CHEMISTRY OF ASPHALT EMULSION

& EMULSION SYSTEMS

(SESSION C)

Speaker:
Stephanie Hogendoorn, Technical Development Manager, AkzoNobel
Asphalt Cement
Residue from the refining of crude oil
Crude oil contains 1-60% asphalt depending on source
Supplied in grades depending on its consistency
(viscosity)
Selection of asphalt viscosity depends on end use
Most asphalt grades can be supplied in emulsion form,
including polymer modified grades

Hard (Low penetration) Soft (High penetration)

Chemical Nature of Asphalt
Predominately SARA fractions
hydrocarbon Separated by chromatography
Carbon 82-88%
Hydrogen 8-11%
5-25%
Sulfur 0-6%
Oxygen 0-1.5%
Nitrogen 0-1%
Trace amounts of metals
Ni, Fe, V, Mg, Ca
5-20%
Acid value 0-4.5 mg KOH/g
High MW naphthenic acids (Aromatics)
40-65%
Small base value
Nitrogen compounds 15-30%
Salt Source: The Bitumen Industry, A Global Perspective,
March 2011 edition, Eurobitume and the Asphalt Institute
Colloidal Structure
Additional Processes
Blending
To obtain required penetration value or PG grade
Air blowing (oxidation)
Raises the asphaltene content
Introduces oxygen atoms
Solvent de-asphalting
Provides very hard residue
Modified asphalt
Polymers (SBS) add flexibility
Polyphosphoric acid (PPA) increase stiffness
Anti-stripping agents improve adhesion to aggregate

Some processes can make emulsification challenging

For Difficult Asphalts
14
viscosity Engler
12 settlement %
particle size, m
10

0
no 0.2% 0.3%
additive additive additive
Additives to the asphalt which stabilize the colloid system (peptizers) can
significantly reduce particle size and improve other emulsion properties
Why Use Emulsion?
A liquid asphalt which can be
used at lower temperatures

Easier handling and storage

Safety
Low fumes, low volatiles (VOC)
Save energy
Low cost in-place/on-site techniques
Easily mixed with latex or cement
Composite binders
Water dilutable
Accurate dosing
Deferred set
Everyday Emulsions

Dispersion of one liquid in another (immiscible) liquid

One of the liquids is usually water
Types of Emulsion
Oil in water Water in oil Water in oil in water
(invert) (multiple)

Source: Steve Karg

Asphalt Emulsion

Source: BASF
100 micron/0.1mm

Photomicrograph of an Asphalt Emulsion

1-20 micron (1/1000 mm) in diameter
Distribution of particle sizes
Some droplets contain water
Components of an Emulsion

water 30-50%

chemicals 0.2-2.5%
solvent 0-10%
polymer 0-4%

asphalt 40-70%
Components of an Emulsion
Asphalt Cement
Generally similar materials as used for hot paving, including PG grades.
Choice depends on the application.
Water
Generally potable water without suspended solids. Some emulsion types
may demand softened water.
Polymer
Many emulsions contain polymer, which can be used as a water dispersion
(latex - natural rubber latex or Styrene Butadiene latex), or solids (like
Styrene Butadiene Styrene) which are dissolved in the asphalt. Modifies
elastic and flow properties of the asphalt to improve performance.
Solvent
Hydrocarbon solvents and fluxes such as mineral spirits and fuel oil are
used to provide workability to emulsion mixtures, and to soften the
emulsion residue.
Components of an Emulsion
Emulsifier
Type of soap which is used to stabilize the emulsion. Mostly derived from
natural fats and oils like beef fat, or from wood products like tall oils and
lignins.
Thickeners
Water soluble polymers which improve the storage stability of the emulsion.
Salts
Used to control viscosity changes in the emulsion.
Making an Emulsion
Asphalt dispersed in a colloid mill into micron-sized
droplets in water
Colloid mill is a high-shear mixer
Solution of emulsifiers in water known as the soap

