SHRP-A/UWP-91-510

Chemical Properties of Asphalts and Their Relationship to Pavement Performance

Raymond E. Robertson Western Research Institute Laramie, WY

Strategic

Highway Research Program National Research Council Washington, D.C. 1991

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 an Aromatic Hydrocarbon of an Aromatic Hydrocarbon

of an Aliphatic and Aromatic Hydrocarbon of a Pyridine of a Thiophene ................................... .................................. ...........................

Showing Benzyl Carbon of a Ketone

....................................

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

16 Molecular Fragment of a Homolog

..................................

8 8 9 9

17 Molecular Fragment of a Quinolone .................................. 18 Molecular Fragment of a Sulfoxide 19 Metalloporphyrin ..................................

...............................................

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

characteristics studies have shown

in

roadways. that there

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

polarity the work

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

non-polar and that

materials this rigid this

also

tend

to

organize at

into low

a very

rigid It

material, is for low

material type of

shrinks shrinkage

temperature.

speculated temperature

that

is

largely

responsible

cracking.

second

major

objective types of

is to research with

translate methods emphasis the same

research have on been

methods employed

into to

test

methods.

Numerous among

differentiate which

asphalts

an in

identifying that

methods they are

distinguish by

among their

asphalts performance

fashion

distinguished

characteristics.

The are to

expected develop

advantages methods for

of this selection

work, of

both asphalts the

technical that

and

economic, in of a

will

perform problem and

predictable premature producers personnel sense of

fashion road of

thereby

alleviating the

current

conunon users

failure.

Throughout asphalt advice have on

program, closely direction in

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

development be required could to

questions for

arise

as

to of

how new

much test methods. but it

specialization Certainly is still is new

implementation

test

methods

become

extraordinarily there is no

complex, more

another absolutely

objective

assure

that of when test

complexity therefore,

than should test and

necessary. and a

Problems so

implementation, one considers in in both

be method

minimized will

espec'ially round The robin

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

Objectives The SHRP

of

the

SHRP

Asphalt area

Program is a highly focused endeavor which

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

meaningful asphalt are

specifications. little more than

The a

current quality

specifications control exercise

for for

petroleum the refiner's

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

properties then select

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

specifications objective of 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

convenient The part first is the

to

divide is

the the

chemistry at

of

petroleum molecular all

asphalt level

into and

parts. second

part

chemistry of

the

chemistry of the

interaction nature

among of

molecular can best be

species described, species asphalt. molecular chemistry to

in asphalt. in terms

Much of

physical as an

asphalt or matrix units at

composition, into large exist levels. molecular is to

assembly

of molecular within the

(building Numerous and of

blocks)

multi-molecular to examine In the asphalt following is

techniques

both

the the reference "building

intermolecular asphalt at the

subsection without of

level

reviewed what

experimental are is

methods. The in used

This

illustrate of interaction

types

blocks" molecules the

present. reviewed being

chemistry the second

among

asphalt to some of

subsection in the SHRP

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

reviewing At is are the

here. molecular of level a wide

Typical total high some have

Species mass of

in Virqin neat (tank)

Asphalt. asphalt Some like

most

of

the of

a mixture aliphatic asphalts) Examples

variety

boiling are

hydrocarbons. (more and in

(waxy and of some such and 2

materials), molecules molecular (aromatic

aromatic aliphatic are shown

air-blown carbon. 1

both

aromatic Structures

fragments type).

(aliphatic

type)

H I

H I

H I C/

H_ C _"C" C_"C"c/C_ _CH2_ICH2 _ _x_CH3 _ x Typically = 15 or More Carbons I I HIC-_c/C_c/C I I H H

Structure represented molecular 1 is by Structure of 3. Both

II

I _c_C_H I H
2 structures

Structure Structure 1 and that carbon 2 is more

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

asphalt have one

combinations

aliphatic

carbon

which

more

branches.

Structure Structure carbon. 4 shows a molecule which is

3 a mixture of aliphatic and aromatic

____CH
Structure While the major also mass contain of asphalt one or 4

2 (CH)x-CH3

is hydrocarbon, more heteroatoms;

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

specific more effective

molecular

a monumental

to

classify

the

chemistry

in

terms

of

the

molecular

types.

