molecular
a monumental
to
classify
the
chemistry
in
terms
of
the
molecular
types.
Oxidation susceptible
to
Form to
New
Molecules. An
Certain aliphatic
types carbon
of next
carbon to an
in
oxidation.
aromatic
ring
is
known
as
a benzyl
carbon
and
is
an
example
of
readily
oxidizable
site.
Structure
is
an
example
of
a molecular
fragment
showing
a benzyl
carbon
in
bold
type
(adjacent
to
the
aromatic
ring).
CH2-(CH2)x
Structure
Sites
such
as
these
oxidize
to
form
ketones
as
shown
in
Structure
8.
C_(cH2)x--
Structure
More
severe
oxidation
may
result
in
formation
of
carboxylic
acids
and
loss
of
part 9.
of
the
molecule
such
as
shown
by
both
versions
of
Structure
r
Structure 9 Carboxylic acids, whether present in the original crude or formed upon oxidation, may be converted to sodium (Na) salts (Structure 10) or
calcium calcium
(Structure compounds.
11)
by
appropriate
reaction
with
sodium
or
II
II
II
oxidation An
on adjacent
example
Structure
0% c/O_c//0
(CH2)xCH3
Structure 12
Another asphalt an
type
of
oxygen as
containing phenols is
molecule oxygen by
which
may
be
present directly
in to
is a class ring.
known This
where
aromatic
class
illustrated
OH
CH3-(CH2)
x'- CH2,_CH
Structure 13
variations, addition of to
or
isomers,
containing
the of
basic
phenol
unit types
isomeric also
all An 16.
molecular example of
homologs series is
each by
homologous
shown
Structures
0 II
-C_cH2 -Structure 14
(CH2) x CH3
II
C_cH2--(CH2)x+I-CH3
Structure
15
O II
C_cH2--(CH2)x+2--CH3
Structure
16
above
case,
each
varies the
only
by
one
aliphatic all of
carbon. these
Each will be
is
molecule,
although
properties
among
quite
Another asphalts is
important quinolones
class as
of
compounds in
typically 17.
found
in
aged
shown
Structure
Structure
17
Many
sulfur
compounds
are
also
susceptible
to
oxidation
and
typically Structure
form 18.
sulfoxides.
sulfoxide
containing
fragment
is
shown
in
O II -(CH2)xCH2-S-CH2-CH structure
2.1.3 Metals. There are also metals 18
2-
present
in
asphalts,
again
in
varying
amounts
and
distributions.
The
most
common
metals
are
vanadium,
nickel,
and
iron
although
other
metals
may
also
be
present.
Typically
metals
are
present
as
organo-metallic
materials,
specifically
as
porphyrins.
An
example
is
shown
by
Structure
19.
CH3CH 2
CH3
CH3@__CH2CH3
3NZ'N(
cH cH2
By now it is obvious
CH3
CH2CH3
19
H3
of unique molecules
Structure
that
hundreds
of
thousands
may
be
found
in
any
given
asphalt.
Further,
the
second,
third
and
so
forth
asphalts
will
contain
hundreds
of
thousands
of
different
molecules.
2.1.4
Polarity.
All
of
the
naturally
occurring
heteroatoms,
nitrogen,
sulfur,
oxygen,
and
metals
contribute
to
polarity
within
these
Likewise, contribute to of
products of the
formed entire
upon
aging
are
polar
and which
polarity within
Polarity, by the of
a molecule,
moment gas
pyridine of
debyes zero. in
phase)
moment
(C6H 6) is also is
is the
analog
pyridine.
exists
other
heteroatom because it
containing tends to
important
in into
asphalt preferred
cause
to been
as
formations
terms
misused. is
A more given in
of molecular
orientation
asphalts
following
Subsection.
2.2
Intermolecular At the
Level level, polar molecules including This their is those attraction charges, in of or
have
behavioral another as
characteristic. a result of
molecule Figure
separated
dipoles.
1 illustrates
this
schematically.
(Figure 1A
+)CFigure IB
10
In
part
the
polar
molecules
are
randomized,
but
in
part
the
molecules
are
well
oriented
with
respect
to
each
other.
Part
represents
a more
stable
thermodynamic
state.
