3/31/2017

BITUMEN

Background
 Asphalt has been used in road
construction since the early 1800s
 It typically comprises graded aggregate
mixed with a bituminous binder which
results in a strong but flexible material
with good durability
 Initially tar was used as the binder which
was later replaced by bitumen which is
refined from crude oil

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Background
 The origins of bitumen as an engineering
material date from 3800–3000 BC when it
was used d as a mortar ffor masonry and d
waterproofing
 bitumen is an extremely temperature
dependent material whose response also
depends on loading time
 In most engineering applications of bitumens,
their inherent temperature susceptibility is
utilized to ensure that they are sufficiently
fluid during application and sufficiently stiff
when in use

Background
 Importance of temperature-viscosity
relationshipp in terms of bitumen
performance
 Bitumen must be;
◦ fluid enough to coat the aggregate
◦ viscous enough not to run off the aggregate
duringg mixingg or transport
p
◦ fluid enough for the mixture to remain
workable during compaction
◦ viscous enough to carry the traffic

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Brief History
 The term ‘bitumen’ originated in Sanskrit,
where the words jatu meaning pitch and
jatu-krit meaning pitch creating, referred
to the pitch produced by certain resinous
trees
 The later Latin equivalent is claimed to be
originally gwitu-men or pixtu-men, which
was subsequently shortened to ‘bitumen’
when passing by way of French to English

Brief History
 There are also Biblical accounts of the use of
bitumen. Noah used it on the ark and Moses
was hidden
hidd as a babyb b in
i a basket
b k
waterproofed with bitumen
 In the middle of the nineteenth century
attempts were made to utilize rock asphalt
from European deposits (mines) for road
surfacing and from this there was a slow
d l
development t off the
th use off natural
t l asphalt
h lt
products, followed by the advent of coal tar
and later of bitumen manufactured from
crude oil

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Bitumen Manufacture
 Although ‘natural’ bitumens, such as Trinidad
Lake Asphalt (TLA), are still used, most
present-day applications make use of
bitumen manufactured from crude oil
 Crude oil consists of a complex mixture of
hydrocarbons of different molecular weight
produced by nature primarily from plant life
and the remains of marine micro-organisms
over millions of years under varied
conditions of temperature and pressure

Crude Oil
 Four principal crude oil producing areas
in the world
◦ USA
◦ Middle East
◦ the countries around the Caribbean
◦ Russia
 Physically, crude oils range from viscous
black liquids to free-flowing straw-colored
liquids

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Crude Oil
 Chemically crude oils are predominantly
pparaffinic,, naphthenic
p or aromatic,, with
combinations of the first two being most
common
 Crude oils vary widely in the amount and
nature of the hydrocarbons they contain
 Bitumen being the residue left, after the
more volatile fractions of the crude oil
have been distilled off, varies significantly
from crude to crude

Crude Oil
 The physical state of crude oil is described by its
API (American Petroleum Institute) gravity
 API gravity is related to the density of the crude
oil
 The API gravity for crude oils generally varies
from 10 to 70˚
 It measures that how heavy or light a petroleum
liquid is, compared to water
 Water has API gravity of 10˚
 Hydrometer is used for the measurement of API
gravity

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Crude Oil
 Crude oils with a low API gravity are viscous with
high density and generally contain a high percentage
of bitumen
 Of the 1300 types of crude oil classified worldwide,
only 10% are suitable for producing bitumen capable
of meeting the specifications
 These crudes are known as ‘bitumen’ crudes and are
defined as ‘heavy’ with an API gravity of <20˚ API
 These crudes also tend to have a high sulphur
content (>1% by weight) and are classified as ‘sour’
sour
compared with the low sulphur content ‘sweet’
crudes used to produce distillate products (LPG
(liquid petroleum gas), naphtha, and kerosene oil etc.