Emulsion

Soap Asphalt
Colloid Mill
Batch Emulsion Plant
acid or
stabilizer alkali emulsifier

asphalt emulsion

batch soap 80-140F

tank water
250-300F 190-210F

colloid mill
Latex
Oil and Water
Without emulsifiers oil and water quickly separate
Oil IN water Oil ON water

Asphalt emulsion without stabilization

Emulsion Droplets Flocculation Coalescence

Like Charges Repel
Positive droplets = Cationic Emulsion
counter-ion
Like Charges Repel
Negative droplets = Anionic Emulsion
counter-ion
Charge from the Emulsifier
Cationic emulsions are generally Acidic
Cationic emulsifiers contain nitrogen (N)
which takes a positive charge in acid
The nitrogen comes from ammonia and
the emulsifiers are called amines
Cationic soap
Fatty-Amine Acid ammonium ion chloride ion

RNH2 + HCl RNH3+ + Cl-

counter-ion

R = hydrocarbon with 12-22 carbons

N = nitrogen, C = carbon, H = hydrogen, Cl = chlorine
Charge from the Emulsifier
Anionic emulsions are generally Alkaline
Anionic emulsifiers contain oxygen (O)
which takes a negative charge in alkali
Anionic soap
Fatty-Acid Alkali carboxylate ion sodium ion

RCOOH + NaOH RCOO- + Na+ + H2O

counter-ion

and/or
R = hydrocarbon with 12-22 carbons
C = carbon, H = hydrogen, O = oxygen, Na = sodium
Charge from the Emulsifier
Some emulsifiers do not need acid or alkali

RN(CH3)3+ Cl- RSO3- Na+

soluble quaternary amine soluble sulfonate

R = hydrocarbon or mostly hydrocarbon with 12-22 carbons

N = nitrogen, C = carbon, H = hydrogen, O = oxygen
S = sulfur, Cl = chlorine, Na = sodium
Emulsifier Sources

N
H H
H

tallow tall oil ammonia

fatty acids O

OH
rosin acids
H
O

OH
linear fatty acids O H
HO
OH O
fatty amines
NH2
Typical Emulsifier Groups

Lipophilic/hydrophobic tail hydrophilic head group counterion

group
R(tallow) ---------------------- N+(CH3)3 Cl-
R(tallow) ---------------------- NH2+CH2CH2CH2NH3+ 2Cl-
R(nonylphenyl) ------------- O---CH2CH2OCH2CH2O---H none
R(tall oil) ---------------------- COO- Na+
R(lignin) ----------------------- SO3- Na+

R = hydrocarbon or mostly hydrocarbon with 12-22 carbons

N = nitrogen, C = carbon, H = hydrogen, O = oxygen
S = sulfur, Cl = chlorine, Na = sodium
Oil-Water Interface
Emulsifier molecules concentrate at the oil-water interface

Tails in the oil (asphalt) and Heads in the water

oil

tail
oil-loving

head
water-loving water
In the Colloid Mill

Emulsification produces interface - 500 sq meters/liter

Emulsifier reduces the interfacial energy and also provides charge to
stabilize the emulsion
Shear Coalescence

Shear can cause coalescence

Large droplets grow preferentially giving shot
Low shear pumps are used for emulsion

Compaction initiates setting in the field

Settlement

Droplets settle during storage

Large particles settle faster
Dense particles settle faster
Low viscous, low residue emulsions are liable to settle
Opposite is called creaming
Less settlement with hot storage temperature
Settlement can be very hard to re-disperse
Emulsion Setting (Breaking)
Destruction of charge by pH change or ions

Destruction of charge by oppositely charged aggregate

Aggregate fines

Evaporation of water
Breakdown of the Emulsion

Alkali added to cationic emulsion to destroy charge

Once droplet charge is destroyed the droplets are strongly attracted to one
another the asphalt coagulates even with water still present
Classification of Emulsions
Emulsions are Classified According to Reactivity and
Particle Charge
cationic anionic
+ -
rapid-setting CRS RS chip-seal

medium-setting CMS MS open-graded mix

slow-setting CSS SS dense-graded mix

Principle: match the reactivity of the emulsion with the reactivity of the aggregate