It
is
important
to
note
here
that
it
makes
little
difference
which
of
the
many
polar
molecules
shown
earlier
is
involved.
Any
one
of
the
many
types
of
polar
molecules
may
fill
the
molecular
schematics
shown
in
Figure
1A
or
B.
The
primary
requirement
is
that
some
sort
of
charge
separation
is
present
in
the
molecules.
It
is
obvious
that
a multi-molecular
structure
may
form
as
illustrated
schematically
in
Figure
2,
although
the
individual
molecular
components
will
vary
from
one
to
the
next
so
that
no
specific
regularity
exists
within
the
organized
zone
(see
note
I).
C+
G 0 0 0
-)C+ -)C+
Figure 2 this schematic shows positive of molecules. The associations among and other short range
-7
(Note
1)
For
simplicity,
and
negative
charges
at
the
ends
molecules
are
combinations
of
electrostatic
forces.
The
actual
charges
are
best
defined
in
terms
of
asymmetric
electron
density
and
are
not
true
plus
and
minus
charges
as
would
be
the
case
with
ions.
Neither
are
charges as
necessarily a convenient
distributed illustration.
end
to
end.
Figure
is
only
intended
11
During
the
organization,
some
amount
of
three-dimensional,
intermolecular
structure
forms.
Historically,
this
has
been
called
the
micelle,
or
colloid. molecules.
While The
it set
is
not
a have
true some
micelle, preferred
it
is
an
organized
set
of as
does
organizational
structure
compared
to
that
shown
in
Figure
IA
where
it
is
only
randomized
molecules.
The
structure
is
held
together
by
electrostatic
and
other
short
range
forces
which
are
weak
compared
to
covalent
chemical
bonds.
Short
range
(non-covalent)
forces
range
from
about
to
I0
Kcal/mole,
while
covalent
bonds
are
much
stronger.
For
comparison,
carbon-carbon
covalent
bonds,
the
bonds
that
hold
organic
molecules
together,
are
80
or
greater Kcal/mole.
Kcal/mole It
and follows
covalent organized
bonds
are
typically
i00 structure
(intermolecular)
may
be
subject or by
to raising
rearrangement its
or
may
be
scrambled this
either will
from occur
physical without
stress
temperature.
However,
changing same. On
All physical
of
the
molecular will
species be
remain
the
properties
different.
When
the
molecules
are
randomized,
they
can
move
about
with
respect
to
each highly
other
more
easily
than
when has
they more
are
more
organized. to motion or
The
more
organized
structure
resistance
deformation.
Said
differently,
structured
asphalt
is
more
of
springlike
material,
more
viscous,
and structure
is
stiffer. depends
The upon
ability the
to
form of
an the
or
selfand
strengths
number
of
sites
where
intermolecular
attractions
Oxidation
has
pronounced
effect
on
the
organized
structure.
As
oxidation
occurs,
new
sites
that
are
greater
polarity
are
formed
and
are
formed
in
larger
amounts
than
in
the
virgin
asphalt.
So
the
propensity
to
self-associate
will
increase.
Also,
the
rate
of
association
depends
12
upon
the
number
of
sites
and
the
magnitudes
of
the
attractions.
The
stronger
the
attractions
and
the
more
there
are,
the
greater
the
driving
force of
to
associate. Hence,
But, the
is
inhibited is slow.
by For
the
high
viscosity in one
asphalt.
example,
experiment,
virgin
asphalt
was
observed
to
double
in
viscosity
over
period
of
few
years.
The
sample
was
protected
so
that
oxidation
did
not
contribute
anything.
After
this
extended
storage,
the
sample
was
heated
to
mix
plant
temperature
while
protecting
it
from
oxidation.
The
viscosity of stiffening
returned of
to asphalt
near
its after
original oxidation,
value. with
The and
rates without
and
magnitudes
aggregate
present, time in
and the
at SHRP
various asphalt
temperatures, program.
are
being
studied
at
the
present
The
degree
of
association
varies
from
one
asphalt
to
another
and
several
methods One
can
be
used
to
determine used at
type the
and
magnitude time is
of size exclusion
association.
method
being
present
chromatography.
It
is
illustrated
in
Figure
3 which
shows
three
size
exclusion
chromatography
(SEC)
experiments,
all
plotted
on
the
same
axes.
