Chemical Properties of Asphalts and Their Relationship to Pavement Performance

SHRP-A/UWP-91-510 Chemical Properties of Asphalts and Their Relationship to Pavement Performance Raymond E. Robertson Western Research Institute Lar...
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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

1993

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

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

1 1 2

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 3 3 5 9 9 10 17

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

4.0 Summary

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

20 20 21 23 24 25 26 29

V

List of Structures

1

Molecular Fragment

of an Aliphatic

2

Molecular Fragment

3

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

4

of an Aromatic Hydrocarbon

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

4

Molecular Fragmem

of an Aromatic Hydrocarbon

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

4

4

Molecular Fragment

of an Aliphatic and Aromatic Hydrocarbon

5

Molecular Fragmem

of a Pyridine

6

Molecular Fragmem

of a Thiophene

7

Molecular Fragmem

Showing Benzyl Carbon

8

Molecular Fragmem

of a Ketone

9

Molecular Fragmem

of a Carboxylic Acid ..............................

6

of a Sodium Carboxylate

7

10 Molecular

Fragmem

Hydrocarbon

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

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

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

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

4 5 5 6 6

11 Molecular Fragment

of a Calcium Carboxylate

12 Molecular Fragment

of a Carboxylic Anhydride

13 Molecular Fragment

of a Phenol

14 Molecular Fragment

of a Homolog

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

8

15 Molecular Fragment

of a Homolog

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

8

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

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

vii

7 7 7

16 Molecular Fragment of a Homolog

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

8

17 Molecular Fragment of a Quinolone ..................................

8

18 Molecular Fragment of a Sulfoxide

9

19 Metalloporphyrin

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

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

Vll"1""

9

List of Figures 1A

Randomized

1B

Organized

2

Three Dimensional

3

S.E.C. Chromatograms

4

Effects of Temperature on Aging Kinetics of an Asphalt Sensitive to Molecular Structuring .......................................

17

Performance

21

5

Molecules Molecules

°

.........

°

°





Molecular



°







°



" "

" *

" " .........

°









°

°







°

°









°

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

• •





10



Matrix ..............................

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

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

ix













.

o •

o

10

11 14

S_Y

F,_C_ZVE

The

chemistry

of

intermolecular

levels

interpretation

and

performance

thousands

of

asphalt.

Asphalts

vary

widely

this

portion

asphalts

strongly

matrix

polar

to

gives

phase

These

polar

form

elastic

gives

while

little

cement

zones

by

the

to

to

adds

binder.

to

leads

the

age

additional

At

very

low

xi

less

of

contributor

to

and

which

which

materials

any

the

chemical

a

set

of

the

It

of

of

of

asphalt.

and

of

polar

continuous

materials

non-polar

involvement

while

to

associate

among

assemblage

cements

of

properties

nature

temperature

that

objective

polar

exact

hardening

polar

tend

The

to

particular

species

major

by

asphalt

to

very

arise

the

brittle

a

may

non-polar

of

characteristics

structuring

the

any

major

structural

overall

component

leads

contributing

within

the

structuring

Oxidation

or

explain

hundreds

molecular

The

materials

in

may

level

within

behavioral

dispersed

data

least

of

Polar

within

viscous

at

of

molecular

exist

intermolecular

character

a

that

combination

the

is

species.

a matrix

are

and

chemical

Polarity

mechanical

than

a

weight.

interactions

important

structuring

stress.

the

and

At

explain

is

chemical

excessive

too

to

the

to

less

materials

is

molecular

comprised

molecular

which

general,

different

is

be

chemistry.

related

components. numerous

work

of

to

the

how

there

species

and

a matrix

In

are

that

known

on

roadways.

characteristics.

into

materials.

are

terms

in

at

herein

placed

molecular

the

performance

specie

discussed

shown

polarity

of

in

have

unique

in

asphalt

speculation

studies

asphalt

is

characteristics

historical

the

petroleum

polar

medium.

