Ucalgary 2017 Sofekun Gabriel

UNIVERSITY OF CALGARY
Rheometric Properties of Pure Liquid Elemental Sulfur
by
Gabriel Oluwaseyi Sofekun
A THESIS
SUBMITTED TO THE FACULTY OF GRADUATE STUDIES
IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE
DEGREE OF MASTER OF SCIENCE
GRADUATE PROGRAM IN CHEMISTRY
CALGARY, ALBERTA
AUGUST, 2017
© Gabriel Oluwaseyi Sofekun 2017

Abstract
Much of the transportation and handling of molten sulfur requires liquid sulfur pumps which are
challenging to operate due to the anomalous behaviour of sulfur’s viscosity around its λ-transition
region. Sulfur’s viscosity increases from ≈ 10 cP upon melting at T = 115 °C to ≥ 90 000 cP at
T = 187 °C. While the temperatures for this viscosity transition is well known, no shear related
information can be found in the literature. Understanding the flow behavior of molten sulfur will
allow for better pump design and/or qualification of their operational limits.
The investigation of the viscosity of molten sulfur was performed using a new Anton Paar
MCR 302 rheometer supplied with a 1000 bar titanium pressure cell. Viscosity profiles including
attenuation during heating or cooling are discussed, as well as the rheological behaviour of molten
sulfur encountered at shear rates experienced within pipe flow and/or commercial sulfur pumps.
ii
Acknowledgements
My sincere gratitude goes to my supervisor, Dr. Robert Marriott for his guidance throughout this
project. His passion, insights and knowledge were crucial to the progress of this study especially
when there was a need to modify the rheometer for this study to continue.
Thank you to Prof. Venkataraman Thangadurai and Dr. Simon Trudel for serving on my committee
and their insightful questions during the committee meetings.
My appreciation also goes to the entire Department of Chemistry office and the graduate program
support staff especially Janice Crawford for her administrative guidance as I progressed through
my Master’s degree program. I would like to appreciate the efforts of Edward Cairns, the Senior
Electronics Technician at the Science workshop for his unrelenting help at fixing parts of the
rheometer whenever it developed electronics faults.
My unreserved appreciation goes to Connor Deering for his help and readiness to assist each time
I came calling throughout this study. I also appreciate the assistance of Dr. Fadi Alkhateeb and the
entire members of Dr. Marriott’s Research group for their constructive criticism each time the need
arose. Kyle Wynnyk was very supportive during various stages of putting the experiment set-up
together. Kai Feng, an honours’ research project student from the Qingdao University of Science
and Technology, China, also contributed and worked on this project for six months towards his
Bachelor’s degree.
iii
I would like to recognize the entire staff of Alberta Sulfur Research Ltd. (ASRL) for the varying
nature of assistance they rendered and creating an enabling atmosphere for me during this study. I
am particularly grateful to Francis Bernard, Kevin Lesage, and Patricia Allegri for unique help and
support they offered me throughout my studies.
I am grateful for financial support from Dr. Marriott`s NSERC - ASRL Industrial Research Chair
in Applied Sulfur Chemistry University of Calgary, Department of Chemistry Graduate
Student Award (2015, 2016 and 2017), Faculty of Graduate Studies and the University of Calgary.
To my amazing and darling wife, Oluwakemi Sofekun, I say a big thank you for your love and
understanding through it all. I also say a big thank you to my mum and siblings: Sade, Kole,
Gbenga and IBK for all their support.
iv
To the loving memory of
Uncle Nat Sofekun
v
Table of Contents
Abstract ............................................................................................................................... ii
Acknowledgements ............................................................................................................ iii
Table of Contents ............................................................................................................... vi
List of Tables ................................................................................................................... viii
List of Figures and Illustrations ......................................................................................... ix
List of Symbols, Abbreviations and Nomenclature ........................................................... xi
CHAPTER ONE: INTRODUCTION ..................................................................................1

1.1 Overview of the Thesis ..............................................................................................1
1.2 Physical Properties of Elemental Sulfur ....................................................................2
1.3 Viscosity of Sulfur .....................................................................................................3
1.4 Elemental Sulfur Production ......................................................................................6
1.4.1 Native Sulfur .....................................................................................................6
1.4.2 Frasch Sulfur .....................................................................................................7
1.4.3 Sulfur Recovery .................................................................................................7
1.5 Handling, Transportation and Storage of Elemental Sulfur ......................................8
1.5.1 Safety Concerns in Transporting Liquid Elemental Sulfur ...............................9
1.6 Motivation ................................................................................................................11
1.7 Review of Rheometry ..............................................................................................14
1.7.1 Definitions .......................................................................................................14
1.7.2 Simple Shear Model ........................................................................................15
1.7.3 Flow Behaviours ..............................................................................................17
1.7.3.1 Newtonian Fluids ...................................................................................17
1.7.3.2 Non-Newtonian Fluids ...........................................................................18
1.7.3.3 Shear Thinning (Pseudo-plastic) Fluids .................................................18
1.7.3.4 Shear thickening (Dilatant) Fluids .........................................................19
1.7.3.5 Bingham (Plastic) Fluids .......................................................................19
1.7.3.6 Thixotropic Fluids..................................................................................19
1.7.3.7 Rheopectic Fluids ..................................................................................20
1.7.3.8 Viscoelastic Fluids .................................................................................20
1.7.4 Shear Rheometers ............................................................................................20
1.7.4.1 Capillary Rheometers ............................................................................21
1.7.4.2 Falling Body Rheometers ......................................................................22
1.7.4.3 Drag Flow Rheometers ..........................................................................23
1.8 Choice of Rheometer Geometry ..............................................................................27
1.9 Rheology Models .....................................................................................................29
CHAPTER TWO: REVIEW OF LITERATURE DATA, EXPERIMENTAL TECHNIQUE

AND MODELS ........................................................................................................31
2.1 Sulfur’s Viscosity Measurements ............................................................................31
2.1.1 Measurements Data for the entire Liquid Temperature Range .......................31
2.1.2 Measurements Data below 160 °C ..................................................................35
2.2 Viscosity Models for Sulfur .....................................................................................37
2.2.1 Equilibrium Polymerisation Theory ................................................................37
2.2.2 Modified Reptation Theory .............................................................................41
vi
2.3 Effects of Impurities on Sulfur’s Viscosity .............................................................44
2.3.1 Effects of H2S on Sulfur’s Viscosity ...............................................................44
CHAPTER THREE: EXPERIMENTAL METHOD AND PROCEDURE ......................47

3.1 LabVIEW Code for Pressure Data Acquisition .......................................................47
3.2 Pressure Transducer Calibration ..............................................................................49
3.2.1 Deadweight Tester ...........................................................................................49
3.2.2 Experimental Methods.....................................................................................50
3.2.3 Results and Discussion ....................................................................................52
3.3 Commissioning the MCR 302 Rheometer ...............................................................55
3.3.1 Operation and Hardware of MCR 302 Rheometer ..........................................56
3.3.2 Controls and Data Logging .............................................................................58
3.3.3 Comparing Measured Results with Standards .................................................59
3.3.3.1 Experimental Method ............................................................................60
3.3.3.2 Results and Discussions .........................................................................61
3.4 Experimental Set-up ................................................................................................63
3.5 Materials ..................................................................................................................64
3.6 Experimental Procedure ...........................................................................................65
3.7 FT-IR Analysis ........................................................................................................67
CHAPTER FOUR: RESULTS AND DISUSSION...........................................................68

4.1 Measured Newtonian Viscosity Data of Liquid Elemental Sulfur ..........................68
4.1.1 The FT-IR Spectroscopy Results.....................................................................76
4.1.2 Average Measured Newtonian Viscosity Data of Liquid Elemental Sulfur ...81
4.1.2.1 Re-Optimising the Modified Reptation Model ......................................84
4.2 Non-Newtonian Viscosity Measurements Results of Liquid Elemental Sulfur ......85
4.2.1 Rheology of Sulfur in Mid-Shear Rate Range ................................................85
4.2.1.1 Rheology of Liquid Elemental Sulfur during Pipe Flow .......................85
4.2.1.2 Rheology of Liquid Elemental Sulfur during Pump Operations ...........87
CHAPTER FIVE: CONCLUSIONS AND FUTURE DIRECTIONS ..............................91
...................................................................................................................95
...................................................................................................................98
REFERENCES ................................................................................................................104
vii
List of Tables
Table 1. Advantages and disadvantages of different rheometers. ................................................ 28
Table 2. Relevant parameters for deadweight calibration ............................................................ 53
Table 3. The corrected theoretical pressures, the measured pressures, and uncertainties of the
measured pressures estimated using the standard deviation and a 95.5 % confidence
intervals. ................................................................................................................................ 53
Table 4. Certified values for NIST rheology standard-SRM 2490. ............................................. 60
Table 5. Result of the total analysis of Keyera air prilled sulfur. ................................................ 64
Table 6. Average measured Newtonian viscosity data of liquid elemental sulfur at different
temperatures for the 1st charge of sulfur into the apparatus. ................................................ 68
temperatures for the 2nd charge of sulfur into the apparatus. ................................................ 69
temperatures for the 3rd charge of sulfur into the apparatus. ................................................ 71
temperatures for the 4th charge of sulfur into the apparatus.................................................. 73
Table 10. Total H2S (H2S+H2Sx) content from FTIR analysis of each charge. ........................... 80
temperatures, averaged for the 9th - 14th charges of sulfur into the apparatus. ..................... 82
temperatures for the 7th charge of sulfur into the apparatus................................................ 101
temperatures for the 8th charge of sulfur into the apparatus................................................ 102
viii
List of Figures and Illustrations
Figure 1. (a) S8 - Crown-shape molecules of sulfur consisting eight atoms, (b) • S8 • - diradicals
molecules of sulfur produced as a result of rupturing of the S8 molecules, (c) • Sn • - long
chain diradicals formed from combination of diradicals. ....................................................... 4
Figure 2. Viscosity of liquid sulfur as a function of temperature over the λ-transition region,
empirical model by Shaui and Meisen (1995) of the measurements data of Bacon &
Fanelli (1943). ......................................................................................................................... 5
Figure 3. (a) Deformation of an ideal solid in a simple shear model, (b) Laminar flow of an
ideal liquid in a simple shear model...................................................................................... 15
Figure 4. Common fluids flow behaviours. ................................................................................. 17
Figure 5. (a) Shear stress vs. shear rate profile of common fluid flow behaviours, (b) Viscosity
vs. shear rate curve of common fluid flow behaviours. ........................................................ 18
Figure 6. (a) Concentric cylinder geometry of a rheometer showing its dimensions and the
inner bob; (b) cross-section of a concentric cylinder geometry of a rheometer. .................. 26
Figure 7. Experimental literature data of sulfur’s viscosity. ........................................................ 35
Figure 8. Front panel of the VI to log pressure from the transducer............................................ 48
Figure 9. (a) DWT without weight on the weight stack. (b) DWT with transducer and weight
on stack at equilibrium with pressurized fluid. Notations: ................................................... 52
Figure 10. Deadweight calibration plot of the calculated applied reference pressure (pcorr)
against their corresponding transducer measurements (pmeas). ............................................. 55
Figure 11. Schematic of the experimental set-up for measurements of the rheometric properties
of liquid elemental sulfur. ..................................................................................................... 57
Figure 12. Picture of the experimental set-up for measurements of the rheometric properties
of liquid elemental sulfur. ..................................................................................................... 58
Figure 13. User interface of Rheoplus 4.14 software used for controls and logging rheological
data from MCR 302 to the computer system showing some input variables. ...................... 59
Figure 14. Comparison of viscosity measurements made using the MCR 302 rheometer and
certified values. ..................................................................................................................... 62
Figure 15. Measurements of NIST’s SRM 2490: ........................................................................ 63
Figure 16. Average measured Newtonian viscosity data of molten sulfur as a function of
temperature for the first four charges. ................................................................................... 76
ix
Figure 17. FT-IR spectra of the 1st, 2nd, 3rd and 4th charges showing the total H2S (H2S + H2Sx)
content and peaks. ................................................................................................................. 77
Figure 18. Measurements data of average Newtonian viscosity of molten sulfur as a function
of temperature for different charges...................................................................................... 79
Figure 19. Experimental Newtonian viscosity data and models of molten sulfur as a function
of T ........................................................................................................................................ 84
Figure 20. Measurement data of the η of molten sulfur as a function of γ̇ up to 100 s-1 at
constant T. ............................................................................................................................. 87
constant T. ............................................................................................................................. 88
Figure 22. Newtonian viscosity data and critical rate of shear thickening of molten sulfur as
function of T .......................................................................................................................... 89
Figure 23. Block diagram of the the VI used to log on pressure measurements from the Keller
pressure transducer to a computer system............................................................................. 95
x
List of Symbols, Abbreviations and Nomenclature
Symbol Definition
Acs Specific area

