Emulsion 101 Alan James AkzoNobel Surface Chemistry

Emulsion 101
Asphalt Residue from the vacuum distillation The Chemistry of Emulsions of crude oil y C d oil contains 1 60% asphalt depending on the source Crude il t i 1-60% h lt d di th The all refineries produce asphalt Not Chemistry of Emulsifiers Themillion ton process 36 Setting asphalt used in USA each year 31 million Formulation construction, Emulsionton used in road construction rest mostly in roofing

Surface Chemistry

Asphalt
Residue from the vacuum distillation of crude oil C d oil contains 1 60% asphalt depending on the source Crude il t i 1-60% h lt d di th 36 million ton asphalt used in USA each year 31 million ton used in road construction, rest mostly in roofing 2 3 million ton used in emulsions rest mostly in hot mix 2-3 emulsions, 7-10 million ton emulsion worldwide

Surface Chemistry

Asphalt
Supplied in grades depending on its consistency/viscosity F emulsions viscosity is defined b t t lik penetration For l i i it i d fi d by tests like t ti and softening point The choice of viscosity depends on the end use.

Surface Chemistry

Why Use Asphalt Emulsion

Cold processes save energy Easier handling and storage Safe and environmentally friendly Low cost in place and onon 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
oil-in-water emulsion

W/O
water-in-oil (inverted emulsion)

W/O/W
multiple 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

volu ume %

median (d50) d50)

particle size (micron)

Surface Chemistry

Components of an Asphalt Emulsion

water 30-50% chemicals 0.2-2.5% solvent 0-10% p y polymer 0-4% % asphalt 40-70%

Surface Chemistry

Production of Bitumen Emulsions

Asphalt dispersed in a colloid mill into micron droplets in water

Emulsion

Soap

Colloid Mill

Asphalt

Surface Chemistry

11

Inside the Colloid Mill

Surface Chemistry

12

Schematic of Batch Emulsion Plant

stabilizer emulsion acid emulsifier

asphalt

140C

90C 50C batch soap tank water inlet

colloid mill

Latex L t
Surface Chemistry

Bitumen loading pump Emulsion tank kit Bitumen tank kit

Drum filli D 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 lsion electrostatic repulsion pre ents close approach emulsion-electrostatic rep lsion prevents of drops

+ +

Anionic emulsion-electrostatic repulsion prevents close approach of drops fd

Surface Chemistry

Breakdown of the Emulsion

Flocculation and Coalescence

Emulsion Droplets Charge on droplets prevents close approach

Flocculation Close approach of droplets leads to adhesion between droplets. Water is squeezed out

Coalescence Water drains between droplets and surfactant film breaks down, Droplets fuse, trapping some water

Coalescence Trapped water diffuses out.

Setting

Curing

Surface Chemistry

Breakdown of the Emulsion

Settlement (Sedimentation)

Asphalt is g p generally denser than water y 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 eventual coalescence d t l 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
cationic

High viscosity (65% asphalt)

slow-setting

CSS - 1h
high-float

hard asphalt Low viscosity (57% asphalt)

HFMS - 2s
medium-setting (anionic)

with solvent

Surface Chemistry

21

Emulsions are classified according to Reactivity and Particle Charge

+ve rapid-setting medium-setting medium setting slow-setting CRS CMS CSS -ve RS chip-seal open-graded MS open graded mix 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 group

counterion

R(tallow) --------------------------------- N+(CH 3)3 R(tallow) --------------------------------- NH 2+CH 2CH 2CH 2NH 3+ R(nonylphenyl) ------------------------ O CH 2CH 2OCH 2CH 2O H O----CH O---H R(tall oil)---------------------------------- COO R(lignin)----------------------------------- SO3R(li i ) R= hydrocarbon or mostly hydrocarbon with 12-22 carbons N= nitrogen C=carbon, H= hydrogen O= oxygen nitrogen, C=carbon hydrogen, S= sulfur, Cl= chlorine, Na = sodium

Cl2Clnone Na + Na +

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) Hydrocarbon Ch i (Oil L i ) H d b Chain Loving) H

N+

C lCounterion (Water Loving)

Surface Chemistry 27

What is Interfacial Tension?

