01 DECEMBER 2017

Fingerprinting Bitumen Chemistry and Quantifying Its

Impact on Microstructural and Engineering Properties

NAZMUS SAKIB
Graduate Research Assistant, The University of Texas at Austin
1.0 Presentation Outline
1. Significance of bitumen chemistry and available technology
2. Development of proposed methods for exploring bitumen
chemistry:
a. Theoretical development
b. Working details and verification
c. Plans for future works regarding bitumen chemistry
3. Exploring thermal history dependency of bitumen on rheology
and strength parameters
a. Thermal history dependent rheology and observation of bitumen
microstructures
b. Plans for future works with bitumen conditioning
1.1 Bitumen Chemistry
1. Bitumen/Asphalt is the distillation residua of crude oil
2. Organic material with thousands of chemical species
3. Mainly hydrocarbon with small amounts of
heteroatoms such as N, O, S, and trace metals
4. Hydrocarbons are aliphatic, aromatic and both together
5. Heteroatoms, large number of branching and rings
introduces polarity in bitumen
1.2 Bitumen Separation Principles
1. Practically impossible to separate all species
2. Can be discretely grouped by using physio-chemical
properties
a. Separation using molecular size (SEC/GPC)
b. Precipitation separation (solubility based)
c. Separation based on polarity and reactivity
3. Continuous distribution can be found from
spectroscopy (UV, FT-IR, NMR, MS)
1.3 SARA Classification
1. SARA (SAR-A) stands for four major ‘fractions’ of bitumen;
Saturates, Aromatics, Resins and Asphaltenes
2. Traditionally asphaltene is separated based on solubility
3. First three (which are collectively called maltenes) is
separated based on polarity
4. Polarity, polarizability, molecular weight and
aromaticity: Saturates<Aromatics<Resins<Asphaltenes
1.4 Typical SARA Fractions

Masson, 2001
1.5 Importance of Bitumen Chemistry
1. Commonly used benchmarks (rheological
and mechanical tests) sometimes fail to
predict performance issues
2. Use of additives, extenders, and recycled
products present compatibility issues
3. With fingerprinting chemistry , binding
capacity, ageing characteristics and
performance can be more accurately
predicted
4. End-user can verify what they are buying
Construction: October 2016
Image Taken: May 2017
 1.6 Current Testing Practice vs. Reality
Tests Conducted by DOTs Modifier Used (Supplier Reported)
100
100 50
41.3

Percentage Response
Percentage Response

80 40
32.6
30 26.1
60 21.7
20 15.2 17.4
40 10.9
23.9 19.6 10
20
4.4 2.2 2.2 0
0
 1.7 Chemical Fingerprinting: Current Tech

Automated LC (Boysen, 2015) IP 469: Iatroscan (TLC-FID)

$$ $$
ASTM D4124 (Sultana, 2015)

1.8 Reason for Lack of Chemical testing

1. Time consuming process

Inconvenient testing 2. Expensive equipment
procedure 3. Use of hazardous solvents
in large amounts

No established formula
linking chemistry and Lack of Data Points
performance
2.0 Bitumen Fingerprinting: Objectives
Introduce a method that is:
a. Low capital cost
b. Low operation cost
c. High throughput
d. Repeatable (intra/inter laboratory)
e. attractive to non-chemists
f. Cross-compatible with present methods
2.0 Bitumen Fingerprinting: Major Steps
1. Mixing bitumen with a non-polar solvent
a. Based on Solubility Index (like dissolves like)
b. Asphaltene (precipitated and filtered out)
c. Maltene: saturates + aromatics + resins
2. Maltene fractionation using chromatography (2 alternatives)
a. Solvent (mobile phase) elutes maltene fraction from stationary phase
(chromatography media)
b. Like dissolves like with a twist (competition between phases)
c. Increasingly polar solvent elutes increasingly polar fractions
2.0 Flowchart of SARA Fractionation
2.2-2.5 Maltene Fractionation and Quantification

Saturates

SPE Liquid Gravimetric

Aromatics
Chromatography Quantification
2.1 Asphaltene & Maltene Separation

Resins
Dissolution
Bitumen Maltene
and Filtration
Saturates
Asphaltene
Thin Layer Densitometric
Aromatics
Chromatography Quanticiation

Resins
2.1.1 Asphaltene
1. Most polar fraction of bitumen
2. Black/Dark Brown, powdery
3. Either stays dissolved in bitumen matrix or
remains in suspension*
4. Generally imparts stiffness, strength,
brittleness to bitumen
5. Easiest to remove among four SARA fractions
2.1.2 Precipitation of Asphaltene: Theory
1. When mixed in a non-polar solvent, most polar fraction will
fail to dissolve
2. Depends on the polarity of solvent and polarity distribution
of bitumen
3. Generally, least polar solvent will result highest asphaltene
yield
4. It is possible to fractionate asphaltene into multiple groups
with choice of solvent
2.1.3 Precipitation of Asphaltene: Solubility
1. Hildebrand δ=f{heat of vaporization / molar vol.} and Hansen
solubility parameters (δ2= δD2 + δP2 + δH2)
2. Relative Energy Difference = ∑(δ1 –δ2) 2 / Radius of Sol. Sphere