Effective area of the piston at ambient pressure and reference
a0
temperature
Ap Temperature-corrected true effective area
as Entropy (S) term due to end effects
A.U. Arbitrary unit
bd Pressure distortion coefficient
bs Entropy (S) term due to chain lengths
c Coverage factor
CEN European Committee for Standardization
COM Data communication line
CR Shear rate controlled
CS Shear stress controlled
DWT Dead weight tester
d1 Width of suspension at the top of a lever system
d2 Width of suspension at the bottom of a lever system
dh Thickness of a body under shear stress

Distance travelled by the imaginary infinitesimal thin upper layer of a
dl
body under shear stress
Ea Activation energy
F Force
FT-IR Fourier Transform Infra-red
g Acceleration due to gravity
gl Local acceleration due to gravity
G Shear modulus
xi
Ge Plateau modulus of an entangled system
HC Hydrocarbon
HP High pressure
Depth of immersion of an inner cylinder of a concentric cylinder
h
rheometer in a sample
ISO International Organization for Standardisation
k Rate constant
kT Temperature dependent constant
K Apparatus’s constant
Kc Consistency factor
Kx Equilibrium constant for sulfur radical formation reaction
Kp Equilibrium constant for sulfur radical propagation reaction
LabVIEW Laboratory Virtual Instrument Engineering Workbench
l Length of suspension in a pulley system
L Depth of inner cylinder in a concentric cylinder geometry rheometer
Lc Length of capillary viscometer
M Torque
Mav Average molecular weight
MCR Modular Compact Rheometer
mp Mass of a suspended body in a pulley system
Mx Ratio of halogen atoms to sulfur atoms
m Flow index or power law viscosity index
N Polymerisation index
NIST National Institute of Science and Technology
p Pressure
pcorr Corrected deadweight pressure
xii
pmeas Measured pressure from the transducer being calibrated
PRT Platinum resistant thermometer
PID Proportional, integral and differential control action
PV Process variable
Q Volumetric flow rate
𝑟̅ 2 Root-mean-square end-to-end average chain length of a polymer
R Ideal gas constant

Average radius of the inner and outer cylinders of a concentric cylinder
R’
rheometer
Ri Radius of the inner cylinder of a concentric cylinder rheometer
Ro Radius of the outer cylinder of a concentric cylinder rheometer
S Entropy
SP Desired control point
SSE Sum of squares due to error
Sμ Polymeric sulfur
Sπ CS2 soluble sulfur

•
Sx• Long chain diradical sulfur molecules
T Temperature
Reference temperature at which the properties of the DWT were initially
Tref
measured.
LVE Linear Visco-elastic range
v Velocity
x Chain length of a polymeric chain
yx Mole fraction of sulfur molecules with length x
y‫٭‬ Mole fraction of S8 rings in equilibrium
Zw Weight of average chain length
α Cone angle of inner cylinder in a concentric cylinder rheometer
xiii
αc Coefficients of thermal expansion for the cylinder in a DWT
αp Coefficients of thermal expansion for the piston in a DWT
α-S8 Orthorhombic sulfur
β-S8 Monoclinic sulfur

Height difference between the transducer and the bottom of the piston
Δh
assembly in a DWT
∆H Enthalpy change
∆H4 Enthalpy of propagation reaction
∆S Entropy change
τ Shear stress
τrep Time taken for a polymer chain to exit a tube in a snake-like diffusion
Time taken for a chain of polymerisation index N, to break into two
τbreak
pieces
τf Friction constant
τ0 Yield stress
τw Shear stress at capillary wall
θ Deflection angle
γ Shear strain
γ-S8 Metastable sulfur
γ̇ Shear rate
γ̇ cr Critical rate of shear thickening
γ̇ w Shear rate at the capillary wall