The

continuous

is

non-

speculated

tends

to

deform

brittleness

to

the

it

appears

that

crack

under

of

asphalt

structured

that

of

the

non-polar and

materials

that

this

speculated

A

rigid

that

temperature

methods.

by

develop

producers

of

personnel

both

with

Certainly

to is

any

is

should test and

give

for

new

test

another

largely

rigid

material, It

is

responsible

asphalt

method

will

for

low

on

The

that

asphalts

that

the

worked

test

to

methods they

closely direction in

each

arise

as

become

Problems

robin

of when

test

robin

xii

conunon

are

with

there

is

and

to

effort,

of

and contractor

maintain

a

to

how

much

of

new

test

methods.

complex,

but

no

in in

problem

a

sector.

more

considers

program

in

SHRP

implementation, one

economic,

perform

users

extraordinarily

that

so

and

will

both

implementation

assure

round

current

program,

program

could

round

fashion

of

the

espec'ially a

identifying

technical

for

enter

into

employed

both

be

and

been

work,

questions

to

on

same

implementable

required

have

methods

characteristics.

development

methods

laboratories.

the

have

advice

research

emphasis

alleviating

necessary.

minimized

in

Throughout

objective

be

an

selection

practically

absolutely

user

a very

temperature.

methods

of this

thereby

will

new

still

low

translate

performance

advantages

petroleum

what

with

asphalts

failure.

specialization

than

their

fashion road

As

into

is

research

asphalts

methods

premature

of

at

shrinkage

is to

of

among

expected

predictable

sense

of

types

distinguish

to

type

organize

shrinks

objective

among

distinguished

is

this

major

differentiate

are

to

material

Numerous

The

tend

cracking.

second

which

also

both

fact,

it

complexity therefore,

that

each

state has

new

highway

already

begun.

Finally,

this

results

that

implemented

are

work

is

supported

into

new

domain.

xiii

by

test

public

funding

methodology

and

will

be

the

public

1.0

i.i

Objectives The

of

SHRP

ultimately

be

known

vacuum

asphalts

and

as

this

a mix

they

than

are

a

of

using

classified

in

the

It

behooves

binders

which

no

are

have

doubt

asphalts

a

set

pavements

of

various

the

user,

reflected

types

therefore, in

desirable

petroleum

that

have

there

of

viscosities

residua

desirable

to

is

be

used

at

material.

Yet,

vary

quite

have

early

been

failures

determine

performance

properties.

will

or

two

no

performance

must

develop

the

refiner's

distinction

elevated

That

AC-20,

their

and

is,

all

all

will

The

rude

surprises

and

with

what and

costly

increasing

properties then

a

be

practical

to

results

frequency.

of

select

modification

characteristics.

of

performance

significantly.

From

require

in

petroleum

for

susceptibility.

example,

to

for

little

mixtures

properties

exercise

for

to

pavement

performance

many

of

and

material

control

hence

asphalts

binders

are

which

asphalt-aggregate

specifications

quality

often

endeavor

and

both

properties

current

focused

binders

fundamental

as,

single

highly

of

oxidation

classified

in

form

a

plant

characteristics

poorly

a

for

the

The

than

be

is

performance

operations,

may

if

area

fundamental

other

asphalts

applied

the

more

tower

temperatures

many

Then

little

crude

among

to

specifications. are

Program

specifications

accomplish

first.

meaningful asphalt

relate

To

Asphalt

research

develop

that

pavements.

SHRP

asphalt

must

mixtures

the

INTRODUCTION

asphalt

binders

viewpoint,

prepare

1.2

Purpose

The

SHRP

of

purpose

chemical

to

correlate

of

some

performance

the

non-chemist

of

the

the

between

the

chemical

studies

are

to

composition.