Water molecules like to bond to Attraction Forces in Water 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 y water molecules have only weak bonds and are not quite so happy This creates tension Water So surface tension is higher
Surface Chemistry 28

Tension = Energy

Surface Activity
Oil Surfactants (Emulsifiers) 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 Manufacture

Water-phase

Emulsion

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.

me edian par rticle size micron e

4.5 45 4 large head group 3.5 3 small head group 2.5 0.2 0.3 0.4 Emulsifier level % 0.5

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 and th t il would penetrate 5 miles d il d the tail ld t t il 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 Sulphonate SO3Ethoxylate (C2H4O)xH Carboxylate COOH/COOAmine A i NH2/NH3+ Quaternary Amine N(CH3)3+ Asphalt Mineral Acid Neutral Alkaline

o o + + + +

o + + o o

o o + 35

Surface Chemistry

Manufacture of Emulsifiers
Animal fat Vegetable oils g water

Splitting
ammonia

Nitrilation
hydrogen

Fatty amines

methylchloride th l hl id Fatty amines Nonyl phenol and Alcohols Ethylene or propylene oxide Olefins alkylbenzenes alkylnaphthalenes Quaternization

Quaternary ammonium salts Alkoxylates

Alkoxylation

Sulfonation
Sulfuric acid, sulfur trioxide

Sulfonates

Surface Chemistry

36

Manufacture of Emulsifiers
Tall Oil Tall Oil Imidazolines and amidoamines

Condensation
p y polyamines

Lignin Lignin Ligninamines

Addition
amine

Surface Chemistry

37

Factors Affecting Breaking and Curing

Aggregate Reactivity surface area, surface charge, surface chemistry f f h f 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 10 8 6 4 2 0 0 60 120 180 Time after Mixing (seconds) 240 no cement 0.5% cement

Surface Chemistry

40

Possible stages in cationic emulsion breaking

contact of emulsion with aggregate gg g

adsorption of 'free' , pH Emulsifier, p rises

Rise in pH leads to flocculation

coagulation/spreading over surface

Surface Chemistry

Breakdown of the Emulsion

Surface Chemistry

Emulsifier Chemistry and Use Levels

level % CRS CMS Micro CSS RS MS SS
0.15-0.30 0.30-0.60 0.6-2.0 0.8-2.5 0.2-1.0 0.6-1.5 1.0-2.5

typical emulsifiers
tallowdiamine tallowdiamine tallowtetramine, tall oil imidazoline tallowdiquaternary, ethoxylates tall oil acids tall oil acids 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 N hth mineral spirits, N 2 f l oil, fl oils Naphtha, i l i it No2 fuel il flux 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 Substantive pH sensitive CRS and CMS

NH

NH 2 2HCl

CH
3 + +

CH
3

2 Cl
3

N CH
3

N CH
3

CH

Tallowdiquaternary dichloride Efficient Substantive Less pH sensitive CSS

R = C16/18
Surface Chemistry

Typical Cationic Emulsion Recipes

Asphalt 150pen Cationic latex Tallowdiamine Hydrochloric acid Calcium chloride C l i hl id Soap pH Water Asphalt Tallowdiquaternary amine a Soap pH Water 67 2.5 0.2 0.1 0.1 01 2 to 100 62 CSS-1 1.2 6 to 100 Soft asphalt for chipseal application CRS-2P

Surface Chemistry

Typical Cationic Emulsion Recipes

Asphalt 150pen Cationic latex Tallowdiamine Hydrochloric acid Calcium chloride C l i hl id Soap pH Water Asphalt Tallowdiquaternary amine a Soap pH Water 67 2.5 0.2 0.1 0.1 01 2 to 100 62 CSS-1 1.2 6 to 100 Polymer modifier Cationic type CRS-2P

Surface Chemistry

Typical Cationic Emulsion Recipes

Asphalt 150pen Cationic latex Tallowdiamine Hydrochloric acid Calcium chloride C l i hl id Soap pH Water Asphalt Tallowdiquaternary amine a Soap pH Water 67 2.5 0.2 0.1 0.1 01 2 to 100 62 CSS-1 1.2 6 to 100 Low concentration cationic emulsifier CRS-2P