Asphalts
AAG,
AAK,
and
AAM
(hereafter
noted
as
G,
K,
and
M)
are
all
similarly
classified
petroleum
asphalts.
All
three
were
separated
by
SEC
in
the
same
fashion. into
The
SEC
process to
separates size at
(in
this or
case,
asphalts)
components
according
multi-
molecular single
level. molecule or
It an
matters associated
not
whether group of
the
size
excluded In the
entity current
is
molecules.
work,
system
was
chosen
that
causes
the
least
possible
disturbance
to
the
association.
The
SEC
separates
asphalt
by
apparent
molecular
size
so
that
if
there
are
associated
groups
of
molecules
in
the
whole
asphalt
they SEC.
will The
also SEC
exist profiles
and
therefore shown in
be Figure
separated 3 are
as plots
an of
group of
by the
13
SEC CHROMATOGRAMS
30 -O
"==
AAM/_\ \
/'
_//1_ I I
25
_AAG
\
20 0 .,. 15
:
0
,
/ f'\ I I I _ / _a
\
\
\
*_ u
(J u_
10
\ \
0 0 20 40 60 80 100 120
Fi 9ure 3
14
whole the
asphalt x-axis.
on The
the three
y-axis
and
the
molecular
or are
size Note
on
materials
illustrated
that
asphalt
has
very
small
fraction
that
is
in
the
large
molecular
size,
and
significantly
larger
fraction
that
is
smaller
molecular
size
(the
right
side
of
the
plot).
Asphalt
is
almost
the
reverse.
Further,
these of
two
are
bimodal size
indicating material in
that either.
there
is Asphalt
relatively M, however,
small is
amount more of
intermediate
continuum.
That
is,
it
is
not
bimodal.
Asphalt
does
have
significant further
amount examinations
of
large of M
molecular and K by
species
present
as
does
K.
Upon weight
vapor-phase-osmometry
molecular
determination
in
pyridine,
it
was
discovered
that
the
large
molecular
species
in
are
comprised
of
many
smaller
molecules
whereas
in
Asphalt
the
largest
(left
of
plot) in M
is
comprised not
of
truly
molecules.
molecules
will
dissociate,
with
an
increase
in
temperature,
whereas
the
large
ones
in
will
dissociate.
If
nothing
else
is
apparent,
note
that
these
three
asphalts
appear
to
be
very tests
different would
from indicate
each that
other all
when three
examined are
by
SEC.
Yet
conventional
similar.
Another
effect
within
asphalts
is
the
behavior
of
the
molecules
which
have
very
little
association.
These
are
not
necessarily
smaller
molecules, of the
but asphalt
are (to
the the
less right
polar of the
and
therefore plot).
less Ion
associated exchange
portions
SEC
chromatography
(IEC)
and
supercritical
fluid
chromatography
(SFC)
have
both
been
used
to
show
that
these
molecules
also
vary
from
one
asphalt
to
another.
Often
called
a maltene
phase,
this
less-associated
material
behaves
as
"solvent"
for
the
polar
materials
and
will
behave
as
dispersing
agent.
It
will
tend
to
reduce
association
of
the
polars.
15
At
this
point,
it
is
worth
considering
a more
integrated
description
of
asphalt.
It
appears
to
be
a material
containing
polar
molecules
that
associate
strongly
into
organized
units
that
are
dispersed
in
less
polar
and
continuous
phase.
The
association
of
polars
appears
to
depend
upon can
of
polars effects
and of
upon the
thermal differing
history. chemistry
Some within
speculation the
continuous
neutral
phase.
First,
it
is
apparent
from
the
SEC
curves
that
asphalt
has
large
fraction
of
small
molecular
species
which
implies
that
the
less
polar
and
non-associated
materials
dominate
its
behavior.
It
would
be
expected
that
would
be
able
to
accommodate
additional
amounts
of
polars
with
minor
changes
in
its
physical
properties.
For
example, before
should
be
able
to
tolerate and
oxidation is observed.
viscosity
change
occurs
Asphalt the
should
be
and
is
the
Oxidation raise
of viscosity
should rapidly
increase with
already
polar is
oxidation.
The
propensity
to
oxidize
has
been
observed
by
another
method
being
used
in
the
SHRP
asphalt
studies.