This

for

a

given

the

manufacture

of

the

producer

to

another.

will

distinguish

the

References

SHRP,

but

based

on

in

many

current

which

in

not

If

It

any

is

is

correlate

with

obvious

properties

that

are

to

research

cases SHRP

has research

ongoing

not

been and

do

no

composition

to

the

a

producer

it

asphalt

many

is

in

compositional

the

that

describe

composition

deficiencies

so

and

vary

from

chemical

a major

goal

to

relate.

which

published. have

has

note

performance

the

to

modify

tests.

correlations

acceptable

that

to

chemical

made

to

pavement

performance-

methods

asphalt

to

property

develop

of

how

important

that

instructive

given

become

with

Further,

definition

turn

of

asphalts

the

be

effort

physical

to

to

of

speculative

analytical

determine

has

is

practical

allow

It

mainly

status

intended

believed

properties.

will

can

be

studies

of

a

generally

will

physical

set

is

current

is

properties

is

binders

asphalt.

deficiency.

asphalt

properties

then

performance

deficiency,

the

a

the

It

further

chemical

It

and

describe

asphalt.

composition

define

to

and

known

for

of

is

petroleum

characteristics.

objective

remedy

report

of

specifications

The

one

this

studies

instructive

based

Report

has

Many

literature

been

reported

statements references.

are

to

2.0

It

is

convenient

two

parts.

The

the

second

part

species

first is

in

species

molecular

and

chemistry

of

techniques

2.1

Molecular

reviewed

is

research

done

by

essentially 2.1.1

most

of

variety

of

materials),

many

molecular

asphalt

can

or

matrix

in

units

is

what

the

both

types

of

the

the the

program.

composition

at the

reference "building

asphalt

reference

SHRP

be

of molecular

without

among

with

best

subsection

reviewed

interaction

and

within

at

following

subsection

total high

mass

are

have

molecular

fragments type).

both

for

material

of

boiling

some

petroleum

workers

Species

molecules

(aromatic

the

level

all

asphalt

illustrate of

currently

on

textbook

Typical

the

used

assembly

level

is to

second

of

into

to

some

of

Level

Extensive been

In

molecular

the

among

examine

asphalt

molecular

multi-molecular to

chemistry

in

the

nature

as an

large

This

The

being

physical

levels.

methods.

at

petroleum

interaction

exist

the

of

chemistry of

into

at

present.

the

chemistry

composition,

techniques

asphalt

is

the

the

intermolecular

experimental

molecules

of

of

blocks)

Numerous

are

is

the

chemistry

Much

terms

asphalt.

has

the

(building

blocks"

divide

part

in asphalt.

described,

to

to

CHEMISTRY

many but

worth

in Virqin neat

aromatic

(more

aliphatic

and

are

in

shown

At

At

asphalt Some

like

this

reviewing

Asphalt.

(tank)

hydrocarbons.

years.

is are

Structures

level

much

of it

here.

the

molecular of

aliphatic

carbon. 1

point,

a mixture

air-blown

aromatic

molecular

a wide

(waxy

asphalts) Examples

(aliphatic

level

type)

and of

some such

and

2

H I

H I

H I

H_ C_"C" C_"C"c/C_ _CH2_ICH2_x_CH3 _ _ x Typically

Structure 1 and that

make

carbon

= 15 or More Carbons

Structure

1

2 is

commonly

3 are up

more

only

carbon

represented

representative

but

chains

in

which

4 shows

a molecule

Structure

fragments

1 is

shown

as

there

are

Structure

typically

by

molecular

asphalt have

one

Structure Structure

II

I _c_C_H I H

Structure

asphalts.

atoms,

aliphatic

I I HIC-_c/C_c/C I I H H

which

is

or

more

a

3. of

straight numerous

2

Both

larger

C/

structures molecules

chain

of

combinations

branches.

3 a mixture

of

aliphatic

and

aromatic

carbon.

2

____CH

2 (CH)x-CH3 Structure

While

the

molecules

major

mass

also

contain

of asphalt one

or

4

is hydrocarbon, more

heteroatoms;

4

of

a large nitrogen,

proportion sulfur,

of oxygen

and

metals.

Nitrogen,

in

the

form

of

a

pyridine

CH2-(CH2)x"Structure

Sulfur,

as

right

is

a

identical

a

benzothiophene,

shorthand

is

notation

molecular

in

the

shown

in

Structure

5.

CH 3

5

shown

of

is

Structure

one

to

6.

the

Structure

left.