Bitumen Manufacture
 The manufacture of bitumen is a very
sophisticated activity requiring extensive
expertise and considerable financial
investment to provide consistent
products meeting the relevant
specification requirements
 Relevant specifications can be found in
the European Standard BS EN12591: 2000

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Bitumen Manufacture
 The manufacture of bitumen from crude oil involves a
number of distillation processes and, if required, further
treatments includingg air blowingg and blendingg
 Initially, crude oil is refined by atmospheric fractional
distillation to separate gas, gasoline, kerosene, gas oil and
long residue (heaviest fraction consisting of a complex
mixture of high molecular weight hydrocarbons)
 The long residue is then further distilled under vacuum at
350–400˚C to produce short residue, which is the feedstock
used in the manufacture of different grades of bitumen
 The physical properties of the short residue may be further
modified by processes such as air ratification (blowing) or
blending of different short residues to produce a range of
bitumens with different consistencies (degrees of hardness)
 Bitumen manufactured directly from the short residue is
known as ‘straight run’ bitumen

BITUMEN MANUFACTURE

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BITUMEN MANUFACTURE

Distillation
 Atmospheric distillation
◦ Separation of mixtures by heating, boiling/vaporizing
and condensing at atmospheric pressure
 Vacuum Distillation
◦ Compounds with high boiling point
◦ Pressure is reduced to achieve boiling at lower
temperatures
◦ Also ggood for compounds
p havingg boilingg temperature
p
greater than their decomposition temperature
 Fractional distillation/successive distillations also
referred as rectification

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PRODUCTION PROCESSES

Cutbacks and Emulsions

 Bitumen Emulsion
◦ Dispersion of bitumen in water by using some
chemical emulsifying agent
 Bitumen Cutback
◦ Bitumen is ‘cutback’ by adding controlled amounts of
petroleum distillates such as kerosene. This is done to
reduce the viscosity of the bitumen temporarily so it
can penetrate pavements more effectively or to allow
spraying at temperatures that are too cold for
successful sprayed sealing with neat bitumen. The
materials used to cutback bitumen will evaporate
after application to leave the remaining material
similar in hardness to the original bitumen

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Emulsion and Cold Mix Asphalt

 In order to adhere bitumen to aggregate it is
important that aggregates are heated
sufficiently
ffi i l to d drive
i off
ff allll the
h moisture
i
 This is a costly and energy intensive
procedure and has strong economic and
environmental impact
 cold-mix technology utilizes a form of
bitumen which is workable at ambient
temperatures and which can mix with cold,
wet aggregate
 cold-mix technology however has its own
drawbacks

Bitumen Emulsions

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Foamed Bitumen
 An alternative form of cold-mix asphalt
utilizes bitumen in the form of a foam
 The foam is produced by the very rapid
transformation of water into steam as it
comes into contact with hot (typically 160-
180°C) bitumen, aided by the addition of air.
 The water content within the foam is
generally between 2 and 5% of the bitumen
volume but, once transformed into steam,
the foam expands to many times the volume
of the bitumen itself, and in this state it can
readily be mixed into an aggregate

Foamed Bitumen
 The ratio of peak foam volume to original
bitumen volume is known as the ‘expansion
ratio’,
i ’ while
hil the
h time
i untilil this
hi peakk volume
l
is halved is known as the ‘half life’
 The expansion ratio is typically between 5
and 20; the half life is typically between 10
and 40 seconds
 Emulsions can be stored for months before
use, whereas foamed bitumen has to be used
immediately
 However, the advantage is that foamed
bitumen requires less water

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Foamed Bitumen

Bitumen Modification
 Unmodified/virgin/raw bitumen has
certain weaknesses;
◦ it can ‘flow’ at high temperature, leading to
pavement rutting
◦ it can fracture at low temperature, leading to
pavement cracking
◦ the
th adhesion
dh i bbetween
t bit
bitumen andd aggregate
t
can break down under a combination of
ageing and water attack

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Bitumen Modification
 Bitumen modifications can be generally
divided into three categories
◦ Polymers
 The word Polymer comes from the Greek "poly"
meaning many, and "meros", meaning parts or units
 A substance that has a molecular structure built up
from a large
g number of similar units bonded
together
◦ Natural rubbers
◦ Simple chemicals