Surface Chemistry

Typical Cationic Emulsion Recipes

Asphalt 150pen Cationic latex Tallowdiamine Hydrochloric acid Calcium chloride C l i hl id Soap pH Water Asphalt Tallowdiquaternary amine a Soap pH Water 67 2.5 0.2 0.1 0.1 01 2 to 100 62 CSS-1 1.2 6 to 100 Acid needed to activate emulsifier CRS-2P

Surface Chemistry

Typical Cationic Emulsion Recipes

Asphalt 150pen Cationic latex Tallowdiamine Hydrochloric acid Calcium chloride C l i hl id Soap pH Water Asphalt Tallowdiquaternary amine a Soap pH Water 67 2.5 0.2 0.1 0.1 01 2 to 100 62 CSS-1 1.2 6 to 100

To control viscosity CRS-2P

Surface Chemistry

Typical Cationic Emulsion Recipes

Asphalt 150pen Cationic latex Tallowdiamine Hydrochloric acid Calcium chloride C l i hl id Soap pH Water Asphalt Tallowdiquaternary amine a Soap pH Water 67 2.5 0.2 0.1 0.1 01 2 to 100 62 CSS-1 1.2 6 to 100

CRS-2P

High Dosage

Surface Chemistry

Typical Cationic Emulsion Recipes

Asphalt 150pen Cationic latex Tallowdiamine Hydrochloric acid Calcium chloride C l i hl id Soap pH Water Asphalt Tallowdiquaternary amine a Soap pH Water 67 2.5 0.2 0.1 0.1 01 2 to 100 62 1.2 6 to 100

CRS-2P

No id N acid needed d d CSS-1

Surface Chemistry

Typical Anionic Emulsion Recipes

For H grade Asphalt PG64-22 Anionic latex Tall Oil Potassium hydroxide naphtha hth Soap pH Water Asphalt Lignin based product Soap p p pH Water 65 2 1.2 0.4 7 11.5 to 100 62 2.0 10.5 to 100

HFMS-2H

SS-1

Surface Chemistry

Typical Anionic Emulsion Recipes

Anionic latex grade Asphalt PG64-22 Anionic latex Tall Oil Potassium hydroxide naphtha hth Soap pH Water Asphalt Lignin based product Soap p p pH Water 65 2 1.2 0.4 7 11.5 to 100 62 2.0 10.5 to 100

HFMS-2HP

SS-1

Surface Chemistry

Typical Anionic Emulsion Recipes

Asphalt PG 64-22 Anionic latex Tall Oil sodium hydroxide naphtha hth Soap pH Water Asphalt Lignin based product Soap p p pH Water 65 2 1.2 0.4 7 11.5 to 100 62 2.0 10.5 to 100 High dosage for High Float properties HFMS-2HP

SS-1

Surface Chemistry

Typical Anionic Emulsion Recipes

Asphalt PG 64-22 Anionic latex Tall Oil Sodium hydroxide naphtha hth Soap pH Water Asphalt Lignin based product Soap p p pH Water 65 2 1.2 0.4 7 11.5 to 100 62 2.0 10.5 to 100 To activate emulsifier HFMS-2HP

SS-1

Surface Chemistry

Typical Anionic Emulsion Recipes

Asphalt PG64-22 Anionic latex Tall Oil sodium hydroxide naphtha hth Soap pH Water Asphalt Lignin based product Soap p p pH Water 65 2 1.2 0.4 7 11.5 to 100 62 2.0 10.5 to 100 To provide workability in the mix application pp HFMS-2H

SS-1

Surface Chemistry

Testing and Specification of Emulsions

Composition Water, asphalt, solvent, Water asphalt solvent polymer Handling and Storage viscosity, storage stability (settlement), sieve Reactivity demulsibility, cement mix test, hand mix tests Residue properties penetration, softening p p , g point, float, ductility, torsional , , y, 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