Oxidation
in
pressurized
vessel
is
being
studied
as
a method
to
simulate
long-term
aging
of
asphalt
in
pavement.
After
400
hours
of
oxidation
at
60C
(140F)
under
pressure,
asphalt
had
an
aging
index
of
17
while
had
an
index
of
23.
When
the
temperature
was
raised
to
113C
(235F)
and
both
oxidized
at
atmospheric
pressure
for
72
hours,
asphalt
had
an
aging
index
(measured
at
60C)
of
only
18
while
jumped
to
530
under
the
same
conditions.
At
the
elevated
temperature,
both
asphalts
are
more
dissociated
and
oxidize
rapidly.
Upon
cooling
both
to
60C,
can
accommodate
its
own
oxidation
products
whereas
the
newly
formed
polars
in
strongly
dominate
its
behavior.
The
16
polars
in
asphalt
associate
very
strongly
and
raise
the
viscosity
quite
The subject
same of
trends differing
have
been of
observed oxidation
with of
other any
rates
at
different
temperatures,
note
in
Figure
4 how
the
viscosity
change
increases
with
increasing
oxidation
temperature.
This
indicates
that
maximum
road
service
temperatures
must
be
taken
into
account
in
the
selection
process
for
asphalts.
60C
POV
Aging
105
"_
10 4
103
I 100 Oxidation
I 200 Time, hr
I 300
I 400
Figure
2.3
Chemical
Model
of
Asphalt
The
model
that
is
emerging
from
this
work
is
built
upon
earlier
models
and
has
been
refined
during
the
SHRP
program.
In
this
case
model
means
nothing
more
than
clear
understanding
of
the
behavioral
of
asphalt.
The
model as
must well
be as
able all
to of
explain the
all
of
the in
characteristics
variations
behavior
from
one
asphalt
to
another.
Here,
it
is
worthwhile
to
review
17
the
manufacture
of
asphalt.
Petroleum
asphalt
is
typically
high
boiling
vacuum
distillation
residuum
which
is
prepared
from
numerous
petroleum
stocks.
Some
asphalts
are
produced
by
alternate
methods
but
generally
very
similar
portions
of
the
crude
oil
ends
up
as
asphalt.
The
and
physical to
therefore, reflects
vary the
quite nature
asphalt
used
to
prepare
it.
The
most
consistent
description,
or
model,
of
petroleum
asphalt
is
as
follows.
Asphalt
is
collection
of
polar
and
non-polar
molecules.
The
polar
molecules
tend
to
associate
strongly
to
form
organized
structures
throughout
the
continuous
phase
of
the
non-
polar indicate
Nuclear
magnetic are
data than
and about
thermodynamic 40 molecules,
data but
associations
some
have
smaller
assemblies
and
again
it
varies
from
one
asphalt
to
another.
Some
show
very
little
association.
The
non-polar
phase,
on
the
other
hand,
has
the
ability
to
dissociate
the
organized
structure,
but
again
it
varies
from
one
asphalt
to
another.
As
temperature
is
raised,
the more
associations dissociated
of and
polar
molecules less
decreases viscous.
and As
the
material is
becomes reduced,
therefore
temperature
the
opposite
occurs.
Recent
observations
indicate
that
the
non-polar
phase
also
organizes,
but
at
very
low
temperature,
temperatures
below
0C.
Further,
asphalt
is
susceptible
to
oxidation
which
increases
both
the
amount
of
polarity
and
the
number
of
polar
sites
present
among
asphalt
molecules.
This
further
contributes
to
the
ability
of
an
asphalt
to
organize,
but
again
varies
from
one
asphalt
to
another.
It
is
important
here
to
point
out
that
the
variations
in
behavioral
of program
asphalts is to
must elucidate
be
And can
again
the
objective among
distinguish
18
asphalts practice.
and
eventually the
reduce quantitation
these of
methods all
to
highway aspects
While
important
has
not
been
completed,
it
is
interesting
to
speculate
on
how
the
variations performance.
in
chemical
properties
may
be
reflected
in
the
pavement
19
3.0
SPECULATION
ON
RELATIONSHIP
OF
CHEMISTRY
TO
PAVEMENT
PERFORMANCE
3.1
General
Co_tnents
While
it
is
unusual
to
describe
performance
in
terms
of
failure,
nevertheless
it
is
instructive
to
do
so
here
since
it
is
generally
understood
that
all
pavements
will
eventually
fail
unless
they
are
rebuilt
periodically.