Polymers
 Additives are designed to enhance the beneficial properties
of bitumen while retarding the less important ones
 Common examples are;
◦ Styrene-Butadiene-Styrene (SBS)
◦ Styrene-Butadiene Rubber (SBR)
◦ Ethyl Vinyl Acetate (EVA)
 These products increase the viscosity (and visco-elastic
stiffness) of the bitumen at high temperatures but not at low
temperatures
 They may also give benefit in fatigue life, particularly in the
case off SBS
 Polymer usage is a specialist field and not all bitumens are
suited to blending with all modifiers
 It is quite possible to blend an otherwise excellent additive
with a given bitumen and to achieve no benefit at all

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Natural Rubber
 Various forms of rubber can be added to
bitumen in an attempt p to enhance the
‘resilience’ of a binder, i.e. the resistance
to damage
 Very recent example and rather hot issue
these days is the use of tyre rubber in
p
asphalt mixtures which mayy be beneficial
for asphalt (debatable) but considered a
very environmental friendly solution of
getting rid of waste tyres

Simple Chemicals
 Sulphur and manganese have both been used in
significant quantities
 Manganese addition is really just a means of increasing
the cross-linkage of bitumen molecules and thereby
increasing viscosity and stiffness. However, the
disadvantage is that the bitumen becomes more
brittle
 Sulphur, which is a liquid at >115°C, enhances
workability at high temperature; as a solid at in-
service temperatures it then acts as aggregate
 One of the inevitable problems with bitumen
modification is its complexity and this means that
modifications are not as straight-forward as they
seem theoretically

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Bitumen Chemistry
 A non-polar material but have very small
amounts of polar organic compounds
 Complex combination of organic
molecules which vary in their
composition
 Components ranging from relatively light
oils to high molecular mass solid
asphaltenes

ELEMENTAL COMPOSITION

 Carbon
C b  82% - 88%
 Hydrogen  8% - 11%
 Sulphur  0% - 6%
 Oxygen  0% - 1.5%
 Ni
Nitrogen  0% - 1%

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MOLECULAR STRUCTURE
H H H H
H H
C C C C
H C H H H
C C C
H H
C C C C
H H H
H Aromatic H H Naphthenic

H H H
H H H
H C C C
C C C H
H H H
H H H Aliphatic

FRACTIONAL COMPOSITION
 The individual molecules in a bitumen are
large and non-uniform, varying
t
tremendously
d l in i molecular
l l weight i ht and
d
therefore in resulting physical attributes
 Separation of bitumen into homogenous
fractions
 Groups or generic fractions based on
◦ molecular
l l sizei
◦ chemical reactivity and/or polarity
 SARA (Saturates, Aromatics, Resins &
Asphaltenes)

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SARA ANALYSIS
 A method for characterization of heavy oils based on
fractionation, whereby a heavy oil sample is separated into
smaller quantities or fractions, with each fraction having a
different composition
 Fractionation is based on the solubility of hydrocarbon
components in various solvents used in this test
 Each fraction consists of a solubility class containing a
range of different molecular-weight species
 In this method, the crude oil is fractionated to four
solubility classes, referred to collectively as SARA:
saturates, aromatics, resins, and asphaltenes
 Saturates are generally paraffins, while aromatics, resins,
and asphaltenes form a continuum of molecules with
increasing molecular weight, aromaticity, and heteroatom
contents. Asphaltenes may also contain metals such as
nickel and vanadium

SARA ANALYSIS
 Asphaltenes
◦ Asphaltenes are ‘polar’, which means the molecules
carry positive and negative charge at different points
and that bonds between the molecules can therefore
form easily. Basically, the more asphaltenes there are
in a bitumen, the harder and more viscous that
bitumen is likely to be
◦ Insoluble in n-heptane, black or brown amorphous
(non-crystalline)
(non crystalline) solids (fairly high molecular weight
1,000 - 100,000)
◦ 5nm - 30nm (30x10-9m) particle size
◦ Principal viscosity enhancing components, constitute
5% - 25% of the bitumen