These

6 on

the

are

fragments.

H

I --H

or

/ Structure

Both

sulfur

molecules.

and

nitrogen

Hence,

molecular

species

different

arrangement

also

follows

molecular

to

2.1.2 asphalt

may

that

any

species

classify

are

the

it

may is

easy

be

present

of

elements

be

chemistry

susceptible

to

definition

would

Oxidation

appear

to

Form to

in

that

in

asphalt

of

terms

Molecules.

oxidation.

An

of

a

task.

the

variety

of

based

on

It

much

Certain aliphatic

is

of

that

different

molecular

sites

thousands

considering

properties

of

a

tens

constitutes

of

New

any

see

a monumental

in

6

within different

every

molecule.

It

specific more

effective

types.

types carbon

of next

carbon to

in an

aromatic

ring

oxidizable

showing

is

known

site.

as

a benzyl

Structure

a benzyl

carbon

7

in

is

bold

carbon

an

and

example

type

is

of

an

example

a molecular

(adjacent

to

the

of

a

readily

fragment

aromatic

ring).

CH2-(CH2)x

Structure

Sites

such

as

these

oxidize

to

form

7

ketones

as

shown

in

Structure

8.

C_(cH2)x--

Structure

More

severe

loss

of

Structure

oxidation

part

of

the

may

molecule

result

in

such

8

formation

as

shown

of

by

both

carboxylic

acids

versions

and

of

9.

°r Structure

Carboxylic

acids,

whether

oxidation,

may

converted

be

present

to

in

sodium

9

the

original

(Na)

salts

crude

or

(Structure

formed

10)

upon

or

calcium

(Ca) salts

calcium

inorganic

upon rings.

An

by

appropriate

reaction

with

O

O

O

II

II

II

i0

acid

oxidation

11)

sodium

or

compounds.

Structure Carboxylic

(Structure

Structure

anhydrides when

example

two is

(typically benzyl

called

carbons

Structure

are

anhydrides) present

11 may

on adjacent

be

formed aromatic

12.

0% c/O_c//0

(CH2)xCH3 Structure

Another asphalt an

type

is a class

aromatic

ring.

of

oxygen

known This

as

containing phenols

class

is

12

molecule

where

oxygen

illustrated

by

which

x'- CH2,_CH Structure

7

13

be

is attached Structure

OH

CH3-(CH2)

may

3

13.

present directly

in to

Again may

numerous exist.

shown

above,

homologous

variations,

In

addition

homologs series

or to

of

is

isomers,

isomeric

each

shown

combinations

also

by

containing

typically

Structures

14,

the of

basic

all

exist.

An

15,

16.

and

phenol

molecular example

unit types

of

a

0 II -C_cH2

--

Structure

14

Structure

15

Structure

16

(CH2) x CH3

O

II

C_cH2--(CH2)x+I-CH3

O II

C_cH2--(CH2)x+2--CH3

In the

above

case,

unique

molecule,

each

varies

although

the

only

by

one

properties

aliphatic

among

all

carbon. of

these

Each will

similar.

Another asphalts

is

important quinolones

class as

of

shown

compounds in

typically

Structure

Structure

17

17.

found

in

aged

be

is

a

quite

Many

sulfur

typically

form

Structure

18.

compounds

are

sulfoxides.

also

A

susceptible

sulfoxide

to

containing

structure Metals.

varying

amounts

nickel,

and

metals

are

There

and

although

present

as

An

also

metals

example

is

shown

present

most

may

organo-metallic

in

CH3CH 2

asphalts,

common

also

Structure

metals

be

materials,

by

shown

in

again

in

18

The

other

is

2-

metals

distributions.

iron

porphyrins.

are

and

fragment

O II -(CH2)xCH2-S-CH2-CH

2.1.3

oxidation

are

present.

vanadium,

Typically

specifically

as

19.