Performance
must
be
defined
as
sufficient
time
to
failure
or
to
reconstruction
to
justify
the
use
of
any
particular
methodology
and
any
given
set
of
materials.
Sufficient
service
life
is
determined
by
cost
of
construction,
traffic
density,
harshness
of
the
environment, determination
soil of
(support) acceptable
and is
other subject
factors. of this
The work.
However,
service
lifetimes
of
few
months
to
few
years,
which
are
experienced
all
too
frequently,
are
unacceptable,
whereas
i0
to
20
years
of
service
gives
more
acceptable
life
cycle
costs.
Neither
is
methodology
the
subject
of
this
work,
so
it
will
be
assumed
that
construction
methodology
is
both
consistent
and
adequate.
The
focus
will
be
upon The
variations significant
in
the failure
quality modes
of in
construction asphalt
related I.
to
materials
are
generally
agreed
to
be
Permanent
deformation
2. 3.
4.
Low
temperature
cracking
5. 6.
damage of adhesion
2O
Some
on
the of
relationships are
of given
these in the
failure sections
modes
to
the the
chemical section
asphalts
following
3.2 Aging
Aging conditioning detrimental already when view may a of be is often step when included which may in be the above list, or but aging is actually It may in be an a
beneficial or other
detrimental.
hardening On the an
stiffening hand,
is observed may be
adequate soft
aging
beneficial
mixture
into
adequate
deform,
stiff
cracking,
either these
traffic
load
thermal
5 illustrates of temperature,
schematically oxidation.
also
includes
time,
PERFORMANCE
Little Association SOFT Well Balanced Highly Associated BRITTLE
Figure
21
or the
oxidative hardening
imparts
permanent and
hardening from
in
temperature
molecular
organization
are
reversible.
That
is,
as
an
asphalt
cement
oxidizes,
whether
in
bulk
or
in
a mixture,
the
cement
becomes
and
stays
stiffer
at
any
given
set
of
conditions.
However,
warming
cold
asphalt
in
the
absence
of
any
other
effects
will
soften
it
to
its
original
value
and
heating
cement
to
an
elevated
temperature
such
as
mix-plant
temperature
will
reverse
the
effects
of
organizational
hardening.
It
is
important
to
note
that
hardening
resulting
from
molecular
organization
can
be
reversed
periodically
by
recycling
pavement.
However,
the
recycling
process
removes
only
the
organizational
hardening, portion is
but not
since removed
pavement during
suffers the
oxidative
hardening
also,
this
recycled
process.
The
events
that
lead
to
aging
in
a pavement
are
very
slow
because
the
driving
forces
for
orientation
(dipole
of
each
molecule)
are
small
and
the
whole
medium
is
quite
viscous
at
road
service
temperature.
slowly orientation,
the
molecules as the
will
shuffle
about
and
eventually state or
find
known
thermodynamic
stable
and
in system.
so
orienting Aggregates,
themselves no doubt,
become have
a a
better distinct
packed effect
and on
this
orientation
but
also
differ
in
their
ability
to
cause
orientation.
The
result
is
an
increasingly is
stiffer achieved.
(more
rigid)
material
until
thermodynamic
equilibrium
In target!
achievement constant
of
thermodynamic in composition
equilibrium which
is result
a moving from
changes
oxidation
of
asphalt.
During
oxidation
polarity
changes,
hence,
the
"best
packing"
changes.
Further,
temperature
changes
constantly
in
22
varies species,
with
temperature. under
Also, heavy
especially of
thermodynamic up orientation
speed or if
molecules
to move
orientation
system one
"stirred." and oxidize in upon saving and feature accommodate other As to it. their asphalts shown their in own as a While own do
interesting G, may
asphalt
products
major in
changes
viscosity, oxidation.
all quench as
quench
oxidation result of
in viscosity Figure
Also, the
noted
earlier
4, this
maximum
temperature dictate of
among as
asphalts
the
that
a result of
oxidation is
temperatures. it the is
While
quenching of an
a measurable
asphalt relates
viscoelastic
therefore
performance
characteristics
asphalt.