2.1.2 asphalt are

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

(Ca) salts inorganic

(Structure compounds.

11)

by

appropriate

reaction

with

sodium

or

II

II

II

Structure Carboxylic upon rings. acid

i0 anhydrides when two is (typically benzyl carbons 12. called are

Structure anhydrides) present

11 may be formed aromatic

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

is attached Structure 13.

aromatic

class

illustrated

OH

CH3-(CH2)

x'- CH2,_CH
Structure 13

Again may shown

numerous exist. above, In

variations, addition of to

or

isomers,

containing

the of

basic

phenol

unit types

isomeric also

combinations typically 14,

all An 16.

molecular example of

homologs series is

each by

exist. 15, and

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

In the unique similar.

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

molecules. further is the

Likewise, contribute to of

oxidation the charge The

products of the

formed entire

upon

aging

are

polar

and which

polarity within

system. can be seen

Polarity, by the of

separation example. is 2.19

a molecule,

following (C5H5 N) benzene Polarity Polarity organize have these been

dipole (in the Benzene all

moment gas

(separation whereas all carbon

of charge) the dipole of

pyridine of

debyes zero. in

phase)

moment

(C6H 6) is also is

is the

analog

pyridine.

exists

other

heteroatom because it

containing tends to

species. molecules these although to

important

in into

asphalt preferred

cause

themselves referred have within

orientations. of micelles, current the

Historically, colloids, understanding etc.,

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

intermolecular another for

asphalt, one polar

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

carbon-hydrogen then that the

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

molecular the other

composition. hand, the

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

organized, attractions occur.

or

selfand

assembled, upon the

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

association overall process

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

materials the molecular

(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

associated the fraction

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

Large Molecular Size

Small Molecular Size

Fi 9ure 3

14

whole the

asphalt x-axis.

on The

the three

y-axis

and

the

molecular

or are

multi-molecular virgin asphalts.

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

fraction The large

(left

of

plot) in M

is

comprised not

of

truly

large for example,

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

composition be made on the

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

asphalt any major

should

be

able

to

tolerate and

significant this is what

oxidation is observed.

viscosity

change

occurs

Asphalt the

should

be

and

is

the

reverse. effect observed. and

Oxidation raise

of viscosity

should rapidly

increase with

already

predominant This likewise

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

substantially. While on the

The subject

same of

trends differing

have

been of

observed oxidation

with of

other any

asphalts. given asphalt

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.

EFFECTS OF TEMPERATUREON AGING KINETICS OF AN ASPHALT SENSITIVE TO MOLECULAR STRUCTURING

106 -

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

characteristics observed 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

chemistry from one

and

physical to

properties, another and each

therefore, reflects

vary the

quite nature

significantly of the crude oil

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

materials. that the

Nuclear

magnetic are

resonance not more

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

characteristics of the SHRP

of program

asphalts is to

must elucidate

be

measurable. methods which

And can

again

the

objective among

distinguish

18

asphalts practice.

and

eventually the

reduce quantitation

these of

methods all

to

highway aspects

laboratory of the model

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

conditions, service life

and is

numerous not the

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

materials. pavement that may be

related I.

to

materials

are

generally

agreed

to

be

Permanent

deformation

2. 3.

Rutting Fatigue cracking

4.

Low

temperature

cracking

5. 6.

Moisture Total loss

damage of adhesion

2O

Some

speculations properties on aging.

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.

excessive pavement. hardens in terms

hardening On the an

stiffening hand,

is observed may be

adequate soft

aging

beneficial

mixture

into

adequate

pavement. properties or may is be

A simplified that too a pavement and or

performance too and soft and

of mechanical rut to and

therefore subject Figure effects

deform,

stiff

brittle under and

therefore stress. the

cracking,

either these

under points and

traffic

load

thermal

5 illustrates of temperature,

schematically oxidation.

also

includes

time,

PERFORMANCE
Little Association SOFT Well Balanced Highly Associated BRITTLE

Permanent Deformation, Rutting Time, Aging, Moisture,

Fatigue and Low Temperature Cracking Cooling Heating

Figure

21

Oxidation, asphalt while

or the

oxidative hardening

hardening, from reduced

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.