 u Extensional viscosity
η Viscosity
ɳmax Maximum viscosity
ɳM Viscosity of a mixture
ρ Density
xiv
η∞ Viscosity at upper shear limit
η0 Viscosity at lower shear limit
ηp Plastic viscosity
ρair Density of air
ρmass Density of a mass
ρfluid Density of the hydraulic fluid
ρB Density of a falling body in a rheometer
ρl Density of a liquid in a rheometer
ρs Density of sulfur
δ Standard uncertainty
ϕ Polymer weight fraction
ɸv Polymer volume fraction
ω Angular velocity
xv
Chapter One: INTRODUCTION
1.1 Overview of the Thesis
Liquid elemental sulfur (S) undergoes polymerisation at the temperature of its λ-transition
(T ˂ 160 °C). As a result, its viscosity behaves anomalously when compared to typical fluid
behaviour. This means that industrially produced molten sulfur must be pumped within a narrow
temperature (T) range below the onset of its λ-transition at T ≈ 160 °C and above its natural melting
point (T ≈ 120°C).1 Some impurities, such as hydrogen sulfide (H2S), have been observed to
modify the viscosity of sulfur. In this thesis, the viscosity of pure elemental sulfur over its entire
λ-transition region initially studied by R. F Bacon & R. Fanelli in 1943 will be re-examined.2 In
addition, the viscosity vs. shear rate, i.e. the rheology of sulfur, will be reported for the first time.
This data is pertinent to optimal functioning of sulfur pumps and possible injection of liquid sulfur
into depleted underground reservoirs for long term storage. A reasonable future extension of this
work will be to further study the rheology of impure elemental sulfur. In order for these and future
studies, a sensitive high-pressure rotational rheometer (Anton Paar MCR 302) has been modified
and commissioned for this investigation.
In chapter one, the properties of elemental sulfur, the anomalous viscosity behaviour of sulfur
around the λ-transition region and some common processes involved in the production of elemental
sulfur will be discussed. Different rheological techniques and the reasons why a concentric
cylinder rotational rheometric technique was chosen for this investigation are explained. In chapter
two, the available literature on the viscosity of elemental sulfur and the modifying effects of H2S
on the viscosity of sulfur are reviewed. In chapter three, pressure (p) data logging using the
1
National Instruments LabVIEW software, the MCR 302 rheometer with concentric cylinder
measuring geometry, and the experimental set-up and methods for this study are discussed. Finally,
in chapter four, the viscosity and rheological data of sulfur from this study are presented. The
conclusions and the contributions of this research to the existing literature as well as possible future
research directions on this study are provided in chapter five.
1.2 Physical Properties of Elemental Sulfur
Elemental sulfur has the most number of solid allotropes of all elements that have been isolated.3
Over thirty well-defined solid allotropes have been characterized using X-Ray diffraction.4 The
discrepancies in literature regarding the names of sulfur’s many allotropes were partly due to the
numerous crystals that were initially yet to be isolated and identified and the difficulty of purifying
elemental sulfur until Bacon & Fanelli’s sulfur purification method.5,6 Low atomic sulfur
molecules of S2 to S5 are present in gaseous and liquid phases of elemental sulfur but these
molecules have no known crystalline forms. S6 to S15, S18 and S20 homocyclic rings have all been
prepared and isolated in solid form. Larger unstable sulfur rings of S > 25 have also been observed
using various spectroscopic techniques.5
At room temperature, crown-shaped eight-membered rings are the dominant sulfur species with
orthorhombic α-S8 crystals as the stable crystal. At 95.24 °C, the α-S8 crystals transform to
monoclinic β-S8 crystals which are thermodynamically stable relative to the liquid up to
T = 115.18 °C and kinetically stable up to T = 120 °C.1 The monoclinic γ-S8 crystals are metastable
form which have been observed at almost all temperatures below the melt. Just above the
2
thermodynamic melting point, T = 115.18 °C, liquid sulfur contains predominantly S8 ring shape
molecules. As temperature rises these rings begin to rupture to form diradical S8 chains. Note that
sulfur melts naturally at a kinetic melting point near 120 °C, due to the slow disproportionation of
the sulfur rings. At T = 160 °C, the liquid diradical species start to concatenate to form long chain
radicals • S n•, i.e., polymeric sulfur, Sμ. Polymeric sulfur can be isolated from liquid sulfur
equilibrated at temperatures between 120 to 250 °C by rapidly quenching to room temperature and
immediately extracting the non-polymeric sulfur with carbon disulfide (CS2).5
The formation of polymeric sulfur in liquid sulfur at T = 160 °C causes abrupt changes to the
physical properties of liquid sulfur. Properties such as heat capacity, dielectric constant and density
undergo second-order transitions, known as the λ-transition. One of the most pronounced effects
of this phenomenon is observed in the behaviour of the viscosity of liquid sulfur; discussed in more
detail in section 1.3. The colour of elemental sulfur gradually changes from light yellow at melting,
through dark yellow at ca. 160 °C (λ-transition), to a dark brown to red above 250 °C. Sulfur has
low thermal conductivity and vapour pressure throughout its solid and liquid phases. The boiling
point of sulfur is Tvap = 444 °C at atmospheric pressure where the species in the sulfur vapour are
primarily S2, S6 and S8, with S2 being the predominant molecular species.
1.3 Viscosity of Sulfur
Viscosity, ɳ, is a measure of a fluid’s internal friction. At melting (T = 115.18 °C), liquid sulfur is
predominantly ring-shaped S8 molecules and has a viscosity of about 10 - 12 cP. As the
temperature increases, like many other liquids the higher energies of sulfur molecules make them
3
easily glide past one another and therefore, its viscosity decreases with increasing temperature to
a minimum of 7 - 9 cP at 157 °C. Above sulfur’s melting point, sulfur rings begin to rupture to
form diradical chains.7 At 160 °C, increased rupturing of sulfur rings leads to the production of
more of the highly reactive radical species which in turn combine to form chains with variable
lengths (Figure 1).
•
S8 S8• •
Sn•
T > 160 °C
T ≥ 115 °C
T > 187 °C
(a) (b) (c)
Figure 1. (a) S8 - Crown-shape molecules of sulfur consisting eight atoms, (b) • S8 • - diradicals
molecules of sulfur produced as a result of rupturing of the S8 molecules, (c) • Sn • - long chain
diradicals formed from combination of diradicals.
This polymerisation of sulfur into long chains brings about a sharp increase in the viscosity of
sulfur above 160 °C due to the entanglements of the chains. The effect becomes more pronounced
as temperature increases further, reaching a maximum viscosity of ≈ 93,000 cP at 187 °C, which
is four orders of magnitude larger than the viscosity at melting.2 As the temperature of elemental
sulfur rises above 187 °C, the diradical chains begin to break due to increased thermal
decomposition, leading to reduced chain lengths and viscosity up until boiling point of sulfur at
4
444 °C (Figure 2). As a result of this anomaly, liquid sulfur is usually flowed or pumped within a
safe temperature range of 135 - 155 °C.8
100000
S8 ⇌ •Sx•
80000
60000
ɳ / cP
40000
20000
0
120 140 160 180 200 220 240 260 280 300
T / °C
Figure 2. Viscosity of liquid sulfur as a function of temperature over the λ-transition region,
empirical model by Shaui and Meisen (1995) of the measurements data of Bacon & Fanelli
(1943).2, 9
Certain impurities, such as: hydrogen sulfide (H2S), sulfur dioxide (SO2), halogens, hydrocarbons
and amines, have been found to modify the viscosity of sulfur by limiting the effective chain
lengths.10,11 Many of these impurities reduce the viscosity of liquid sulfur by reactions that shorten
5
the polymer chains of sulfur, where the sulfur diradical chains abstract hydrogen or halogen atoms
in terminal positions thereby shortening the average length of the sulfur chains.12 For example, in
reaction 1-1, H2S reacts with a diradical chain to form polysulfane (H2Sx);
2H2S + ˙S˙x ⇌ HSxH. (1-1)
As a result of the shorter chain lengths, the viscosity of molten sulfur that contains dissolved H2S
is much lower than that of pure liquid sulfur. This also explains why the viscosity of sulfur
contaminated with certain impurities such as hydrocarbons (RH) is lower than the viscosity of pure
liquid sulfur around the λ-transition region, as hydrocarbons can react with sulfur at elevated
temperature to produce H2S and polysulfide (RSxR), as shown in reaction 1-2;
2 RH + Sx → RSxR + H2S, (1-2)
which in turn can decompose to produce CarSul - an insoluble compound of carbon and sulfur.13
1.4 Elemental Sulfur Production
Elemental sulfur can be mined from sulfur deposits close to the ground surface (native sulfur) or
deep-lying sulfur formations by the Frasch process. Currently, nearly all Frasch sulfur has been
replaced by sulfur recovered from the Claus process, which is the partial oxidation of H2S obtained
as by-products from gas purification or hydrodesulphurization of hydrocarbon mixtures in oil
refinery processes.
1.4.1 Native Sulfur
Native elemental sulfur mines can be found trapped in gypsum-anhydrite (CaSO4 ∙ 2H2O - CaSO4)
deposits.14 The mining of this elemental sulfur can be done by open excavation or underground
6
mining depending on the nature of the deposit. Aside from producing elemental sulfur in a pure
form, iron sulfide (FeS) is also mined and subsequently distilled to produce elemental sulfur.
1.4.2 Frasch Sulfur
Frasch sulfur is obtained by pumping superheated water into the matrix of sulfur bearing rocks to
melt the entrapped sulfur. The molten sulfur is then forced to the surface by pumping compressed
air into the deposits. Injection of superheated water is continuous to keep the sulfur in the molten
state. A major challenge in this process is the energy requirement to produce superheated water.
Depending on the complexity of the formation, it can take between 3 - 38 m3 (4 - 50 t) of
superheated water at T = 160 - 165 °C to produce one ton of sulfur, which averages 15.8 GJ energy
demand per ton of sulfur produced.15,16 As a result of the energy intensive nature of the Frasch
process and the abundance of sulfur containing hydrocarbons, operations have since closed and
given way to sulfur recovery from oil and gas production. The increased exploration of sour oil
and gas reservoirs, which were hitherto problematic because of their sulfur content, had
inadvertently led to the replacement of conventional sulfur production through mining by the sulfur
recovered as a by-product of sour crude oil and gas production.
1.4.3 Sulfur Recovery
The original Claus process was a one-step reaction process in which H2S is oxidized with air or
oxygen over a catalyst to form elemental sulfur and water at temperature between 200 - 300 °C.17
2H2S + O2 → S2 + 2H2O. (1-3)
Though highly exothermic, much of the energy given off during this reaction process could not be
harnessed and the sulfur yield was thermodynamically limited to 80 - 90 %.17,18 In order to
7
overcome these short-comings, the modified Claus process was developed and introduced by I.G
Farbenindustrie (ca. 1937).16,17,18 The modified Claus process consists of two reaction steps: the
first step being the highly exothermic partial combustion of H2S to SO2 at about 950 - 1350 °C in
a reaction furnace, from which much of the heat of reaction can be recovered in the form of high
pressure steam from a waste steam exchanger (reaction 1-4). Followed by the catalytic
comproportionation of SO2 and unburned H2S to form elemental sulfur and water (reaction 1-5) at
T = 170 - 370 °C in a catalytic converter:
H2S + 3/2O2 ⇌ SO2 + H2O, (1-4)
2H2S + SO2 ⇌ 3/x Sx + 2 H2O, (1-5)
for an overall reaction:

3H2S + 3/2O2 ⇌ 3/x Sx + 3 H2O. (1-6)
Following the initial reaction furnace, up to four catalytic converters are arranged in series to
ensure yields of sulfur of greater than 99.9 %.17 The elemental sulfur is continually removed from
the condensers after the reaction furnace and each catalytic converter to shift the equilibrium
towards increased elemental sulfur production.
1.5 Handling, Transportation and Storage of Elemental Sulfur
With the production of liquid elemental sulfur, the liquid (rundown) is flowed into holding tanks
or pits, before being transported as liquid, formed into a solid block or other solid products forms
for sales. Blocked sulfur is susceptible to contamination by moisture, soil, rust, or other impurities
during outdoor storage and handling.19 Blocked sulfur can be crushed or re-melted for
transportation as the need arises.