Rapid set emulsions are used with low-reactive, low surface area aggregates
Slow set emulsions are used with reactive, high surface area aggregates
Adapting Reactivity
Concentration of emulsifier more chemical less
reactive
Rapid set emulsions use 0.2% chemical, slow set use 2%

Less pH sensitive emulsifier is less reactive

Rapid medium and quick-set recipes use emulsifiers very sensitive to pH
(or to calcium ions)
Slow set emulsions use emulsifiers less sensitive to pH changes
Headgroup Charge and pH
Headgroups Acid Neutral Alkaline
Sulphonate SO3- - - -
Carboxylate COOH/COO- o - -
Ethoxylate (C2H4O)xH o o o
Amine NH2/NH3+ + + o
Quaternary Amine N(CH3)3+ + + +
Asphalt + o -
Mineral + o -
Emulsion Reactivity
level % emulsifier chemistry

CRS 0.15-0.30 pH sensitive

CMS 0.30-0.60 pH sensitive
Micro 0.6-2.0 pH sensitive
CSS 0.8-2.5 not pH sensitive
RS 0.2-0.4 pH and ion sensitive
MS 0.6-1.5 pH and ion sensitive
SS 1.0-2.5 not pH or ion sensitive
Aggregates and Emulsion
Emulsions react with the
surface of the aggregate coarse (+ 2.36mm)
Surface area and surface
chemistry of the aggregate SA <1 sq m/kg
important
Most surface area and
reactivity is in the fines
Reaction rate depends on
temperature sand (-2mm)
SA 1-20 sq m/kg

filler/dust (-75micron)
SA >20 sq m/kg
Chemistry of Aggregates
Mineralogy influences adhesion and reactivity
marble
limestone
basalt
dolomite
sandstone
granite
quartzite
0 silica content 100
Basic Acidic
Aggregate Surfaces

Examples of washed coarse (+4 mesh) aggregates from actual slurry mixes

100 micron 100 micron

Basalt (Trap Rock) Slag

pH Changes after Mixing
pH
12 0.5% cement
10
8 no cement
6
4

2
0
0 60 120 180 240
Time after Mixing (seconds)
Setting Mechanisms
Cationic emulsions
pH changes due to chemistry of aggregate or filler
Heteroflocculation between emulsion droplets and oppositely charged
mineral filler and aggregate
Adsorption of free surfactant onto aggregate
Adsorption of water into porous substrates
Evaporation of water

contact of emulsion adsorption of free rise in pH leads coagulation/spreading

with aggregate emulsifier, pH rises to flocculation over surface
Setting and Curing Factors
Emulsion Reactivity
Emulsifier chemistry, concentration
Other additives
Asphalt viscosity
Aggregate Reactivity
Surface area, surface charge, surface chemistry
Filler chemistry e.g. cement, lime
Road and Air Temperature, Humidity, Wind Speed
Remove water from the system
Mechanical Treatment e.g. compaction
Squeeze the droplets together and squeeze out water
Sources of Information
AEMA Asphalt Emulsion Manufacturers Association
www.aema.org
AI Asphalt Institute www.asphaltinstitute.org
ISSA International Slurry Surfacing Association
www.slurry.org
ARRA Asphalt Recycling & Reclaiming Association
www.arra.org
NCPP National Center for Pavement Preservation
www.pavementpreservation.org
Foundation for Pavement Preservation www.fp2.org
IBEF International Bitumen Emulsion Federation
www.ibef.net
Contact Information

Stephanie Hogendoorn
Akzo Nobel Surface Chemistry LLC
281 Fields Lane
Brewster, NY 10509
Phone: 845-276-8329
E-mail: stephanie.hogendoorn@akzonobel.com