3.3
on
the
Relationship
of
Composition
to
Various
Failure
chemical structural is
that of
are
believed are of
to
relate
to Again
the from
or it
a pavement is a of set
believed units)
asphalt consist
agglomerates
(structured
polars
in
23
less
polar
to
nonpolar
phase.
The
result
is
a material
which
has
an
elastic molecules,
behavior but it
as is
result also
of
the
network with a
formed viscous
by
the
a material
behavior
flow
or
creep
because
various
parts
of
the
network
can
move
with
respect
to
each
other
under
prolonged
stress.
The
relative
contributions
of
the
elastic
and
viscous
behavior
vary
with
composition.
3.3.1
Ruttinq
and
Permanent
Deformation.
Again,
consider
asphalts
G,
K,
and
M.
Their
SEC
plots
are
shown
in
Figure
3.
Asphalt
is
largely
the
dispersing
phase,
not
much
elastic
in
character.
One
would
expect
it
to
be
very
compatible
as
is
observed
in
oxidation
and
compatibility oxidation. It
index does
Asphalt well
G which
is
somewhat makes it
insensitive a material
to that will
rut
or
deform,
especially
at
higher
temperatures.
It
has
little
of
the
compositional
feature
of
large
molecular
size
to
give
it
elasticity.
Asphalt
is
mostly
the
non-associated
material
which
does
tend
to
organize
and
harden
at
low
temperature.
Therefore
would
be
expected
to
be
very
stiff
(susceptible
to
cracking)
at
very
low
temperature.
In
fact,
these
are
observed
behaviors
for
in
roadways.
Contrast
this
with
the
SEC
plot
for
asphalt
K.
Asphalt
has
large
amount
of
agglomerated
material
and
would
be
expected
to
have
greater
elastic
modulus
at
high
temperature
than
asphalt
and
not
have
the
propensity
to high
rut;
and
this
is weight,
also
what should
is and
Asphalt somewhat
M,
with like
its
truly K at
molecular
asphalt
high
temperature.
Asphalt
is
also
a more
homogeneous
material
than
or
G.
This
feature to M,
should and
impart this
relatively is
low
temperature
susceptibility
likewise
observed.
24
If properties
the been
relationship obvious,
of
composition some
to recent
consider
blending
of
dispersed
and
dispersing
phases
of
asphalts.
These
separated were
phases in
were an
generated asphalt
by
SEC. by
Major blending
changes
in
properties of different
observed
prepared
fractions
asphalts.
In
one
case,
the
dispersed
phase
of
one
asphalt
was
mixed
with was
the more
phase times
of the
second
asphalt. of either
The
resulting
asphalt The
viscosity
original
material!
dispersing
phase
of
the
second
asphalt
is
not
good
"solvent"
for
the
dispersed
phase
of
the
first.
By
appropriate
cross
blending,
one
can,
within pushed
reason, up or
achieve down at
a will.
wide
of
properties. of
can
be
(a measure
contribution
of
the
elastic
and
viscous
moduli)
can
be
varied
significantly.
This
area
is
not
yet
fully
understood
and
is
under
intensive of this
at
the is as
present needed
Obviously,
clear
specification different
asphalts
mixtures
3.3.2
Thermal
and
Fatigue
Cracking.
Cracking
is
another
serious
failure the
in
roadways, network
and
again
can
be
related
to
binder or
If
molecular
(agglomerate,
micelle,
colloid,
is
preferred)
becomes
too
rigid,
the
ability
of
an
asphalt
to
deform
elastically will be
will separated
be to
lost. a point
Instead, that
the healing
asphalt cannot
fractures occur.
and The
likely constant
working
of
very
rigid
matrix
will
eventually
suffer
fatigue
and
crack.
The
potential
to
crack
is
compounded
by
yet
another
organizational
feature. organize
At into
low
temperature, structured
the
more form as
neutral can be
materials seen by
begin
to
a more
differential
25
scanning
calorimetry
(DSC).
Now,
the
asphalt
is
quite
brittle
and
subject
to
cracking
under
stress.
To
make
matters
worse,
some
cements
shrink
significantly
at
low
temperature
as
result
of
the
organization
of
low
polarity
and
nonpolar
components.