8
When solid sulfur cools, it transitions from β-S8 crystals transforms to α-S8 which are 5% more
dense. This structural destabilization makes sulfur friable.14 The dusts produced when sulfur
crumbles can constitute a safety and environmental hazard as it can easily reach its low explosion
level of 3.5 % volume in air. For example in late 1971, the Vancouver port authority, which is the
port where majority of Canada’s exported sulfur, banned the shipment of crushed sulfur into its
terminal after a major explosion involving sulfur dusts.20
Currently forming elemental sulfur into shapes, sizes and thickness that are more resistant to
attrition are practiced in the sulfur industry. Sulfur prilling, pastillation or pelletizing is a forming
technique used to produce a more satisfactory product for handling and transportation.
About 70 million tons of elemental sulfur (all forms) was consumed globally in 2016.21 Most of
this sulfur was used in the production of sulfuric acid, for which purpose it will be preferred in the
liquid state.22,23 Sulfur is produced in sulfur production facilities in the liquid state and so,
transportation to consumers without solidification can be done, although normally the distance is
too large to viably hold as a liquid. The transportation of liquid elemental sulfur is done using
heated tankers, rail cars, barges, and vessels as well as heated pipelines for short distances.
However, certain challenges are associated with the handling of molten sulfur that makes its large
scale and long distance transportation difficult.
1.5.1 Safety Concerns in Transporting Liquid Elemental Sulfur
There are hazards associated with the equilibrium decomposition of H2Sx in liquid sulfur to H2S
(reaction 1-1). Unlike in most other liquids the solubility of H2S gas in liquid sulfur increases with
9
increasing temperature.12, 24 This is made possible by the reactions of sulfur diradicals present in
liquid sulfur around the λ-transition. As the temperature rises, more sulfur diradicals react with
H2S to form H2Sx. As a result, more H2S gas molecules are absorbed into liquid sulfur.24
When temperature is reduced in molten sulfur facilities (such as holding tanks, rail cars, or
tankers), the reverse reaction (reaction 1-1) is favoured and so, the H2S gas will be slowly released
and saturate the confined headspace or be released upon opening to the surroundings. The 600 ppm
lethal dose (LD50) of H2S can easily be reached should the gas leak out of confined facilities. In
cases where the H2S gas cannot escape directly into the surrounding, there is also a risk of H2S gas
exceeding its lower explosion limit of 3.5 mol % (in air).
Liquid sulfur is effectively transported in pipelines within a narrow temperature range within
which liquid sulfur possesses an optimum viscosity for flow. Most liquid sulfur handling
equipment have a heating mechanism for temperature control and are usually designed to operate
between 135 - 145 °C. In the event that the temperature of sulfur rises above T = 160 °C, the
viscosity of sulfur will increase rendering it impossible to flow. This can lead to pump failure due
to operation at higher load, temperature and shear operation. In converse, if the T of liquid sulfur
inadvertently drops below the melting temperature solid sulfur can cause failure. When this
happens in a pipeline, elemental sulfur will gravitate towards the low bends of the pipeline leaving
behind empty sections. During re-melt operations heat needs to be applied from one end of the
pipeline, otherwise sulfur could melt between adjacent solid sulfur within the pipeline. This would
lead to the expansion of the melt, thereby generating extreme pressures that can rupture the
pipeline.25
10
A number of authors have suggested that elemental sulfur transport using pipeline will reduce the
environmental, safety and operational concerns associated with handling sulfur using other
methods. Estimations made by H. W. Habgood of the Research Council of Alberta suggested liquid
sulfur transportation through pipeline is the most efficient way to transport sulfur compared to
other alternatives based on the increasing production of large tonnage of sulfur and the potential
need to transport elemental sulfur in quantities possibly in excess of 0.5 million tons per year over
distances of 965 km.25,26 Pipelines are still scantily used in transporting liquid sulfur for moderate
to long distances in the industry. Some of the few sulfur pipelines in operation are: the 7 km
pipeline in the north of Germany; the 14.5 km undersea pipeline between Grande Isle, Gulf of
Mexico and USA main land; the 24 km pipeline from the Berri natural gas plant to the Jubail sulfur
terminal in Saudi Arabia; the 33 km pipeline in Carter Creek, Wyoming, U.S.A; and the Shell’s
underground sulfur pipeline spanning a distance of 41 km between Caroline and Shantz, Alberta,
Canada16,25,27,28 Some of these pipelines are electrically heat-traced, while the Shell’s sulfur
pipeline is hot-water heat traced.
1.6 Motivation
The global demand for elemental sulfur has continually been on the rise with the increasing need
to feed the world’s increasing population.15 Sulfuric acid produced from elemental sulfur is used
for the digestion of phosphate in the production of phosphate fertilizers. Using elemental sulfur is
the most viable route to the production of soluble phosphates.15 The increased global energy
demand has led to increased production of sour oil and gas which in turn has increased sulfur
recovery. Environmental and safety concerns in addition to strict government legislations have
11
also contributed to the unprecedented amount of elemental sulfur inventory. For example in North
America, the maximum allowable dissolved H2S in liquid sulfur is 10 ppm and the average Claus
recovered sulfur contains 200 - 300 ppm dissolved H2S.18 Hence, the need to further degas the
produce sulfur of dissolved H2S which may be recycled as feed to a sulfur recovery unit or directly
converted to elemental sulfur.
In order to accommodate the potential future over production of sulfur, suggestions have been
made about the long-term storage of sulfur.23 Acid gas injection is already practiced for the
disposal of sulfur in the form of H2S; however, there are strict regulations around the practice and
at times suitable injection reservoirs may not be available for this purpose. Conversion of H2S to
sulfuric acid is another possible sulfur storage method but the toxicity, corrosive nature and its low
sulfur density makes it more expensive to transport and store than elemental sulfur.
Much of the transportation and handling of liquid sulfur requires sulfur pumps which may be
challenging to operate due to the anomalous behaviour of sulfur’s viscosity around its λ-transition
region. High shear deformation will be experienced in pumps as liquid flow within the pumps. At
high temperature and high shear, sulfur pumps can fail. At present, the viscosity versus shear rate
data, i.e., rheometric data of liquid sulfur, is not available in open literature.29 The availability of
this data will help to optimize the functioning of liquid sulfur pumps and improve the handling
process of molten sulfur in general. One of the goals of this thesis is to better understand sulfur’s
flow behaviour.
12
Despite being a major safety concern, the presence of dissolved H2S in liquid sulfur is an advantage
to the flow properties of liquid sulfur. The reaction of H2S with sulfur diradicals reduces the chain
lengths of the diradicals causing a reduced viscosity of liquid sulfur. The modifying effects of
some impurities such as H2S and halogens on the viscosity of liquid sulfur have been reported in
literature.10,11 Bacon & Fanelli (1946) have measured the modifying effects of H2S on viscosity of
liquid sulfur after treatment with H2S gas but these measurements were not correlated with the
actual concentration of dissolved H2S in liquid sulfur.2 Providing a correlation between dissolved
H2S concentration and sulfur viscosity will be a future goal for this type of research.
In comparison to other forms, liquid elemental sulfur is benign, non-toxic and safer to handle
because of its low vapour pressure throughout its liquid state.30,31 As a result, the injection of liquid
sulfur into depleted reservoir has been suggested as a safe alternative for long term storage of
elemental sulfur. In order to achieve this injection there is again, the need to define the flow
properties of liquid sulfur, i.e., the rheometric properties. In addition to the high shear deformation
experienced within pumps, high shear will also be experienced near the well-bore region of
reservoirs. It is therefore not sufficient to know the viscosity of liquid sulfur without relating it to
shear rate. The polymerisation of sulfur around its λ-transition suggests that liquid sulfur may
possess non-Newtonian properties like most polymers, and so a thorough understanding, the
mitigation of the anomalous behaviour of liquid sulfur’s flow property may be achieved by
investigating sulfur’s viscosity with respect to shear, i.e., its rheological properties.
13
1.7 Review of Rheometry
1.7.1 Definitions
Rheology is the study of flow and deformation of materials under the influence of stress. An ideal
solid, also known as a Hookean solid, obeys Hooke’s law and deforms reversibly in response to
an applied stress.32 The energy expended for its deformation is fully recovered when stress is
removed. Conversely, an ideal liquid obeys Newton’s law and deforms irreversibly. The energy
expended for the deformation of an ideal liquid is dissipated within the liquid in the form of heat
and is not recovered when the stress is removed.33 In other words, the response of an ideal solid to
shear stress is a reversible elastic deformation while that of an ideal liquid is an irreversible viscous
flow. Most materials of practical importance are neither ideal solid nor ideal liquid and are
therefore commonly referred to as viscoelastic materials.33 Their rheological properties fall in
between that of ideal solids and ideal liquids.
At early stages of its development, rheometry was defined as standard techniques for measuring
shear viscosity. However, as interest in non-Newtonian fluids (fluids whose viscosity change with
respect to shear rate) grew, rheometry expanded to include techniques such as measurements of
normal stress and elongation viscosity.34 The modern definition of rheometry includes techniques
in which viscosity and viscoelastic properties of a material are studied as a function of temperature,
time, shear rate, or stress while the material is subjected to controlled temperature, shear rate, or
stress program.35 Whereas, in viscometry, viscosity is measured as a function of temperature, time,
shear rate, or stress while the material is subjected to a constant temperature, shear rate, or stress
program. Viscometry is therefore a branch of rheometry.
14
1.7.2 Simple Shear Model
In order to establish the basic parameters necessary to define the flow properties of materials, a
simple shear two parallel-plate deformation model is used to mimic a simple laminar flow regime
in both solids and liquids.
Shear Strain,
τ = (F/A) Shear Stress,
dl
Uniform Velocity, v τ = (F/A)
dh
h 0
Area (A) dv
(a) (b)
Figure 3. (a) Deformation of an ideal solid in a simple shear model, (b) Laminar flow of an ideal
liquid in a simple shear model.
In Figure 3a, an ideal solid is subjected to a shear stress, τ, (defined as the force, F, per unit area, A)
tangentially applied in the direction of shear (deformation). When F is applied to the solid with
thickness, h, the top of the solid moves a certain distance dl, then stops in the new position for as
long as the force is applied. The response of the solid material is defined by the shear strain,
γ (dl/h). The shear modulus G, (equation 1-7) is a measure of stiffness linked to the chemical
make-up and physical nature of the solid under investigation.32 It defines the resistance of the
solid to deformation:
dl
  G  G  (1-7)
h
15
In a liquid, the shear stress, τ, applied to the liquid acts tangentially to the surface of the liquid as
if it were stacks-of-cards sandwiched between a moving upper and fixed lower parallel plates
(Figure 3b). As a result, a sliding of one infinitesimal layer, dh over another layer is produced in
the liquid.36 When a shear force is applied to the surface of the liquid, the upper plate moves at a
constant velocity, v, for as long as the force is applied. When the shear stress is removed the plate
stops moving and retains its new position (unless the inertia due to its mass continues its motion
for a short time). The velocity decreases linearly across the thickness (h), between the moving
upper plate and the fixed lower plate. Similar to the solid, a shear strain rate or shear rate,
γ̇ (dv/dh), is produced in the liquid as a result of the shear stress applied. In an ideal liquid, the
shear rate is proportional to the shear stress and the constant of proportionality is the viscosity,
η (equation 1-8). This is a measure of the resistance a liquid possesses against any irreversible
positional change of its volume elements.
dv
       (1-8)
dh
Flows in liquids can generally be divided into extensional and shear flows. For extensional flow,
adjacent elements flow away or towards each other, whereas in shear flow, liquid elements flow
past each other.37 There have been little extensional rheological measurements available in
literature due to the difficulty involved in their measurements. However, the Trouton rule
(equation 1-9), had been widely used to predict uniaxial extensional viscosity of a fluid, ηu, from
its viscosity, η values.
u  3 (1-9)
Experimental data later showed that extensional viscosity could be a lot larger than predicted by
Trouton’s rule at higher shear rate.38 Henceforth, no attention will be given to extensional
16
Rheometry in this thesis because in the liquid sulfur processing facilities, such as sulfur pumps
and drainage pipes, shear flow is the dominant flow and this thesis seeks to establish flow
parameters that would address problems in such facilities.
1.7.3 Flow Behaviours
A material’s response to shear stresses can generally be characterised as Newtonian or non-
Newtonian. Non-Newtonian material behaviour is further divided into various groups as shown in
Figure 4:
Figure 4. Common fluids flow behaviours.
1.7.3.1 Newtonian Fluids
Fluids that deform uniformly with respect to shear rate are defined by Newton’s law of viscosity,
equation (1-8). The viscosity of these fluids is independent of shear rate and are referred to as
Newtonian fluids i.e., an ideal fluid. Liquid water is an example of a fluid that exhibits this flow
behaviour.
17
1.7.3.2 Non-Newtonian Fluids
Many fluids that have industrial applications do not shear uniformly and cannot be defined
perfectly by Newton’s law of viscosity (Figure 5). The viscosity of these fluids vary with shear
rate and /or time and are further classified as: shear thinning, shear thickening, Bingham,
thixotropic, rheopectic, and visco-elastic fluids.