(Redelius 2004)
2.1.4 Method Selection for Precipitation
Current practices:
1. 1:10 w/v solution in n-pentane swirled in a warm water bath dissolved;
filtered using rapid filter paper (ASTM D2007, 2016)
2. 1:30 w/v solution in n-heptane prepared under reflux for 60 minutes;
filtered with Whatman Grade 42 (2.5 m pore) filter paper (ASTM D6560)
3. 1:100 w/v solution in n-heptane prepared under reflux for 20 minutes;
filtered using a glass microfiber filter pad with 1.5 μm pore size (ASTM
D3279, 1997).
4. 1:100 w/v solution in iso-octane (previously n-heptane) prepared under
reflux for 3-4 hours; filtered using a medium porosity (10-15 m pore size)
Buchner funnel fritted glass filter (ASTM D4124, 2001)

Our Choice: 1:100 w/v n-heptane stirred at RT for 24 hours, PTFE syringe filters
2.1.5 Scaling Up the Operation
~0.4 g binder Vacuum
Manifold

Syringe
Filters

Stirring plate
Dissolution of maltenes: Asphaltene filtration:
• existing practice (left): reflux, 1-2 g • existing practice (left): fritted glass,
bitumen, 2-3 hours operation + cleaning time: 3-4 hours
• proposed method (top): no heat, 0.4 g • proposed method (top): commercial
bitumen, 24 hours PTFE filters, time required= 15 min
2.1.7 Method Verification: Materials
1. Two bitumen samples were divided into SARA as a part
of a previous study using ASTM D4124 (Sultana 2014)
2. Each fraction was used to ‘spike’ its parent binder
(~34% increase of that individual fraction)
3. A set of (1+4)+(1+4)=10 binders of known SARA
fractions were prepared
2.1.8 Method Verification: Asphaltene
1. Solvent:
a. ASTM D4124 used iso-octane
b. proposed method uses n-heptane
2. Filter pore size:
a. ASTM D4124: 10-15 µm fritted glass
b. Proposed Method: 0.2 µm PTFE filter
2.0 Recap: Flowchart of SARA Fractionation
2.2-2.5 Maltene Fractionation and Quantification

Saturates

SPE Liquid Gravimetric

Aromatics
Chromatography Quantification
2.1 Asphaltene & Maltene Separation

Resins
Dissolution
Bitumen Maltene
and Filtration
Saturates
Asphaltene
Thin Layer Densitometric
Aromatics
Chromatography Quanticiation

Resins
2.2.1 Elution of Maltene Fractions: Theory
1. Chromatography is a versatile tool for separating slightly different
materials
2. Bitumen is polarity continuum so perfect fractionation does not exist
3. Solvent type determines how ‘hard’ it is going to ‘fight’ with
stationary phase for a given bitumen molecule
4. Wide variety of solvents are used for bitumen fractionation, all which
are commonly called as SARA
5. Elution is done in the order of increasing polar elution products
 We propose two new methods for Maltene fractionation:
1. Thin-layer Chromatography with Densitometry
2. Miniaturized Colum Chromatography use Solid Phase Extraction technique
2.2.2 Solvent Selection for Elution (1/2)
1. Considerations:
a. The solvent set should elute three fractions which corresponds
qualitatively/semi-qualitatively with existing standards
b. Increasing order of polarity/ elutropic series
c. Compatibility with other standards
d. Toxicity and availability of solvents
2.2.2 Solvent Selection for Elution (2/2)
2.2.3 Choosing Stationary Phase (SPE/TLC)
1. Option for Normal-phase chromatography are:
– Alumina
– Silica gel
2. Common practice:
a. Iatroscan TLC-FID uses Silica gel rods (IP 469)
b. ASTM D4124 uses calcined alumina
c. Other options are bonded forms: cyano/amino group

For availability, convenience and compatibility, we have selected Silica

Gel as stationary phase (in SPE cartridge and on TLC plate)
2.3.1 Features of SPE Based method
1. Setup includes Vacuum manifold, SPE cartridges, vacuum
pump and drying oven
2. Use of commercially available SPE cartridges replace time-
consuming and less-controlled LC columns
3. Takes about 30-35 minutes for eluting 4+ specimens (ASTM
D4124 process takes about 4 hours for one specimen)
4. Consumes 100 ml solvent per specimen (ASTM D4124 uses
575 ml)
 2.3.2 Elution of Saturates (SPE)

SPE (Si) cartridge

Fig. 3: Pre-wash with n-Heptane Fig. 4: Maltene application Fig. 5: Collected Saturates
(15 mL + 10 mL n-Heptane)
2.3.3 Elution of Aromatics (SPE)

Fig. 6: Elution of Aromatics with 80% Fig. 7: Collected Aromatics

Toluene and 20% n-Heptane (25 mL)
2.3.4 Elution of Resins (SPE)

Fig. 8: Resins elution with 90% DCM Fig. 9: Collected Resins

and 10% Methanol (40 mL)
Thank You!