This
aggravates
cracking.
Again,
it
varies
with
composition
from
one
asphalt
to
another.
All
other
things
being
equal,
the
more
linear
aliphatic
materials
show
the
most
pronounced
tendency
to
shrink
with
decreasing
temperature.
Hence,
cracking
at
low
temperature
would
be
expected
if
shrinkage
occurs,
and
is
expected
to
be
most
closely
related
to
the
compositional
feature
of
aliphatic/aromatic
ratio
when
all
other
characteristics
are
equal.
Aliphatic/aromatic
ratios
can
be
determined
by
NMR,
but
it
is
probably
more
practical
to
either
measure
shrinkage
directly
or
predict
it
from
very
rapid 3.3.3
DSC
Adhesion
go
together
only
to
point. problem,
While
loss
of forms
adhesion of
certainly damage
is may
a also
serious
moisture
damage
other
moisture
occur.
At
this
point,
consider
only
adhesion.
By
definition,
it
must
involve to
both
asphalt the
and
aggregate. of
While asphalts
SHRP and
has
commissioned the
studies
investigate
interaction
aggregates,
examination
of
adhesion,
per
se,
is
not
within
the
scope
of
the
binder
composition
studies.
Nevertheless,
some
interesting
observations
can
be
made
considering
only
the
binder.
Adhesion
of
components
in
asphalt
to
aggregate
appears
to
be
governed
as
much
at
the
molecular
level
as
at
the
inter-molecular
level.
Specific Certainly
functional overall
groups polarity,
types) separation
seem of
to
be
very
important. the
charge
within
organic
molecules,
promotes
attraction
of
polar
asphalt
components
to
26
the
also
polar
surface
of
aggregate.
Several
workers
within
the
Strategic substantially,
Highway and
Program in some
have cases
shown
that
aggregates behavior
vary varies
quite with
aggregate
environment.
Some
aggregates
have
positive
sites,
some
negative,
and
some
show
variation
in
polarity
with
moisture
content,
temperature,
etc.
For polar
this
discussion,
aggregate arises
will
be
considered of the
to
be
simply of
a the
highly polars
surface.
Adhesion
because
interaction
in in
asphalt asphalt
with may
the not
polar be
surface
of to
an
aggregate. good
But adhesion
polarity in
alone
sufficient
achieve
pavement
because
asphalt
is
affected
by
its
environment.
Asphalt
has
the
capability
of
incorporating
and
transporting
water.
More
on
this
in
the
moisture
damage
section.
Absorption
of
water,
like
all
other
behavior,
varies
with
asphalt
composition
including
changes
in
composition
as
result
of
oxidation.
Incorporation
of
water
is
measurable
as
are
the
effects
of
the
invasion
of
water
into
the
asphalt
aggregate
mixtures.
At
the
molecular
level
in
asphalt
it
has
been
observed
that
basic
nitrogen
compounds
(pyridines)
tend
to
adhere
to
aggregate
surfaces
tenaciously.
Carboxylic
acid
salts,
while
quite
polar,
tend
to
be
removed
from
aggregate
more
easily,
but
this
varies
with
the
type
of
salt.
Monovalent
cation
salts,
such
as
sodium
or
potassium,
of
acids
tend
to
be
removed of
from acids
quite more
easily. resistant
Calcium to the
or action
other of water.
divalent
salts
From
practical
viewpoint,
it
would
behoove
the
user
to
assure
the
acids of
in
asphalts and
are sodium
not
in salts
the are
form
of
monovalent the
salts. and
The it
examples should be
pyridines
somewhat
extremes
obvious
that
there
is
spectrum
of
tenacity
of
adhesion
among
the
organic done
molecules elsewhere
in within
asphalt. the
The
evaluation
of
this
spectrum
is
being
program.
27
Moisture problem reducing omnipresent For water will this and come in
damage pavement.
without
apparent
loss
of
adhesion is clear,
is
another factor is
common in
Certainly, of
highway but
design to be
the
availability in roadways,
water,
so the
effects design in
of moisture is adequate
discussion, also in to
that
invasion in into
Still, affect
asphalt soaks
performance aggregate, into polar effect chemical asphalt reduced Aged or the
is
a highly by
polar of
material attraction
asphalt
virtue
asphalt the
components.