Shear stress, τ / Pa
Viscosity, η / cP Newtonian
Bingham
Yield stress, Shear rate, γ˙ / s-1 Shear rate, ˙γ / s-1

τ0 / Pa
(a) (b)
Figure 5. (a) Shear stress vs. shear rate profile of common fluid flow behaviours, (b) Viscosity vs.
shear rate curve of common fluid flow behaviours.
1.7.3.3 Shear Thinning (Pseudo-plastic) Fluids
Shear thinning behaviour is a common flow behaviour in materials. The viscosity of shear thinning
materials decreases with increasing shear rate (Figure 5). At rest, these materials contain randomly
distributed particles/molecules with irregular shapes and sizes. As flow begins, these particles are
forced against one another causing moderate resistance to flow.33 But, as shear rate increases, the
particles become aligned to the direction of flow and as a result, the viscosity reduces until it gets
to a constant value where there is little or no interaction among material particles. For example,
18
squeezing ketchup out of a flexible bottle increases the shear rate and reduces the viscosity of the
fluid making more of the ketchup flow out of the bottle.
1.7.3.4 Shear thickening (Dilatant) Fluids
Some materials undergo an increase in viscosity as the shear rate increases (Figure 5). The
application of shear force to this group of materials causes layers to slide against each in other to
flow. As shear rate increases, irregularities in particle ordering results in increased resistance to
flow and eventually leads to particles jamming together.39 Suspensions of corn starch in water is a
typical example of a shear thickening fluid.
1.7.3.5 Bingham (Plastic) Fluids
Bingham flow behaviour is similar to shear thinning behaviour except that a certain shear stress
value known as yield stress, τ0, must be attained before flow can commence at all for fluids that
exhibit this behaviour, (Figure 5a). At rest the microstructures of these materials contain networks
that greatly resist deformation like a solid. These networks are broken down at the yield stress,
which is unique for the material, before viscosity can start to decrease with increasing shear rate.
Toothpastes and gels show this flow behaviour.
1.7.3.6 Thixotropic Fluids
This is one of the two time-dependent flow behaviours in fluids. Thixotropic materials undergo
shear thinning as a function of shear rate and time. The shear history of the materials influences
their flow behaviour. If the shear rate is varied in a cycle of an increasing shear rate followed by a
decreasing shear rate, the viscosity vs. shear rate curve obtained will be anisotropic, indicative of
19
partial recovery of the molecular structure of the materials. An example of a thixotropic material
is cement paste.
1.7.3.7 Rheopectic Fluids
This is a time-dependent shear thickening behaviour in materials. Rheopectic materials show an
increase in viscosity as a function of shear rate and time. The viscosity vs. shear rate curve is also
anisotropic, though in a counter-clockwise manner, i.e., the downward viscosity vs. shear rate
curve is above the upward curve. Essentially, the structure of rheopectic materials break down at
rest and is built up while being subjected to shearing. For example, 42 % aqueous gypsum paste
at rest solidifies after 20 s if gently rolled out of a container onto a surface.40
1.7.3.8 Viscoelastic Fluids
A viscoelastic materials’ response to shear stress is both elastic and viscous. Discrepancies exist
in literature in designating materials as an ideal solid, ideal liquid or viscoelastic. This is because
the response of a material to shear depends on its structure and the condition it has been subjected
to. A dynamic shear stress experiment is often carried out to establish the strain within which the
response of a material is both elastic and viscous. A material property obtained is known as linear
viscoelastic limit (LVE).41
1.7.4 Shear Rheometers
In order to classify the flow behaviour of a fluid, shear rheometers are often used to measure
rheometric properties. They can be divided into: capillary rheometers, falling body rheometers and
drag-driven flow rheometers.
20
1.7.4.1 Capillary Rheometers
Capillary rheometers are also referred to as pressure driven flow rheometers or Poiseuille
rheometers. It is worthwhile to mention here that for Newtonian fluids, viscosities are normally
obtained in capillary viscometers in terms of kinematic viscosity, ν, (ɳ/ρ). Because the force of
gravity is oftentimes the driving force that pushes the liquid through the capillary, then the density
(ρ) of the liquid becomes an additional parameter and is used to convert measured kinematic
viscosities to dynamic or absolute viscosities. In capillary rheometry, a plunger, an extruder, or
any other source of pressure drives the fluid through the capillary either at a constant flow rate (Q)
or with a predetermined pressure drop (∆p). The flow rate is obtained by timing the movement of
plunger or extruder. In capillary flow rheometers, the Hagen ̶ Poiseuille expression (equation 1-10)
applies, assuming a steady, laminar and isothermal flow.36 where r is the radius of capillary, ∆p is
the pressure drop through the capillary, V is the volume of liquid that flows in time t, and Lc stands
for length of the capillary tube:
r 4 pt
 . (1-10)
8VLc
The shear rate at the capillary wall, γ̇w and shear stress at the capillary wall, τw are obtained from
equations (1-11) and (1-12) respectively, where Q represents the volumetric flow rate;
4Q
w  , and (1-11)
r 3
rp
w  . (1-12)
2L
Equation (1-10) can be reduced to ɳ = Kt, for a particular capillary rheometer. K is the instrument
constant obtained by measuring the viscosities of standard samples using the instrument. The
21
viscosity of any sample under investigation is determined by multiplying K with the efflux time, t.
The pressure losses as a result of the turbulence and elasticity witnessed at the entry and exit of
capillary are referred to as end-effect losses. These are corrected for, depending on the capillary
instrument. In addition, because a velocity gradient exists from the center of the capillary to the
wall, the non-linear velocity gradient is corrected for by multiplying the η in equation (1-10) with
the Rabinowitsch correction factor (3m + 1)/4m to convert the apparent shear rate to a true shear
rate where m is the power law coefficient which is an experimentally determined material
property.36
Capillary Rheometers for Use with Molten Sulfur
Sulfur undergoes polymerisation reaction around T = 160 °C, which makes non-newtonian
behaviour probable, as most polymers have non-Newtonian characteristics.36 The fact that a new
volume element flows through the capillary over some time, makes it impossible to define shear
for an extended time in capillary rheometers. In addition, thermal degradation and equilibration of
polymeric sulfur are time dependent and are at the crux of this thesis and so, capillary rheometers
cannot be used in this study.
1.7.4.2 Falling Body Rheometers
Some examples of falling body rheometers are: falling sphere, falling needle, and sliding ball. For
example the design of falling sphere rheometer is based on the Stoke’s law, which relates the
viscosity of a fluid to the velocity of the sphere falling through it. In equation 1-13, r, is the radius
of the sphere, ρB and ρl are the densities of the falling body and the liquid respectively; g is the
acceleration due to gravity and v is the velocity of the falling body:
22
2 gr 2 (  B  l )
 (1-13)
9v
These instruments are rarely used for rheological measurements due to the difficulties involved in
accurately correcting for non-Newtonian behaviour.38
1.7.4.3 Drag Flow Rheometers
In drag flow rheometers, the motion of a moving surface in the rheometer causes the shearing of
the fluid sandwiched between the moving surface and a stationary surface. The fluid imparts a
drag on the stationary surface of the equipment which is measured alongside the velocity of the
moving part. The shear rate and shear stress are respectively obtained from the velocity of the
moving part and the force per unit area required for the motion. The viscosity and other rheological
data are calculated from these parameters based on the geometry of the drag flow rheometer as
highlighted below.
Sliding Plates Rheometers
A rheometer with parallel plates’ geometry is a direct development from the simple shear model
(Figure 1b). A steady simple shear is generated by placing materials between a fixed plate and
another plate moving at a constant velocity.38 In these instruments, shear stresses are derived from
the force acting to displace the moving plate or keeping the stationary plate in position. These
instruments are equipped with shear stress transducers to measure local shear stresses.42 Though,
these rheometers are more suitable for measurements of viscosity at high deformation rates, the
challenges of operating them include errors due to edge effects and the difficulty of confining less
viscous fluids within sample space.
23
Rotational Rheometers
There are two methods to induce shear in a rotational rheometer. One way is to pre-set a rotational
speed in the instrument and then, the torque generated by the fluid is measured. The other way is
to impact the fluid with a known torque, then the rotational speed response is measured. At the
advent of rotational rheometric techniques, instruments that were designed to operate base on the
pre-set rotational speed were referred to as controlled rate rheometers (CR), while those that were
based on the pre-set torque were called controlled stress rheometer (CS).33 In most cases, as a
result of the power of computing, these instruments have long been replaced by more sophisticated
designs that could operate in both CR and CS modes. In addition, many new rheometers are now
modular, thus users can easily switch from one measuring configuration to another on the same
rheometer.
There are three basic shear induced flow models in laminar flow regimes upon which the designs
of rotational rheometers are based. Below are the descriptions of the three models vis-à-vis their
geometries and instrument designs.
Parallel Disks
In this design, one of the two parallel circular plates with small gap between them rotate around a
central axis as the fluid under investigation is sandwiched between them. Either the upper or lower
plate can serve as the stationary plate while the other will be the moving plate. A laminar flow is
assumed, similar to sliding motion in a pack of cards. The major challenges in the use of this
geometry are the edge effects and fluid inertia. The edge effects which may be as a result of
24
evaporation or aeration of samples at the edges of plates. To minimise edge errors, the gap (h)
value must be at least fifty times the average dispersed particle diameter.32,39 Fluid inertia depends
on the nature of material under investigation. Both of these sources of error are concerns in
measuring the rheometric properties of sulfur and will greatly reduce the accuracy of
measurements. Finally, because the studies within this thesis are aimed at a wide temperature and
longer periods of investigation, fluid loss due to evaporation would be problematic.
Cone and Plate
Because a constant velocity gradient is assumed for two-plate rheological model, the variation in
angular velocity of fluids under investigation in the parallel plate geometry from the centre of the
moving plate to the edge of the plate is another trade-off. The angular velocity increases linearly
as a function of the distance from the centre of the moving plate. Consequently, shear rate varies
across the plate. In order to make the shear rate independent of the distance from the centre of the
moving plate, one of the plates is substituted for a cone whose tip almost touches the other plate
at the centre. The angular velocity still increases linearly with the distance from the centre of the
moving plate, but now so does the gap between the plates, which in turn makes the shear rate
constant for the distance from the centre of the moving plate and therefore constant across the
plate. According to the ISO 3219:1994E, CEN standard, the cone angle, α is preferably close to
1°, and must not be greater than 4°.43 This geometry is an improvement on the parallel plate
because it requires smaller sample size and ensures homogenous deformation within the sample.44
The errors due to inertia and edge effects (where sulfur would be evaporating) are again significant
as with the cone and plate geometry. Therefore, it is also not suitable for accurate measurements
of rheometric properties of sulfur.
25
Concentric Cylinders (Cup and Bob)
The concentric cylinder rotational rheometer will be used for this study. In these rheometers,
materials are kept in the gap between a cylindrical cup and a bob. Maurice Couette in 1890 was
the first to make a practical rotational rheometer with concentric cylinder geometry.38 In Couette’s
design, the outer cylinder is made to rotate at a known speed while the inner stationary cylinder is
suspended by a torsion wire. A mirror was used to measure the angular deflection as a result of the
drag by the fluid on the inner cylinder. The angular deflection is indicative of the torque.
The second design of cup and bob geometry is the Searle geometry. In contrast to Coutte’s design,
Searle’s design has an outer fixed cup and an inner rotating bob to induce shearing, (Figure 6).
The shaft of the inner rotating bob also has attached to it the sensor of the torque required to sustain
the rotational motion.
ω
Inner cylinder
Ro
Sample space
L ω
Ri Outer cylinder
(a) (b)
Figure 6. (a) Concentric cylinder geometry of a rheometer showing its dimensions and the inner
bob; (b) cross-section of a concentric cylinder geometry of a rheometer.
26
By keeping the radii of the cylinders large and the gap between the cylinder inner wall and the bob
small, the difference in radial velocities at the two walls is small and negligible. Thus, the shear
rate between the walls is constant. In both Couette and Searle designs, the simple shear model is
assumed (Figure 3b). The inner bob is thought of as a folded upper plate and the outer cup as a
folded lower plate. The torque and rotational speed are the raw data obtained from rotational
rheometers. These data are combined with the physical dimensions of the measuring geometries
to obtain shear stress and shear rate, respectively, from which the viscosity is calculated. The shear
rate, γ̇ is obtained from equation (1-14), where Ro, is the radius of the outer cylinder, Ri, is the
radius of the inner bob, and ω is the angular velocity:
Ro 
  . (1-14)
Ro  Ri
If the torque is represented by M, then the shear stress, τ is obtained by equation (1-15),
M
  . (1-15)
2Ro2 L
It follows from equation (1-2), that viscosity, η measured at the inner shear rate is given by;
M ( Ro  Ri )
 . (1-16)
2Ro3L
1.8 Choice of Rheometer Geometry
Several factors are considered in determining the appropriate geometry to meet an experimental
need. Some of these criteria include the need to operate at high shear rate, uniform flow and
controlled temperature.45 Having described different rheometer designs, below is a summary of
their important of advantages and disadvantages:
27
Table 1. Advantages and disadvantages of different rheometers. (Adapted from Macosko, W. C.,
1994).38
Method Advantages Disadvantages
Capillary - High shear rate - Pressure drop correction is

