Emulsion 101

Alan James
AkzoNobel Surface Chemistry
 Emulsion 101

• Asphalt
• •The
Residue from the
Chemistry vacuum
y of distillation of crude oil
Emulsions
• Crude
C d oilil contains
t i 1 1-60%
60% asphalt
h lt depending
d di on theth source
• •The Chemistry
Not all of Emulsifiers
refineries produce asphalt
• •The Setting
36 million ton process
asphalt used in USA each year
• •Emulsion Formulation
31 million ton used in road construction
construction, rest mostly in roofing

Surface Chemistry 2
Asphalt

• Residue from the vacuum distillation of crude oil

• Crude
C d oilil contains
t i 11-60%
60% asphalt
h lt depending
d di on theth source
• 36 million ton asphalt used in USA each year
• 31 million ton used in road construction, rest mostly in roofing
• 2-3
2 3 million ton used in emulsions
emulsions, rest mostly in hot mix
• 7-10 million ton emulsion worldwide

Surface Chemistry 3
Asphalt

• Supplied in grades depending on its consistency/viscosity

• For
F emulsions
l i viscosity
i it is
i defined
d fi d bby ttests
t lik
like penetration
t ti
and softening point
• The choice of viscosity depends on the end use.

Surface Chemistry 4
Why Use Asphalt Emulsion

Cold processes save

energy
Easier handling and
storage
Safe and environmentally
friendly
Low cost in place and on-
on
site techniques
Easily mixed with latex
and cement
Water dilutable
Deferred Set

Surface Chemistry
Emulsions around the Home

• Dispersion of one liquid in another (immiscible) liquid

• One of the liquids is usually water
Surface Chemistry
Emulsion Types

O/W W/O W/O/W

oil-in-water water-in-oil multiple
emulsion (inverted emulsion) emulsion

Surface Chemistry
Asphalt Emulsion

100 micron/0.1mm

Photomicrograph of An Asphalt Emulsion

Droplets are 1-20 micron in diameter

Source :BASF
Surface Chemistry
Size Distribution of Asphalt Emulsion
Droplets

ume %
volu

median (d50
d50))

particle size (micron)

Surface Chemistry
Components of an Asphalt Emulsion

water 30-50%

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

asphalt 40-70%

Surface Chemistry
Production of Bitumen Emulsions

• Asphalt dispersed in a colloid mill into micron

droplets in water

Emulsion

Soap Asphalt
Colloid Mill

Surface Chemistry 11
Inside the Colloid Mill

Surface Chemistry 12
 Schematic of Batch Emulsion Plant

stabilizer acid emulsifier

asphalt emulsion

140C 90C
50C
batch soap
tank water inlet

colloid
L t
Latex
mill
Surface Chemistry
 Bitumen loading pump
Emulsion tank kit
Bitumen tank kit

D
Drum filli
filling

Emulsion plant

Control room

Of loading pump
and flow meter
for emulsion Batch soap tank kit
and heating

Water-phase mixing unit

Surface Chemistry 14
 Stabilization of Asphalt Droplets
no charge- droplets can come into contact and
coalesce

Cationic em
emulsion-electrostatic
lsion electrostatic repulsion
rep lsion pre
prevents
ents close approach
of drops

+ + + + + +
Anionic emulsion-electrostatic repulsion prevents close approach
off drops
d

- - - - - -
Surface Chemistry
 Breakdown of the Emulsion

Flocculation and Coalescence

Emulsion Droplets Flocculation Coalescence Coalescence

Charge on droplets Close approach of Water drains Trapped water
prevents close droplets leads to between droplets diffuses out.
approach adhesion between and surfactant film
droplets. Water is breaks down,
squeezed out Droplets fuse,
trapping some water

Setting Curing

Surface Chemistry
Breakdown of the Emulsion

Settlement (Sedimentation)

•Asphalt
p is g
generally
y denser than water
•Sedimentation may lead to irreversible
flocculation and/or coalescence

Surface Chemistry
Breakdown of the Emulsion

Evaporation of Water

•Evaporation of water forces droplets together

and
d eventual
t l coalescence
l

Surface Chemistry
Breakdown of the Emulsion

Flocculation and Coalescence

•Flocculation and Coalescence in contact with

Aggregate

Surface Chemistry
Classification of Emulsion by Reactivity

rapid-setting:
reactive emulsion sets quickly even with unreactive
aggregates

medium-setting:
medium setting:
medium reactive emulsion which can be mixed with open
graded aggregates with low fines content

slow-setting:
low reactive emulsion which can be mixed with reactive
aggregates with high fines content