H

CH3

H

CH2CH3

CH3@__CH2CH3

3NZ'N(

cH cH2

CH3

Structure

By

may

forth

be

now

it

found

in

asphalts

2.1.4

nitrogen,

is

any

will

Polarity.

sulfur,

obvious

given

that

contain

All

oxygen,

and

the

of

thousands

Further,

hundreds

of

19

hundreds

asphalt.

of

naturally

metals

H3

the

unique

second,

thousands

of

occurring

contribute

of

to

third

different

molecules

and

so

molecules.

heteroatoms,

polarity

within

these

molecules. further is

Likewise, contribute

the

to

separation

following

of

example. 2.19

(C5H5 N)

is

benzene

(C6H 6) is

Polarity

is

organize

themselves

these

terms

have

the

asphalt, one

polar

dipoles.

in into

been

within

all

as

phase)

because

orientations.

formations

of

A more given

in

the

by

of charge)

of

the

moment

dipole

analog

to

of

which

pyridine of

pyridine.

species.

cause

colloids,

molecules

to

these

etc.,

understanding

following

and

the

Historically,

micelles, current

polar

Polarity,

seen

containing tends

are

although

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Subsection.

Level

another

molecule Figure

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1 illustrates

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10

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3.1

SPECULATION

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21

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bulk

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target!

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to

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of

packing"

aging

in

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in

of

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changes

changes.

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road

and

mix-plant

hardening.

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also,

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have

and

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temperature.

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(more

very

service

shuffle

their

thermodynamic in

oxidation

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cause

material

equilibrium

composition

polarity

temperature

22

at

the

find

or

packed

and

effect

orientation.

until

achieved.

achievement

asphalt.

in

value

hardening

thermodynamic

stiffer is

of

themselves

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increasingly

are

at

stiffer

organizational

a pavement

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recycling

the

stays

process.

(dipole

Aggregates,

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asphalt

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orienting

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the

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cold

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the

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oxidation

medium

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bound

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lead

forces

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hardening

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temperature

process

orientation,

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note

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cement

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equilibrium,

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result

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the

in

on

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tends

to

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loads

and

equilibrium. providing

is

slowed

is

aging

oxidation

such

products

substantial

Figure

has

in

so

result

oxidation. varies

Compositional

variations

increase

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temperatures. it

is

the

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as

was

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up

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orientation

orientation

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3.3

on

the

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of

their

Figure

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in own as

a

4, this

oxidation.

the

oxidation

therefore

of

of

shown

in viscosity

in

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asphalts

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quench

increase

quenching

it. their

other

oxidation.

dictate

to

accommodate

viscosity,

earlier

of

property and

and

temperature

chemistry

feature

eventually

asphalts

characteristics

Speculation

heavy

thermodynamic

speed

saving

upon

their

a result

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under

loads

oxidize

asphalts

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chemical

viscoelastic

as

among

observed

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changes

quench

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viscosity

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G,

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asphalt

in

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and

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phenomenon

system

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4 earlier,

of

as

for

temperature.

achievement

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energy

with

species,

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varies

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further

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show

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fully

asphalt

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to

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to

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Composition

viscosity

understood, relate

to

performance

Failure

Modes The the from

measurable

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or

model,

agglomerates

it

chemical

properties

structural

strength

of

that

asphalt

is

believed

(structured

units)

that

23

that

are

believed

a pavement

consist

are

is a

set

of

polars

of

to

relate

several.

to Again

"hardcore" dispersed

in

a

less

polar

elastic

to

behavior

molecules,

flow

to

or

each

other

under

the

expect

it

to

be

G

organize

to

be

and

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fact,

with

is

harden

at

SEC

modulus

at

to

and

plot

material

high

molecular

high

temperature.

G.

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susceptibility

is

observed

in

oxidation

what should

Asphalt

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should M,

and

M

size

impart this

G

in

G

observed.

also

a

likewise

24

the

a more

is

very

a

to

have

not

low

to that

a

have

M,

will

of

the

elasticity.

tend

be

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temperature.

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observed.