- Wide viscosity range time consuming
- Sealed - Unsuitable for time dependence
Sliding Plates - Simple design - Shear rate limited to 10 s-1

- Homogenous flow - No gap control
- Best for high viscosity fluids - Difficult to load
Cone and Plate - Constant velocity gradient - Edge failure for high viscosity
- Induces homogenous flow fluids
- High inertia effects
- Evaporation of samples
Parallel Disks - Easy to load viscous samples - Non-homogenous

- Variable shear rate - Edge failure
- Evaporation
Concentric - Best for high shear measurements - Difficult to clean

Cylinders - Homogenous flow if cylinder ratio - Difficult to load with sample
( Ri / Ro ) ≥ 0.95
In addition to the advantages listed in Table 1, concentric cylinder rheometers possess some other
important characteristics that made it the most suitable geometry for the investigation of sulfur’s
viscosity. The concentric cylinder is the only rotational geometry in which samples are fully
confined to the annular region of the measuring profile to prevent undesired interaction from the
surrounding, evaporation and materials from being thrown out at high shear rate (Figure 6a).
Furthermore, this study aims at defining rheological parameters necessary to inject molten sulfur
at high shear rate into underground reservoirs for long term storage. It follows that a suitable
28
measuring configuration must be good for high shear rate measurements. The concentric circle is
unique for such measurements.
1.9 Rheology Models
Rheological data are oftentimes fitted to empirical or theoretical models. Equation (1-8) is a
constitutive equation that expresses viscosity as a material constant. In order to accommodate non-
Newtonian behaviour in materials, the exponent of the shear rate in the Newtonian constitutive
equation takes a value other than unity.46 The shear stress now depends on some power of the shear
rate, equation 1-18. This model is known as the power law or Ostwald-deWaele model:
  K c  m (1-18)
Where Kc, defined as consistency replaces viscosity in equation 1-18 and the exponent m is the
flow index. The value of m indicates the dependence of viscosity on shear rate. When
equation 1-18 is divided through by γ̇ , the power law equation takes the form in equation 1-19:
  K c  m1 (1-19)
A value of m ˂ 1 corresponds to shear thinning material behaviour and m ˃ 1 to shear thickening
material behaviour. When m = 1, equation 1-18 reverts back to the Newtonian constitutive equation
(equation 1-8).
Other variants of the power law model are the Sisko and Cross models.36,38 The Sisko model,
(equation 1-20) is an extension of the power law model with the addition of an upper limiting
Newtonian viscosity, η∞:
     K c  m1 (1-20)
29
For cross model, equation 1-21, reduced viscosity is used instead of viscosity to incorporate a
wider flow regime. Where η∞, is viscosity at upper shear limit and η0 is viscosity at lower shear
limit.
0 
 ( K c  ) m (1-21)
 