Surface Chemistry 20
Naming of Emulsions

cationic rapid-setting

CRS - 2 High viscosity

(65% asphalt)
cationic slow-setting

CSS - 1h hard asphalt

Low viscosity
high-float (57% asphalt)

HFMS - 2s with solvent

medium-setting
(anionic)

Surface Chemistry 21
 Emulsions are classified according to
Reactivity and Particle Charge

+ve -ve

rapid-setting CRS RS chip-seal

medium setting
medium-setting CMS MS open-graded
open graded mix
slow-setting CSS SS dense-graded mix

The principle is to match the reactivity of the emulsion with the reactivity of the
aggregate
Rapid set emulsions are used with unreactive, low surface area aggregates
Slow –set emulsions are used with reactive high surface area aggregates

Surface Chemistry
Functions of the Emulsifier

determines type of Emulsion formed. i.e. O/W or W/O

reduces energy needed to emulsify asphalt
determines charge on emulsion droplets
stabilizes emulsion droplets as they are formed in the
colloid mill
stabilizes the droplets during storage of the emulsion
provides the right setting behavior
influences the physical properties of the emulsion
influences properties of cured road material.

Surface Chemistry
 Typical Emulsifier Structures

Lipophilic/hydrophobic tail hydrophilic head counterion

group

R(tallow) --------------------------------- N+(CH 3)3 Cl-

R(tallow) --------------------------------- NH 2+CH 2CH 2CH 2NH 3+ 2Cl-

R(nonylphenyl) ------------------------ O----CH

O CH 2CH 2OCH 2CH 2O---H
O H none

R(tall oil)---------------------------------- COO - Na +

R(li i )
R(lignin)----------------------------------- SO3- Na +

R= hydrocarbon or mostly hydrocarbon with 12-22 carbons

N= nitrogen
nitrogen, C=carbon,
C=carbon H= hydrogen
hydrogen, O= oxygen
S= sulfur, Cl= chlorine, Na = sodium
Surface Chemistry
 Cationic emulsions tend to be acidic,
anionic emulsions alkaline

RNHCH2CH2CH2NH2 + 2HCl = RNH2+CH2CH2CH2NH3+ 2Cl-

insoluble neutral form + acid = soluble cationic 'soap'

RCOOH + NaOH = RCOO- Na +

insoluble neutral form + alkali = soluble anionic 'soap'

R= hydrocarbon or mostly hydrocarbon with 12-22 carbons

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

Surface Chemistry
Some charged emulsifiers do not need
pH adjustment

RN(CH3)3 + Cl -

soluble quaternary amine

RSO3- Na+

soluble olefin sulphonate

R= hydrocarbon or mostly hydrocarbon with 12-22 carbons

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

Surface Chemistry
 Cationic emulsifier
Head Group
(Water Loving)
H d
Hydrocarbon
b ChChain
i (Oil L
Loving)
i )

H
C N+

C l-

Counterion
(Water Loving)
Surface Chemistry 27
 What is Interfacial Tension?

Attraction Forces in Water Water molecules like to bond to

are stronger than most other liquids - each other
In bulk water molecules have
Oil
lots of close friends and are
happy.
At the oil/water interface the
water molecules have only y weak
bonds and are not quite so
happy
This creates tension
Water Tension = Energy
So surface tension is
higher

Surface Chemistry 28
Surface Activity

Surfactants (Emulsifiers)
Oil p
separate oil and water
Surfactant Head group can bond
with water
Water can make new friends!
This reduces tension and makes
it easier to make new interface

Water

Surface Chemistry 29
Emulsifier Molecules concentrate at
the oil-water interface
“Tails” in the Oil and “Heads” in the Water

oil

water
Surface Chemistry
 Emulsifiers in Emulsion Emulsion

Manufacture

Water-phase Colloid Mill Bitumen

Emulsification produces interface. 500 sq meters/liter.

Emulsifier reduces the interfacial energy and also
provides charge
Surface Chemistry 31
More Emulsifier Gives Smaller Particles.

45
4.5
e micron
4
edian parrticle size

large head group

3.5

3
me

small head group

2.5
0.2 0.3 0.4 0.5
Emulsifier level %
Surface Chemistry
Emulsifier Molecules are very small!
If an asphalt droplet were the size of the world, then the
emulsifier head group would occupy an area of 4 square
miles
il andd th
the ttailil would
ld penetrate
t t 5 miles
il d deep

emulsifier length
3/1 000 000 mm

asphalt droplet
diameter 3/1000 mm

Surface Chemistry
Emulsifier generates charged Asphalt
Droplets

Counterions diffuse into the water phase leaving the

asphalt surface with a net positive charge
Surface Chemistry
Headgroup Charge and pH