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G

homogeneous

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and

has

give

has

and

G

a material

roadways.

expected

does

of

asphalts

Asphalt

It

to

at

K

asphalt

and

it

Therefore

Asphalt

is

is

makes

material

be

respect

insensitive

temperatures.

for

than

3.

somewhat

cracking)

K.

would

Figure

is

molecular

asphalt

also

weight,

G which

behaviors

and

is

to

character.

to

with

consider

in

temperature.

temperature

this

high

or

for

in

non-associated

observed

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elastic

higher

can

contributions

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large

low

relative

that

move

not

well

(susceptible

are

agglomerated

rut;

the

stiff

these

the

mostly

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behavior

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of

network

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composition.

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at

by

viscous

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which

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as

studies.

feature

with

a

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compatible

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compositional

stress.

plots

not

of

a material

formed

with

parts

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is

network

a material

phase,

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result

the

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SEC

does

deform,

Asphalt

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index It

of

behavior

dispersing

oxidation.

or

also

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compatibility

rut

result

various

viscous

M.

The

prolonged

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and

largely

is

because

3.3.1

K,

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a

creep

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phase.

as

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this

amount

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of

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with

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like

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material

temperature

truly K

than

at

K

If

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properties

has

blending

of

separated were

not

phases

observed

with

more

one

than

within

reason,

pushed

up

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down

of

intensive

study

3.3.2

failure the

is

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potential

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organize

into

to

low

variety

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area

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not

present needed

fully

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be

the

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rigid

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structured

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a

crude

by

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25

of

yet

can

the

one

is

clear

can,

can

be

under

understanding since

many

oils.

another

an

or

whatever

asphalt

occur.

suffer

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term

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materials seen

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composition.

fractures

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varied

binder

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to

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the

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the

material!

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can

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micelle,

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cross

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moduli)

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to

crack

a

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specification

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time.

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cross

properties

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wide

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elastic

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fractions

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asphalt.

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second

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molecular

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the

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of

phase

performance

recent

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in

of

a

SEC.

dispersed

the

at

phenomenon are

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the

by

to

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phases

prepared

times

achieve

significantly.

asphalts

asphalt

of

phase

dispersing

phase

i000

composition

consider

generated

case,

phase

dispersed

this

an

of

obvious,

and

dispersing

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of

been

were

in

In

the

relationship

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was

the

begin

to

differential

scanning

calorimetry

subject

to

cracking

shrink

significantly

of

polarity

low

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it

other

with

to

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ratio

Aliphatic/aromatic

ratios

the

to

very

rapid

measurements.

go

Adhesion

together

only

serious

moisture

occur.

At

involve

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to

either

to

of

adhesion,

composition

studies.

considering

governed

as

Specific

functional

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overall

organic

much

molecules,

per

se,

is

the

components

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the

promotes

of

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SHRP and

the

it

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probably

predict

it

moisture

is

damage

a

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definition,

it

commissioned

interesting

from

damage

certainly

scope

of

equal.

aggregates,

within

and

feature

moisture

While

asphalt

molecular

polarity,

or

and

By

some

occurs,

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must

studies

the

of

the

binder

observations

can

be

binder.

in

groups

but

the

Hence,

are

NMR,

adhesion.

not

show

shrinkage

adhesion

forms

asphalts

Nevertheless,

only

of

of

All

temperature.

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other

interaction

another.

materials

directly

of

organization

compositional

by

cements

cracking.

characteristics

loss

aggregate.

the

to

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the

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only

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shrinkage

consider

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to

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asphalt

determined

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the

examination

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point.

point,

asphalt

all

Moisture

damage

this

investigate

made

a

one

related

be

a

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be

measure

and

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with

would

is

matters

linear

shrink

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practical

3.3.3

more

when

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make

from

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DSC

To

components.

to

most

asphalt

temperature

temperature

be

the

composition

tendency

low

expected

low

nonpolar

being

at

Now,

stress.

at

and

pronounced

cracking

is

under

varies

things

most

(DSC).

level

(molecular that

to

aggregate

as

at

types)

is,

attraction

26

the

polar

to

be

inter-molecular

seem

separation

of

appears

to of

be

charge

asphalt

very

level.

important.

within

components

the

to

the

also

polar

Strategic

surface

Highway

some

and

Some

show

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with

in

asphalt

may

not

asphalt

is

capability

of

moisture

with

result

of

effects

a

acids of

removed

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of

practical

in

pyridines

that

organic

molecules elsewhere

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from

aggregate

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is

in within

it

in salts

a

the

more

would

are

been

sodium

easily.

of

of

The

tenacity

evaluation

program.