The Bingham model is a modified Newtonian (equation 1-8) constitutive law with the addition of
plastic yield stress for material behaviour that requires yield stress to flow, equation (1-22). In this
equation, yield stress, τ0 and plastic viscosity, ηp are empirical constants.
   0   p   (1-22)
30
Chapter Two: REVIEW OF LITERATURE DATA, EXPERIMENTAL TECHNIQUE
AND MODELS
Physical parameters such as temperature and shear rate have important effects on the flow
properties of liquid sulfur. Some important conditions include: (i) the freezing point of sulfur at
1 atm is approximately 115 °C, (ii) the viscosity of liquid sulfur abruptly increases to about four
orders of magnitude at T = 187 °C, and (iii) the auto-ignition of sulfur vapour at 3.5% mol (in air)
which will produce highly toxic SO2 gas must also be considered in the choice of experimental
technique for molten sulfur analyses. As a result, there are few experimental data for the viscosity
of sulfur. In this chapter, the available experimental techniques, data, as well as theoretical models
for sulfur’s viscosity will be reviewed. The deficiencies and strengths of these methods, the data
and models also will be highlighted.
2.1 Sulfur’s Viscosity Measurements
2.1.1 Measurements Data for the entire Liquid Temperature Range
Before Bacon & Fanelli reported their sulfur viscosity measurements in 1943 there had been two
data sources reporting the viscosity of sulfur without agreement. Rotinjanz (1908) used a modified
Ostwald viscometer (capillary viscometer) to measure the viscosity of sulfur in the entire liquid
range. The Ostwald viscometer is a U-tube which comprises of two bulbs separated by a capillary
section. The liquid sulfur is drawn into the upper bulb and the efflux time t, required for the liquid
to pass between two etched lines along the capillary tube while it drains into the lower bulb under
gravity is recorded. t is then multiplied by the apparatus constant K, to obtain; η = K t as explained
in subsection 1.7.4.1. Rotinjanz did not equilibrate the liquid sulfur before taking measurements
31
but carried out the experiment at heating rates ranging from 0.27 to 1 °C per minute.10,11,47 He
reported that η was dependent on the heating rate, with higher heating rate showing lower
maximum viscosity, ηmax values. His reported ηmax at 187 °C was 52,000 cP (52,000 units relative
to the η of water).2,10,48 It was also reported that the ηmax obtained was lower on cooling than it was
while heating the same sample. The latter are now understood to be due to reactions of impurities
in the liquid sulfur.
Later, Farr and Macleod (1928) found the modified Ostwald viscometer unsuitable for
measurements of liquid sulfur’s viscosity above 160 °C.10,11 They used a coutte-type rotating
cylinder viscometer for their measurements. In their set-up, they suspended a sealed glass tube
containing a mercury thermometer using a two-wire suspension system over a light pulley to
achieve equal tension across the rotating system.11 This glass tube was lowered into a test-tube
containing the liquid sulfur to be analyzed. The test-tube was suspended by a different one or two
suspension pulley system. The pulley was equipped with a motor with magnetic brake to vary the
speed of rotation. The rotation of the test-tube was followed by a mirror attached to the test-tube
from where the reflection of a spot of light on a circular scale was measured. The speed of rotation
was generally in the order of one revolution in five seconds and was recorded using a stop watch.11
A paraffin bath was used to maintain the temperature in the system up to 220 °C. The general
expression for pulley systems were combined with equations representing the rotation of cylinders
to calculate η, for the two suspension system is
( Ri  Ro )( Ri  Ro )m p gd1d 2
  sin θ , (2-1)
16Ri Ro hl
2 2
32
where Ri and Ro are the radii of the inner and outer cylinders respectively; d1 and d2 are the width
of suspension at the top and bottom respectively; h is the depth of immersion of glass tube in liquid
sulfur; l is the length of suspension; θ is the deflection angle; mp is the mass of suspended system.11
Just like Rotinjanz, Farr and Macleod had difficulties with the purity of sulfur. They observed that
the ηmax of sulfur was lower when cooling than heating and that a higher maximum heating
temperature gave lower ηmax value. Amongst many other observations, it was also concluded that
the ηmax of 21,500 cP of gas-free sulfur was reached at 200 ˚C. An air-exposed sulfur maintained
all night at 125 °C gave an ηmax of 42,750 cP while after exposure to air for a prolonged period at
about 190 °C, the viscosity of liquid sulfur could rise as high as 80,000 cP. They believed H2SO4
was the major impurity that greatly influenced the viscosity of air-exposed liquid sulfur.10,48
Bacon & Fanelli went the extra mile to purify the sulfur for their experiment by a rigorous
procedure they developed.6 These authors felt that most organic matter in liquid sulfur reacted
after a few hours of boiling, but the products of the decomposition reactions appeared to be
resistant to further destruction by heating (now referred to as CarSul production). They subjected
the commercial grade sulfur (Frasch) to a prolonged cycles of heating, boiling, solidification,
melting, crystallisation and vacuum treatment in the presence of magnesium oxide. The
magnesium oxide reacts with acid impurities and catalysed further decomposition of H2Sx present
in liquid sulfur. The liquid sulfur was then filtered and tested for organic matter to confirm it was
free of these impurities. Four cycles of heating for thirty hours were suggested to achieve complete
elimination of carbonaceous matter, H2S and H2Sx in liquid sulfur.6
33
For their measurements, Bacon & Fanelli used a modified Ostwald viscometer for the temperature
range between 118 °C and 160 °C and a paraffin bath for temperature control. For measurements
above 160 °C, they used a pipet graduated in milliliters. A known vacuum pressure was impressed
on the capillary tube immersed in the liquid sulfur to be measured. The time taken for the sulfur to
rise to a marked length of the capillary was recorded using an electric stop clock. This set-up was
housed in a glass wool lagged electric air-bath for temperature control. The viscosity was
calculated using the Poiseuille’s equation,
r 4 pt .
 (2-2)
8VL
From this measurement, ηmax of liquid sulfur was reported to be 93,200 cP at 187 °C. They also
treated different portions of their purified sulfur under vacuum and equilibrated at different
temperatures for different durations. After several measurements, they concluded that the rate of
heating, cooling and thermal history have no effect on the viscosity of sulfur; and from their data
the heating curve of η vs. T measurements of pure sulfur coincided with the cooling curve. They
also assigned the discrepancies in previous literature data to the impurities present in sulfur used
for the experiments. Doi (1963) also made measurements using a rolling ball viscometer. His data
are in agreement with the experimental data of Bacon & Fanelli. (Figure 7).49
34
Bacon & Fanelli
λ-transition
50000
5000
Farr & Macleod
Sn ⇌ •S•n
ɳ / cP
500
50
Ruiz-Garcia et. al
Doi
5
120 160 200 240 280 320
T / °C
Figure 7. Experimental literature data of sulfur’s viscosity. ▲, data of Farr & Macleod;48 ●, data
of Doi;49 ♦, data of Ruiz-Garcia et al.;29 ■, the heating profile data of Bacon & Fanelli; 2 ■, cooling
profile data of Bacon & Fanelli.2
2.1.2 Measurements Data below 160 °C
Ruiz-Garcia et al. (1989) used a falling ball viscometer for their measurements. A high-purity
sulfur sample (99.999%) was degassed by melting, followed by the evacuation of evolved gasses
for fourteen cycles.29 The degassed sample was sealed into a glass tube containing glass a ball and
having two reference marks. A stopwatch was used for timing the fall time of the glass ball between
the reference marks. Stokes’ law was used for the calculation of the viscosity:
35
  K  B  l   t , (2-3)
where K is the instrument constant, ρB the density of the glass ball and ρs is the density of sulfur.
Within the temperature of interest (118 °C - 163 °C), ρ of sulfur changes by 1 %, while the density
of the glass ball changes by 0.02 %.18,29 Ruiz-Garcia et al. observed a reduction of viscosity values
i.e., relaxation when measurements were collected continualy for three days. These viscosity data
were still larger than those reported by earlier authors. When data were collected within three
hours, not more than 0.5 – 1 % relaxation in the viscosities were observed. The reported data of
Ruiz-Garcia et al. corresponded to sulfur being heated versus cooled between experiments. Like
previous authors, they concluded that the relaxation was due to a trace amount of impurities present
in liquid sulfur. Like many other authors, they reported only the highest viscosities obtained at
each T during their measurements.2,10,49 Their data appear to be the better than all earlier data
reported considering the higher purity of the sulfur for their experiment. Figure 7 shows the
experimental data of the workers whose methods have been discussed above. The data of Farr and
Macleod, Bacon & Fanelli, and Doi are within (1 - 2% ) of one another for the measurements
between the sulfur melting point and T = 160 °C.
Apart from the response of the timer being a limitation of the method of Ruiz-Garcia et al., they
also acknowledged that liquid sulfur might possess a non-Newtonian behaviour especially at the
higher ranges of T and η. This they claimed can have an insignificant effect on sulfur’s viscosity
within the temperature of their interest which is between melting and 160 °C.29 They also claimed
that the shear rate for their measurements must have varied only between 6 s-1 to 60 s-1. Previous
authors neither mentioned nor accounted for the shear effect on the η data of liquid sulfur they
reported. It is therefore important to revalidate the viscosity data especially for temperature above
36
160 °C, knowing that previously reported measurements might have been influenced by shear rate
which was not accounted for.
2.2 Viscosity Models for Sulfur
Because of the wide industrial applications of sulfur, there is need for accurate estimation of its
viscosity among other physical properties. This will help in optimizing the Claus plant operations;
and processes involving sulfur pipelines, pumps, tankers and storage tanks. To define the region
with a sharp rise in viscosity after the onset of λ-transition of sulfur, a number of authors have
developed several models based on the theoretical principles discussed below.
2.2.1 Equilibrium Polymerisation Theory
Powell & Eyring (1944), Gee (1952), Tobolsky & Eisenberg (1958), and Touro & Wiewioroski
(1966) have all worked on modelling sulfur’s viscosity based on the theory of equilibrium
polymerisation.50,51,52 The objective of these studies was to quantify the polymer - monomer
equilibria of molten sulfur and in turn correlate η of sulfur to its equilibrium polymer concentration.
Powell & Eyring assumed that the net reaction taking place was breaking the rings which leads to
the formation of radicals of different chain lengths. And thus was represented by the reaction
x
S8 (ring) ⇌ • Sx• (chain) where 0 < x < ∞. (2-4)
8
Assuming a constant enthalpy of reaction ∆H, the equilibrium constant Kx is given by
yx
Kx  x /8
 e  H / RT  ( as x bs ) / R , (2-5)
(y )
where R is the ideal gas constant, x is the chain length, yx is the mole fraction of molecules with
length x and y‫ ٭‬is the mole fraction of S8 rings. as and bs are entropy terms due to end effects and
37
chain lengths respectively. They calculated the mole fraction of the molecules in • Sx• to that in S8
rings and in turn the weight fraction, ϕ of polymer to monomer in liquid sulfur as a function of T.
This calculation was compared to the sulfur polymer equilibrium experimental data of Hammick,
Cousins and Langford obtained by quenching liquid sulfur rapidly to room temperature before
extraction with CS2 to find its equilibrium compositions.50,51,52 There was a good agreement where
the experimental data were reliable.50 Two further assumptions were made to correlate the
calculated ϕ to the viscosity of sulfur;
(1) The η of sulfur can be represented by the Flory equation for molten polyester, relating η to
average chain length and molecular weight; η α (𝑟̅ 2)3/2 / Mav , where 𝑟̅ is the
root-mean-square end-to-end average chain length of a polymer and Mav is the average
molecular weight of the polymer,
(2) The general η equation for a polymer mixture holds for the • Sx• and S8 mixture;
M  (rings)1 (chains) (2-5)
Calculating η from a sulfur-halogen system resulted in the following expression:
1/ 2  
ln = ln  M 
BZ w 1 1  (2-6)
R  1 M x Z 
 
Where ηM is viscosity of mixture, η is viscosity of sulfur, Mx is the ratio of halogen atoms to S
atoms and Zw is the weight average change length. B and Z are constants calculated from other
available literature and theoretical data. Even though the shape of the plot of this model nearly
matched the data of Bacon & Fanelli, it over-predicted the maximum viscosity of sulfur by at least
a factor of two.51
38
Gee (1952) pointed out that the theoretical model of Powell & Eyring did not account for the
critical temperature at which a sharp rise in viscosity occurred.50 He then proposed an equilibrium
based on removal of S8 rings from the ends of a diradical chains as

•
Sx• ⇌ • S •x-8 +S8 (2-7)
By applying Flory’s law of polymer mixtures and neglecting the T dependence of ρ, ϕ of polymer
in equilibrium was obtained as
 H  1 1  
 1 exp      . (2-8)
 R  TΦ T  
According to this expression there is a discontinuity at Tϕ (transition temperature), and ϕ will be
stable below or above Tϕ depending on whether or not the ∆H is negative or positive.50 This made
the equation invalid below Tϕ, even though the hypothesis that the production of polymer started
at a critical temperature was satisfied. Because this theory could not satisfactorily predict the ϕ
below Tϕ and at T very near Tϕ, Gee applied a different theoretical approach to predict the ϕ below
Tϕ. He used the Arrhenius equation, which fit well to sulfur’s η experimental data between melting
at 115°C and 160 °C to account for the low values of η below Tϕ. Using the experiment data of
Hammick, Cousins and Langford, a plot of -ln (1 – ɸ) against 1/T gave a satisfactory straight line,
from which Tϕ and ∆H4 / R were obtained to be 150 °C and 16,736 K respectively. A general
expression for η dependence on chain length was used to account for sulfur’s polymer chain
length.50
That is,
2
  AP 3 , (2-9)
where A is a constant which depends on T, and P is the average polymer chain length, and for
polymer concentration, equation (2-10) was used,
39

 0 1  kT  ,
2 2
(2-10)
where kT is another constant that vary as T, Tϕ was adjusted from the calculated 150 to 159 °C to
fit the region of rapid η increase. Gee’s final expression for the dependence of η on T was obtained
as
 2 ΔH 5  1 8   
ln η=B   2940+  + ln 1- exp ΔH 4  1  1   . (2-11)
 3R  T 3  R  Tφ T  

In this expression, three unspecified constants were combined into B, then B and ∆H5 were used
as fitting parameters. The predictions from this model matched experimental data well except for
the narrow T range around Tϕ where the predictions are poor.
Tobolsky & Eisenberg proposed a unified theoretical treatment to account for sulfur’s ϕ below and
above Tϕ by using two equilibrium reactions to describe the polymerisation in liquid sulfur. The
first reaction was ring opening while the second was polymer propagation reaction:
S8 ⇌ • S8• (2-12)
•
S8• + x S8 ⇌ • Sx• (2-13)
Tobolsky & Eisenberg’s equilibrium concentrations were calculated in molality (m; mol kg-1) to
avoid the use of ρ, whose dependence on T would have impacted uncertainties into the predictions
from Gee’s model.50,52 In agreement with Gee, ∆H4 / R from Tobolsky & Eisenberg’s theory was
obtained to be 16,520 K for reaction 2-12 and 15,960 K for reaction 2-13.52 Moreover, Eisenberg
(1969), using Fox and Allen’s extended viscosity theory based on molecular flow, found the power
law index of 3.4 to be operative for sulfur polymer entanglement system. Combined with the above
unified theory of polymer chain length, concentration and using the modified William-Landel-
40
Ferry (WLF) empirical equation for monomeric friction factor, η was calculated. ηmax was four
orders of magnitude higher than that of the experimental data.53 Eisenberg then suggested that
theory based on molecular flow alone could not accurately predict the η of sulfur.53
2.2.2 Modified Reptation Theory
Though Eisenberg developed further equations based on bond interchange and chain-end
interchange theories, both over predicted η of sulfur by four orders of magnitude.53 Cates (1987)
incorporated bond breaking into the reptation theory, combined with existing sulfur polymer
equilibria theories established by earlier authors. Reptation motion is the thermal motion of long
linear entangled polymers in polymer melts or concentrated polymers, analogous to snakes
slithering through one another.54 A polymer chain is restricted to motion along a tube of
entanglements made by other polymers. By exiting the tube in a snake-like diffusion, relaxation
takes place in a time scale known as reptation time (τrep). τbreak represents the time taking for a
chain of polymerisation index N, to break into two pieces. For τrep ˂˂ τbreak, the rate-limiting step
in relaxation of stress associated with a particular portion of the chain would be the waiting time
for a break to appear within a certain distance of chain length. In modifying this motion to
accommodate chain breakage and recombination, the following assumptions were made:
(1) Recombination of chains is typically at the end of another chain, rather than the one
that immediately dissociated from the chain
(2) Breaks can occur anywhere along the • Sx• with equal probability per unit time
(3) Addition and breaks of S8 monomers were disregarded in finding the lifetime of chains
Assuming breaks can occur with equal probability per time, the Flory expression for polymer chain
conformation is used to obtain stress relaxation time as
41
Nl 2
 rep  break
r   ,
2
break
(2-14)
where l, is a monomeric chain length and r2 (t) is the mean-square displacement of a chain end in
time t in reptation model.38 For this time scale, the η obeys
  Ge , (2-15)
where Ge is the plateau (equilibrium) modulus of the entangled polymer system. For the liquid
sulfur system, Cates reasoned that the recombination time, τbreak is so short that the motion of chain
end is on the time scale of its recombination is always Rouse-like.55 Therefore,
N
   break , (2-16)
n
 f n 2   Rouse(n)   break , (2-17)
where, τf is the friction constant and n is the number of monomers. To calculate η; N, Ge, τf and
τbreak must first be obtained as functions of T. N and the volume fraction (ϕv) were obtained from
the equilibrium theories of Gee;
  1 1 
v 1 exp 11610    , and (2-18)
  4321 T  
ln N    4.14  ln  v  .
7550
(2-19)
T
Ge, the plateau modulus was found as
cRT  N 
Ge  1  2 e  , (2-20)
Ne  N
where c is the number density proportional to ϕ and Ne is the polymer entanglement length.55,56
The temperature dependence of τf was obtained using the WLF empirical equation, with the
parameters of Eisenberg (1968),53 as
42
1510 26.2T  243
ln  f  C  
T 195
, (2-21)
T
The expression for τbreak was found to be
 break  Nk 1 , (2-22)
where k is the first-order rate constant for the dissociation of S-S bonds in polymerised sulfur.
Bacon & Fanelli’s data were fit to a modified Arrhenius equation in the form: By combining
equations 2-14 to 2-22, the expression for η was found to be;