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SARA ANALYSIS
 Saturates
◦ At the other end of the scale,, saturates are a
lighter non-polar fraction and they form a ‘soup’
surrounding the other types of molecule, giving
fluidity to the overall compound
◦ A bitumen with plenty of saturates will be softer
and have a lower viscosity and may also be more
readily able to ‘heal’, i.e. to self-repair and reform
broken bonds
◦ Viscous oils, straw or white in colour
◦ 5% - 20% of the bitumen

SARA ANALYSIS
 Resins
◦ Resins are highly polar and they strongly affect
the degree to which asphaltenes are dispersed
within the bitumen
◦ Soluble in n-heptane, dark brown solid or
semi-solid
◦ Dispersing agents (peptisers) for asphaltenes
◦ 1nm - 5nm particle size (molecular weight
500 - 50,000)
◦ Constitute 5% - 20% of the bitumen

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SARA ANALYSIS
 Aromatics
◦ Aromatics make up the largest volume
fraction; they are non-polar and act as a
solvent to both asphaltenes and resins
◦ Dark brown viscous liquids with high
dissolving ability
◦ 40% - 65% of the total bitumen (lowest
molecular weight 300 - 2,000)
◦ Resins and aromatics, are intermediate
components in the soup

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BITUMEN TESTS (Physical

Properties)

 Needle Penetration Test

 Ring & Ball Softening Point Test
 Viscosity Tests
 Fraass Breaking Point
 Ductility Test

Viscosity
 How a material will behave at a given
temperature & over a temperature range
 Measured in pascal second (Pa.s) or centi
stokes (cSt)
 Absolute/dynamic viscosity; applied shear
stress divided by shear rate per second
 Kinematic viscosity; dynamic viscosity divided
byy densityy
 Capillary Viscometer; Time required for a
fixed quantity of material to flow through an
orifice

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Viscosity
 High Temperature Measurements
 Absolute Viscosity @ 6060C
C (poises)
 Kinematic Viscosity @ 135C (centistokes,
1cSt = 1 mm²/s)
 Rotational Viscometer; torque required to
rotate the spindle at a pre-specified shear
rate is measuredd and
d convertedd to viscosity
 1 Pa.s = 10 P = 1000 cP
 1 cP = 1 mPa.s

Viscosity
 In general, about 0.2Pa.s is required for mixing,
giving a temperature range of 140 to 180°C
 30Pa.s is a maximum value for compaction, giving
a minimum compaction temperature of between
70 and 80°C
 Temperature variations between a hot summer’s
day, when the pavement temperature is well over
40°C, and that expected
p in the winter are qquite
high. It is therefore immediately obvious that
asphalt performance will be quite different in
summer compared to winter

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Viscosity

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Rotational Viscometer

Fraass Breaking Point

 Temperature at which bitumen reaches a
critical stiffness and cracks
 Fraass temperature
p is equivalent
q to the
temperature at which the bitumen has a
penetration of 1.25
 Low Temperature Measurements
 Less than 0C
 Fracture strength of bitumen
 St l plaque
Steel l coated
t d with
ith bit
bitumen is
i flexed
fl d
and released
 Temperature of the plaque is reduced at 1˚C
per minute

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Fraass Breaking Point

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Bitumen Test Data Chart (BTDC)

 The Bitumen Test Data Chart (BTDC) was
developed
p for showingg the effect of
temperature on the mechanical behaviour of
bitumens utilising an approximate
relationship between penetration and
viscosity
 The BTDC provides a convenient means of
plotting
l tti routine
ti bitumen
bit d
data,
t enabling
bli
interpolation and tentative extrapolation of
data, since the majority of bitumens produce
data that plot as a straight line on the chart

Bitumen Test Data Chart (BTDC)

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Bitumen Test Data Chart (BTDC)

Bitumen Test Data Chart

Fraass

Penetration

Softening Point

Viscosity

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