Upon
invasion
into
mechanical
typically water is
dilution results
molecular further
solvent. in rutting
typically other of
strength oxidized
and
greater water
amounts to
products), This of
a greater
be
polarity
invasion, aged
chemical also
pavements
are
harder
new counter in
effects The
are
combined properties
terms varies
behavior
composition.
28
4.0
SU_a4ARY
The
chemistry
of levels
asphalt discussed.
at
the It
molecular is clear
intermolecular
thousands
of
molecular
species
exist
within
any
particular
asphalt.
The
polarity
among
asphalt
molecules
varies
widely
and
the
physical
properties
are
governed
by
the
balance
of
polars
and
nonpolars
components. cause
Polars
tend
to
associate speculations
while on
less the
polar effects
and of
nonpolars chemical
dissociation.
Several
composition mechanical
on or
pavement structural
performance properties
have of
been asphalt
In
general, to the
the
intermolecular
structuring
among
the
polars.
These
interactions
may
arise
by
involvement
of
any
of
numerous
different
chemical
species.
The
exact
nature
of of
the
chemical within
specie the
is
less
important molecule.
than
the
distribution
charge
specific
Excessive
structuring little
leads
to
brittle to
cements materials
which which
tend
to
crack, under
while stress.
too
structuring
leads
deform
Oxidation contributing
adds to
to
age
hardening
and zones
brittleness within
of binder.
asphalt
cement
by
the
structures
Finally,
the
word
asphalt
should
be
used
in
the
same
sense
as
the
word
glue.
As
much
as
there
are
significant
differences
among
glues,
e.g.,
carpenters
glue,
airplane
glue
and
rubber
cement
perform
very
differently asphalts.
from The
each
other,
so among
are
there
differences as the
among diversity
differences
asphalts
of new
the
crude
oils
used to
to
manufacture and
them. achieve
The
objective
of
developing and
specifications
describe
consistent
behavior,
therefore
consistent
performance,
is
of
high
priority
from
the
user's
29
cost
standpoint.
But
the
user
must
also
realize
that
the
cost-effective
supply
line
(crude
oil)
consists
of
a wide
variety
of
materials,
and
there That
is is,
little the
chance
of of
limiting set of
the crude
source oils
of to
supply.
selection
manufacture
asphalts
is
impossible.
It
is
therefore
obvious
that
achievement
of
consistent
performance
with
asphalts
frequently
will
require
modification
of
materials
that
are
produced
today.
principal
value
of
the
composition
studies
is
to
develop
an
understanding
of
what
compositional
features
are
needed
to
produce
material
with
the
desired
properties.
Then
this
information
can
be
used
to
select
and/or
modify
asphalts
to
obtain
binders
that
will
perform
in
cost-effective
manner.
3O
Asphalt
Advisory
Committee
George West Shell Oil Company Liaisons Avery D. Adcock United States Air Force Ted Ferragut Federal Highway Administration Donald G. Fohs Federal Highway Administration Fredrick D. Hejl
Thomas D. Moreland, chairman Moreland Altobelli Associates, lnc. Gale C. Page, vice chairman Florida Department of Transportation Peter A. Bellin Niedersachsisches fiir Strass7enbau Dale Decker National Asphalt Paving Association Joseph L. Goodrich Chevron Research Company Eric Harm Illinois Department Charles Hughes Virginia Highway Robert G. Jenkins University of Cincinnati Anthony J. Kriech Heritage Group Company Richard Langlois Universite Larval Richard C. Meininger National Aggregates Association Nicholas Nahas EXXON Chemical Charles F. Ports APAC, lnc. Ron Reese California Department & Transportation Research Council of Transportation
Landesamt
Transportation
Research
Board
Aston McLaughlin Federal Aviation Bill Weseman Federal Highway Administration Administration
of Transportation
Donald E. Shaw Georgia-Pacific Corporation Scott Shuler The Asphalt Institute Harold E. Smith City of Des Moines Thomas J. Snyder Marathon Oil Company Richard H. Sullivan Minnesota A. Haleem Department Tahir of Transportation
of Transportation
Paving Association
American Association of State Highway and Transportation Officials Jack Telford Oklahoma Department of Transportation