27

the

the

the

user

of

this

are

to

the

a

the

be

type

of

or

The it

among

spectrum

acids

of

assure

and

of

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of

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the

surfaces

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Calcium

resistant

in

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alone

composition

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the

other

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a

the

on

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etc.

pavement

has

all

in

asphalt

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form

spectrum

asphalt.

as

in

More

like

and

polarity

adhesion

is

this

quite

the

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Asphalt

adhere

but

such

much

of

water.

while

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with

simply

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aggregate.

water,

the

temperature,

to

the

water

to

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cation

are

and

tend

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of

it

acid

acids

of

of

asphalt

some

content,

transporting

into

more

sites,

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(pyridines)

varies

environment.

water

viewpoint,

asphalts

obvious

done

in

behavior

achieve

Incorporation

aggregate

Monovalent

divalent

its

composition

Carboxylic

be

to

Absorption

level

to

of

section.

compounds

salt.

surface

of

vary

considered

because

and

molecular

from

be

within

aggregates

moisture

will

incorporating

invasion

removed

with

by

workers

positive

sufficient

oxidation.

tenaciously.

have

affected

the

nitrogen

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be

that

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arises

polar

asphalt

of

the

tend

the

damage

varies

cases

polarity

Adhesion

Several

shown

aggregate

asphalt

because

some

in

discussion,

surface.

have

aggregates

in

At

in

variation

this

aggregate.

Program

substantially,

environment.

of

water.

the

examples should

the

is

being

be

Moisture problem

damage

in

reducing

pavement.

the

this

water will

in

also

come

in

performance

into

asphalt

the

chemical

by

soaks

into

polar

components.

viewpoint,

Upon

with

reduced

strength

and

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oxidized

asphalts,

or

(oxidation new

asphalts.

This of

pavement

counterpart

age. new

counter

measured

in

behavior

would

But

pavements, to

terms varies

of

each the with

of

to be

polar

have

mechanical

a

chemical

are

also

28

some

affect

its

water

like

is transported molecules

asphalt, it. like

From the

typically other of

to

water

will a

dilution

of

results

in

deformation. polars

a greater

extent

than

considerations. viewpoint,

harder

effects of

most

Still,

water

of moisture

combined

remove

extent

amounts to

is

Water,

polarity

properties

composition.

or

water

effects The

This

rutting

from

will

somewhat

greater

from

to

softening

is

in

pavements

other.

the

solvent.

expected

so the

some

into

incorporate

invasion, aged

of

water

results which

tend

to

typically

weight

further

moisture

somewhat

the

molecular

products),

probability with

a low

action

asphalt

and

invasion

properties, the

concrete.

in

unavoidable.

to pavement.

the

attraction

are

common

factor

water

adequate

and

another

a major

clear,

pavement

material

of

is

in

water

virtue

mechanical

invasion in

be

is

is

of moisture

design

asphalt

a highly

asphalt

effect

the

to

effects

with

adhesion

design

but

that

its

of

highway

so the

resist

loss

water,

consider

contact

is

the

polar

to

when

aggregate,

of

roadways,

discussion,

and

apparent

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availability

omnipresent For

without

the

than

The

increases their

and

oxidation

are

better

mix.

As

usual,

are

4.0

The

chemistry

of

intermolecular

levels

thousands

of

polarity

among

properties

has

molecular

on

mechanical

tend

or

by

involvement

exact

nature

of

of

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distribution

of

charge

structuring

leads

little

structuring

Oxidation

adds

contributing

to

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word

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differently asphalts.

new

the

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crude

as

consistent

used

and

to

are

airplane

other,

be

among

and

are

performance,

and

in

rubber

are

achieve

29

of

to

the

the

may

species.

