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
Surface Chemistry 3
Asphalt
Surface Chemistry 4
Why Use Asphalt Emulsion
Surface Chemistry
Emulsions around the Home
Surface Chemistry
Asphalt Emulsion
100 micron/0.1mm
Source :BASF
Surface Chemistry
Size Distribution of Asphalt Emulsion
Droplets
ume %
volu
median (d50
d50))
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
Emulsion
Soap Asphalt
Colloid Mill
Surface Chemistry 11
Inside the Colloid Mill
Surface Chemistry 12
Schematic of Batch Emulsion Plant
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
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
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
Surface Chemistry
Breakdown of the Emulsion
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
Low viscosity
high-float (57% asphalt)
medium-setting
(anionic)
Surface Chemistry 21
Emulsions are classified according to
Reactivity and Particle Charge
+ve -ve
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
Surface Chemistry
Typical Emulsifier Structures
R(li i )
R(lignin)----------------------------------- SO3- Na +
Surface Chemistry
Some charged emulsifiers do not need
pH adjustment
RN(CH3)3 + Cl -
RSO3- Na+
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?
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
45
4.5
e micron
4
edian parrticle size
3.5
3
me
emulsifier length
3/1 000 000 mm
asphalt droplet
diameter 3/1000 mm
Surface Chemistry
Emulsifier generates charged Asphalt
Droplets
Sulphonate SO3- - - -
Ethoxylate (C2H4O)xH o o o
Carboxylate COOH/COO- o - -
A i NH2/NH3+
Amine + + o
Asphalt + o -
Mineral + o -
Surface Chemistry 35
Manufacture of Emulsifiers
methylchloride
th l hl id
Quaternary
Fatty amines Quaternization ammonium
salts
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
Surface Chemistry
Setting Mechanisms Cationic Emulsions
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
Surface Chemistry
Breakdown of the Emulsion
Surface Chemistry
Emulsifier Chemistry and Use Levels
Surface Chemistry
Other Emulsion Ingredients
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
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
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 62
Lignin based product 2.0 SS-1
SoappppH 10.5
Water to 100
Surface Chemistry
Typical Anionic Emulsion Recipes
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