Headgroups Acid Neutral Alkaline

Sulphonate SO3- - - -
Ethoxylate (C2H4O)xH o o o
Carboxylate COOH/COO- o - -

A i NH2/NH3+
Amine + + o

Quaternary Amine N(CH3)3+ + + +

Asphalt + o -
Mineral + o -

Surface Chemistry 35
 Manufacture of Emulsifiers

Animal fat Splitting Nitrilation Fatty amines

Vegetable
g oils
ammonia
water hydrogen

methylchloride
th l hl id
Quaternary
Fatty amines Quaternization ammonium
salts

Nonyl phenol Alkoxylates

and Alcohols
Alkoxylation
Ethylene or propylene oxide

Olefins
alkylbenzenes Sulfonation Sulfonates
alkylnaphthalenes Sulfuric acid, sulfur trioxide

Surface Chemistry 36
 Manufacture of Emulsifiers

Tall Oil
Tall Oil
Imidazolines
Condensation and amidoamines
p y
polyamines

Lignin
Lignin
Addition Ligninamines

amine

Surface Chemistry 37
Factors Affecting Breaking and Curing

Aggregate Reactivity
surface
f area, surface
f charge,
h surface
f chemistry
h i t
filler chemistry e.g. cement, lime
Emulsion Reactivity
emulsifier chemistry, concentration
other additives
asphalt viscosity

Temperature, Humidity, Wind Speed

Mechanical Treatment e.g.compaction

Surface Chemistry
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.

Absorption of water into porous substrates

Evaporation of water

Surface Chemistry
pH changes after mixing emulsion with
Aggregate

pH
12 0.5% cement

10

8 no cement

0
0 60 120 180 240
Time after Mixing (seconds)

Surface Chemistry 40
 Possible stages in cationic emulsion
breaking

contact of emulsion adsorption of 'free' Rise in pH coagulation/spreading

with aggregate
gg g pH rises
Emulsifier,, p leads to over surface
flocculation

Surface Chemistry
Breakdown of the Emulsion

Surface Chemistry
 Emulsifier Chemistry and Use Levels

level % typical emulsifiers

CRS 0.15-0.30 tallowdiamine

CMS 0.30-0.60 tallowdiamine
Micro 0.6-2.0 tallowtetramine, tall oil imidazoline
CSS 0.8-2.5 tallowdiquaternary, ethoxylates
RS 0.2-1.0 tall oil acids
MS 0.6-1.5 tall oil acids
SS 1.0-2.5 lignosulphonates, ethoxylates

Surface Chemistry
Other Emulsion Ingredients

• Polymer – modify binder properties

• SBR, NR or PC Latex added via soap or asphalt
• SBS, EVA polymer added via asphalt
• Solvents – modify binder properties
• Naphtha,
N hth mineral
i l spirits,
i it N No2
2 ffuell oil,
il fl
flux oils
il
• added via asphalt, soap or to finished emulsion
• Rheology Modifiers – modify emulsion properties
• Calcium or sodium chloride to reduce viscosity
• water soluble polymers from cellulose, xanthan etc to
increase viscosity and reduce settlement
• Associative polymers like acrylates to increase
viscosity
• Adhesion promoters, biocides, pigments

Surface Chemistry
 Typical Emulsifiers

Tallowdiamine hydrochlorides
Efficient
R NH NH 2 2HCl Substantive
pH sensitive
CRS and CMS

Tallowdiquaternary dichloride
CH
Efficient
+
3
+
CH
3
2 Cl Substantive
R N N Less pH sensitive
CH
3

CH CH CSS
3 3

R = C16/18
Surface Chemistry
Typical Cationic Emulsion Recipes

Soft asphalt for

Asphalt 150pen 67 chipseal application
Cationic latex 2.5
Tallowdiamine 0.2 CRS-2P
Hydrochloric acid 0.1
C l i
Calcium chloride
hl id 01
0.1
Soap pH 2
Water to 100

Asphalt 62
Tallowdiquaternary CSS-1
amine a 1.2
Soap pH 6
Water to 100

Surface Chemistry
Typical Cationic Emulsion Recipes

Polymer modifier
Asphalt 150pen 67 Cationic type
Cationic latex 2.5
Tallowdiamine 0.2 CRS-2P
Hydrochloric acid 0.1
C l i
Calcium chloride
hl id 01
0.1
Soap pH 2
Water to 100

Asphalt 62
Tallowdiquaternary CSS-1
amine a 1.2
Soap pH 6
Water to 100

Surface Chemistry
Typical Cationic Emulsion Recipes

Low concentration
Asphalt 150pen 67 cationic emulsifier
Cationic latex 2.5
Tallowdiamine 0.2 CRS-2P
Hydrochloric acid 0.1
C l i
Calcium chloride
hl id 01
0.1
Soap pH 2
Water to 100