The

the

Excessive

crack,

while

under

stress.

asphalt

the

same

cement

tremendous

them.

is

than

differences

asphalts

general,

too

cement

by

binder.

used

there

manufacture

describe

of

significant

glue

so

deform

within

should

chemical

to

brittleness

zones

there

to

which

chemical

interactions

molecule.

tend

nonpolars

of

In

important

which

materials

asphalt

differences

oils

specific

cements

to

different

the

and

related

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nonpolars

effects

are

of

asphalt.

offered.

less

hundreds

physical

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the

polars.

is

the

and

less

asphalt

specie

hardening

word

each

specifications

therefore

brittle

glue,

from

numerous

structures

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carpenters

of

within

age

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the

glue.

e.g.,

to

of

that

particular

and

been

and

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polars

on

have

the

any

leads

of

speculations

chemical

to

any

while

among

is

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balance

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molecular

It

varies

performance

structural

the

within

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structuring

arise

exist

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to

at

discussed.

Several

pavement

intermolecular

of

by

dissociation.

composition

been

molecules

governed

Polars

asphalt

species

asphalt

are

components. cause

petroleum

SU_a4ARY

as

The

as

among

glues,

perform

differences great

as

objective

consistent

high

sense

priority

the

of

behavior,

from

the

the

very

among diversity

developing and

user's

cost

standpoint.

supply

line

there That

is

But

(crude

little

is,

the

selection

asphalts

achievement

of

value

of

the

properties.

obtain

of

a very

limited

are

needed

that

is

with

that

is

are

to

to

information

binders

variety

set

It

performance

studies

3O

of

perform

cost-effective

materials,

the

source

crude

oils

produced

today.

to

in

a

with

select

supply.

that

will

A

understanding

material

used

of

obvious

frequently

an

and

to

asphalts

develop

be

the

of

therefore

produce

can

will

that

limiting

impossible.

materials

realize

a wide

of

composition

this

also

significantly

of

features

must

of

consistent

Then

to

user

consists

is

modification

compositional

asphalts

oil)

chance

manufacture

require

the

principal

of

what

the

desired

and/or

modify

cost-effective

manner.

Asphalt

Advisory

Committee

George West Shell Oil Company

Thomas D. Moreland, chairman Moreland Altobelli Associates, lnc.

Liaisons

Gale C. Page, vice chairman Florida Department of Transportation

Avery D. Adcock United States Air Force

Peter A. Bellin Niedersachsisches

Ted Ferragut Federal Highway Administration

Landesamt

fiir Strass7enbau

Donald G. Fohs

Dale Decker

Federal Highway Administration

National Asphalt Paving Association Fredrick D. Hejl Joseph L. Goodrich Chevron Research Company

Transportation

Research

Board

Aston McLaughlin Eric Harm

Federal Aviation

Illinois Department

of Transportation

Bill Weseman

Charles Hughes Virginia Highway

Administration

Federal Highway & Transportation

Research

Administration

Council

Expert Task Group

Robert G. Jenkins University of Cincinnati Anthony J. Kriech Heritage Group Company

Wayne Brule New York State Department

Richard Langlois Universite Larval Richard C. Meininger National Aggregates Association Nicholas Nahas EXXON Chemical

Ernest Bastian, Jr. Federal Highway Administration

of Transportation

Joseph L. Goodrich Chevron Research Company Woody Halstead Consultant

Co. Gayle King Bituminous Materials

Charles F. Ports APAC, lnc.

Co., lnc.

Robert F. LaForce Ron Reese California Department

Colorado Department

of Transportation

of Transportation Mark Plummer

Donald E. Shaw Georgia-Pacific Corporation

Marathon Oil Company Raymond Pavlovich Exxon Chemical Company

Scott Shuler The Asphalt Institute

Ron Reese Harold E. Smith City of Des Moines

California Department

Thomas J. Snyder Marathon Oil Company

Colorado

of Transportation

Scott Shuler

Richard H. Sullivan Minnesota

Department

A. Haleem

Tahir

of Transportation

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

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