Nonetheless, the best

slowly orientation,

the

molecules as the

will

shuffle

about

and

eventually state or

find

known

thermodynamic

stable

equilibrium, bound together

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!

roadway, There are

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

pavement traffic traffic

and tends loads

thermodynamic to and It disorient this is not

equilibrium molecular effects whether for

varies species,

with

temperature. under

Also, heavy

especially of

further clear energy

achievement traffic loads

thermodynamic up orientation

equilibrium. by is providing slowed

speed or if

additional the has as

molecules

to move

orientation

by keeping aging such

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

Oxidative some asphalts,

interesting G, may

asphalt

oxidation show Figure

products

without increases virtually so doing

major in

changes

viscosity, oxidation.

substantial 4 earlier, and in

viscosity asphalts their was

all quench as

eventually own increase in of

quench

oxidation result of

in viscosity Figure

oxidation. varies with

Also, the

noted

earlier

4, this

phenomenon Compositional increase

maximum

temperature dictate of

oxidation. amount at not and to of viscosity

variations is observed the

among as

asphalts

the

that

a result of

oxidation is

different fully does the understood, relate to

temperatures. it the is

While

chemistry property and

quenching of an

a measurable

chemical properties, of the

asphalt relates

viscoelastic

therefore

performance

characteristics

asphalt.

3.3

Speculation Modes The measurable

on

the

Relationship

of

Composition

to

Various

Failure

chemical structural is

properties strength that that

that of

are

believed are of

to

relate

to Again

the from

mechanical the model,

or it

a pavement is a of set

several. "hardcore" dispersed

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

polar that can

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

studies. not harden

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

observed. does behave

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

heretofore has not

the been

relationship obvious,

of

composition some

to recent

performance results from cross

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

dispersing than i000

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

variety Tan deltas

of

properties. of

Viscosities the relative

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

study phenomenon are sold

at

the is as

present needed

time. for from

Obviously,

clear

understanding since many

specification different

purposes, crude oils.

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

composition. whatever term

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

measurements. and Moisture Damaqe. Adhesion and moisture damage

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,

(molecular that is,

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

aggregate are much

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

a major water are to

the

availability in roadways,

water,

so the

effects design in

of moisture is adequate

unavoidable. remove most some its like water

discussion, also in to

consider resist with water its

that

invasion in into

to pavement. and will

Still, affect

contact when the

asphalt soaks

pavement the and

performance aggregate, into polar effect chemical asphalt reduced Aged or the

concrete. to of some polar the

Water, extent water

is

a highly by

polar of

material attraction

is transported molecules water From the a of in to will

asphalt

virtue

asphalt the

components.

Upon

invasion

into

asphalt, it. like

mechanical

properties, the action of weight

typically water is

softening somewhat This or

viewpoint, with a low

dilution results

molecular further

solvent. in rutting

typically other of

strength oxidized

and

results which to have

deformation. polars extent than The

asphalts, tend would

greater water

amounts to

(oxidation new asphalts.

products), This of

incorporate expected from from a

a greater

be

polarity

considerations. viewpoint, increases their

probability with pavement

moisture age. But

invasion, aged

chemical also

pavements

are

harder

than and are mix.

counterpart somewhat measured the

new counter in

pavements, to of each the with

so the other. mechanical

effects The

of moisture effects of the

oxidation better As usual,

are

combined properties

terms varies

behavior

composition.

28

4.0

SU_a4ARY

The

chemistry

of levels

petroleum has been

asphalt discussed.

at

the It

molecular is clear

and that hundreds of

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

offered. are related

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

tremendous are as great

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

significantly a very limited

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

Expert Task Group

Ernest Bastian, Jr. Federal Highway Administration Wayne Brule New York State Department Joseph L. Goodrich Chevron Research Company Woody Halstead Consultant Co. Gayle King Bituminous Materials Robert F. LaForce Colorado Department of Transportation Mark Plummer Marathon Oil Company Raymond Pavlovich Exxon Chemical Company Ron Reese of Transportation Co., lnc.

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

California Department Scott Shuler Colorado

of Transportation

Paving Association

American Association of State Highway and Transportation Officials Jack Telford Oklahoma Department of Transportation