Asphalt 62
Tallowdiquaternary CSS-1
amine a 1.2
Soap pH 6
Water to 100

Surface Chemistry
Typical Cationic Emulsion Recipes

Acid needed to activate

Asphalt 150pen 67 emulsifier
Cationic latex 2.5
Tallowdiamine 0.2 CRS-2P
Hydrochloric acid 0.1
C l i
Calcium chloride
hl id 01
0.1
Soap pH 2
Water to 100

Asphalt 62
Tallowdiquaternary CSS-1
amine a 1.2
Soap pH 6
Water to 100

Surface Chemistry
Typical Cationic Emulsion Recipes

Asphalt 150pen 67
Cationic latex 2.5 To control viscosity
Tallowdiamine 0.2 CRS-2P
Hydrochloric acid 0.1
C l i
Calcium chloride
hl id 01
0.1
Soap pH 2
Water to 100

Asphalt 62
Tallowdiquaternary CSS-1
amine a 1.2
Soap pH 6
Water to 100

Surface Chemistry
Typical Cationic Emulsion Recipes

Asphalt 150pen 67
Cationic latex 2.5
Tallowdiamine 0.2 CRS-2P
Hydrochloric acid 0.1
C l i
Calcium chloride
hl id 01
0.1
Soap pH 2
Water to 100 High Dosage

Asphalt 62
Tallowdiquaternary CSS-1
amine a 1.2
Soap pH 6
Water to 100

Surface Chemistry
Typical Cationic Emulsion Recipes

Asphalt 150pen 67
Cationic latex 2.5
Tallowdiamine 0.2 CRS-2P
Hydrochloric acid 0.1
C l i
Calcium chloride
hl id 01
0.1
Soap pH 2
Water to 100
N acid
No id needed
d d
Asphalt 62
Tallowdiquaternary CSS-1
amine a 1.2
Soap pH 6
Water to 100

Surface Chemistry
Typical Anionic Emulsion Recipes
For “H” grade
Asphalt PG64-22 65
Anionic latex 2
Tall Oil 1.2 HFMS-2H
Potassium hydroxide 0.4
naphtha
hth 7
Soap pH 11.5
Water to 100

Asphalt 62
Lignin based product 2.0 SS-1
SoappppH 10.5
Water to 100

Surface Chemistry
Typical Anionic Emulsion Recipes
Anionic latex grade
Asphalt PG64-22 65
Anionic latex 2
Tall Oil 1.2 HFMS-2HP
Potassium hydroxide 0.4
naphtha
hth 7
Soap pH 11.5
Water to 100

Asphalt 62
Lignin based product 2.0 SS-1
SoappppH 10.5
Water to 100

Surface Chemistry
Typical Anionic Emulsion Recipes

Asphalt PG 64-22 65 High dosage for High

Anionic latex 2 Float properties
Tall Oil 1.2 HFMS-2HP
sodium hydroxide 0.4
naphtha
hth 7
Soap pH 11.5
Water to 100

Asphalt 62
Lignin based product 2.0 SS-1
SoappppH 10.5
Water to 100

Surface Chemistry
Typical Anionic Emulsion Recipes

Asphalt PG 64-22 65 To activate emulsifier

Anionic latex 2
Tall Oil 1.2 HFMS-2HP
Sodium hydroxide 0.4
naphtha
hth 7
Soap pH 11.5
Water to 100

Asphalt 62
Lignin based product 2.0 SS-1
SoappppH 10.5
Water to 100

Surface Chemistry
Typical Anionic Emulsion Recipes

To provide workability
Asphalt PG64-22 65 in the mix application
pp
Anionic latex 2
Tall Oil 1.2 HFMS-2H
sodium hydroxide 0.4
naphtha
hth 7
Soap pH 11.5
Water to 100

Asphalt 62
Lignin based product 2.0 SS-1
SoappppH 10.5
Water to 100

Surface Chemistry
Testing and Specification of Emulsions

• Composition
•Water asphalt
•Water, asphalt, solvent
solvent, polymer
• Handling and Storage
• viscosity, storage stability (settlement), sieve
• Reactivity
• demulsibility, cement mix test, hand mix tests
• Residue properties
•ppenetration,, softening
gppoint,, float,, ductility,
y, torsional
recovery, elastic recovery, PG grading(?)
•Performance tests
• adhesion, mix designs, application specific tests

Surface Chemistry
Alan James
AkzoNobel Surface Chemistry LLC
Croton River Center
281 Fields Lane
Brewster NY 10509
Desk: 845 276 8298
Cell: 914 525 5307
E-mail alan.james@akzonobel.com

Surface Chemistry