1
 12
  Ge N  f k
1
2 2 . (2-23)
Bacon & Fanelli’s data were fitted to a modified Arrhenius equation in the form;
k/λ2 = A exp (-B/T), while A & B, along with C in equation 2-21 were used as fitting parameters. λ
is a constant of the order of unity used to absorb possible errors in equation 2-20.55 The following
equation was therefore obtained by Cates
k  15400 
 7.11013 exp  , (2-24)
 2
 T 
where B (15,400 K) is the activation energy for the dissociation in the form Ea / R, and λ is a
product of constants independent on T. Only A and B in the expression for k were used as fitting
parameters as k from previous works are not in agreement.45,52,55 The activation energy, B was
obtained as 15,400 K which differs from the value 16,500 K of both Gee and Tobolsky &
Eisenberg.45,52,55,57 This was attributed to the uncertainties in the WLF parameter’s
pseudo-Arrhenius behaviour at T > Tɸ, which was confirmed by extrapolating the model to a lower
T range to obtain k values that are within the range of estimates of previous works. However, this
model fit well to the experimental data of Bacon & Fanelli (1943).6 Cates calculated τrep for a
hypothetical, unbreakable and entangled polymer from this model, to be 1500 s. This is five orders
43
of magnitude larger than τrep of 1.5 x 10-2 s obtained for sulfur polymers using this model. Again,
this confirmed the hypothesis by Eisenberg that models based on the molecular flow of sulfur
alone would overestimate the η of sulfur up to four or five orders of magnitudes.
Being the only model that incorporated bond breakage into the polymerisation theory, this model
far better represents the liquid sulfur equilibria compared to earlier efforts. Again, the verifiable
assumptions made for this model were validated. The sulfur viscosity data of this thesis will be
fitted to the modified reptation model of Cates (equations 2-23 and 2-24).
2.3 Effects of Impurities on Sulfur’s Viscosity
The following impurities: H2SO4, H2S, amines, halogens and hydrocarbons have been shown to
have a modifying effect on the viscosity of molten sulfur.10,58 Of these impurities, H2S is of most
importance for reasons mentioned in section 1.6, and so, its modifying effect on the viscosity of
sulfur will be reviewed in this thesis.
2.3.1 Effects of H2S on Sulfur’s Viscosity
Fanelli (1946) studied the modifying effects of H2S on the viscosity of molten sulfur and later, in
a separate study, measured the solubility of H2S in molten sulfur.10,12 For the determinations of the
viscosity modifying effects, a known amount of H2S was introduced into a specialized capillary
viscometer in the form of liquid H2S or sulfur disulfide (H2S2) before viscosity measurements were
made. In the latter, H2S2 readily decomposed into H2S. The H2S content was calculated from the
H2S2 added as weight percent of the total weight of mixture. It was observed that much of the H2S
remained in the vapour space during the η determination. After saturation with H2S, while the
44
capillary viscometer was being sealed before viscosity determination, it was reported that some
H2S gas escaped. This caused underestimation of the modifying effects of the dissolved H 2S on
the viscosity of sulfur.10
Rubero (1964) used a two autoclave capillary-viscometer-system to re-examine the solubility of
H2S in molten sulfur.58 He completely filled the first autoclave with molten sulfur and subsequently
with H2S as a portion of the molten sulfur was drained out. The second autoclave, which was
connected to the first by a metering tube, was filled with nitrogen gas. The two autoclaves were
connected to a mercury barometer from which the pressure was directly recorded. By using the
Poiseulle’s equation (equation 2-2), the viscosity was calculated from the pressure difference (∆p)
and the instrument constant (K). To quantify the dissolved H2S, the molten sulfur was allowed to
flash into a tared container in the second autoclave which was connected to an iodine filled
absorption train. The excess H2S in the absorption train was obtained by titrating with thiosulfate
and the weight of sample was obtained by reweighing the tared container after the experiment. As
expected, Rubero recorded a higher suppression of sulfur’s viscosity than Bacon & Fanelli for the
same amount of dissolved H2S.58 However, elemental mercury (Hg) reacts with sulfur to produce
cinnabar (HgS) which is a very stable compound. There is a high likelihood of occurrence of this
reaction as sulfur vapour was in contact with mercury in the barometers used for pressure
measurements. Hence, this method is inherently defective.
Touro & Wiewiorowski (1965) showed that pure molten sulfur is absorption free for infra-red (IR)
vibration spectroscopy between 1400 to 4000 cm-1 and so, can serve as a solvent for the IR
determination of dissolved H2S in sulfur.59,60 They scanned molten sulfur treated with H2S in the
45
region of S-H stretching (2400 – 2600 cm-1) where absorption peaks at 2498 cm-1 and 2570 cm-1
were observed.59 They assigned the former to H2Sx and the later to H2S after analyses of the rate
at which each peak developed.
Finally, Marriott et. al. (2008), used a more sensitive IR vibration spectroscopic technique to
measure the solubility of H2S (H2S+ H2Sx) in liquid sulfur, and to further characterize the
physically adsorbed species (H2S) from those chemically dissolved H2S (H2Sx) at different T and
p corresponding to conditions encountered during the industrial processing of molten sulfur.24
They observed the asymmetric vibrational IR absorption of the S-H bond for H2S in liquid sulfur
at a wavenumber of 2571 cm-1, while the S-H bond for H2Sx was observed at 2498 cm-1.24 The
ratios of H2Sx : H2S in liquid sulfur obtained from this method were different from those reported
by Touro & Wiewiorowski.24,59,60 Note that the deficiencies highlighted above in the experimental
solubility data of Bacon & Fanelli must have imparted the H2Sx : H2S ratio reported by
Touro & Wiewiorowski as the latter’s T correction factors were derived from the former’s
experimental data. In addition, the long formation time necessary for H2Sx and in turn possible
absorption from unterminated HSx• radical species which also must have imparted the experimental
data of Touro & Wiewiorowski likely contributed to the discrepancy. The IR technique of
Marriott et. al. will be used in this study.24
46
Chapter Three: EXPERIMENTAL METHOD AND PROCEDURE
An Anton-Paar Modular Compact rheometer (MCR 302) rated to 1000 bar was purchased for this
study. To commission this instrument, it will first be used to analyze available certified viscosity
and rheology standards. Unique procedures must be established to safely deliver molten sulfur into
the pressure cell while accurately measuring the head pressure and the rheometric properties of
liquid elemental sulfur.
3.1 LabVIEW Code for Pressure Data Acquisition
LabVIEW code (Laboratory Virtual Instrument Engineering Workbench) was written to log
pressure measurements from a Keller PA-33X transducer (0 - 1000 bar) to a computer file. The
LabVIEW environment is different from text based programming languages (such as Fortran
and C), in that LabVIEW uses a graphical programming language known as the G programming
language to create programs relying on graphic symbols to describe programming actions.61,62
LabVIEW has two interfaces that are connected to each other. The front panel which has the
controls and the indicators, and the block diagram which contains the actual executable program.
Once the Virtual Instrument (VI) is made and running, a user may control or give instructions to
the VI through the front panel but cannot interfere with the block diagram until the program is
stopped.
Figure 8 shows the front panel of the VI created for this study while its block diagram can be found
in the Appendix A. In this front panel, two numeric controls B and C were created: B is used to
key in the respective file name, while C is used to select the communications port of the transducer
47
on the computer (COM 5). In addition, separate numeric controls were created to input the
calibration constant and the vacuum correction constant into the VI.
A F
H
I
A
E
Figure 8. Front panel of the VI to log pressure from the transducer. Notations: A, pressure readings
indicator; B, numeric control for file name; C, communication port selector; D, boolean for data
saving; F, pressure reading graphical display ; G, transducer communication indicator; H,
calibration constant input numeric control; I, vacuum correction input numeric control.
Two indicators A and F were drawn: “A” displays the real time numeric pressure measurements
while “F” is a graphical display of the pressure measurements history. Boolean was created: one
was to give the command whether or not to save data (D), while the other was to indicate whether
or not the transducer was communicating with the program (G). A while loop was drawn to give
conditions for the continuous running of the VI (E); however, the loop and program could be closed
by pressing the “Stop” switch. Numeric controls H and I were also created to input the calibration
48
constant and vacuum corrections respectively. The wirings between controls and indicators of the
VI can be found in the corresponding block diagram in Appendix A.
3.2 Pressure Transducer Calibration
3.2.1 Deadweight Tester
A deadweight tester (DWT) or piston gauge uses a known mass, m, of a set of weights to generate
a force, F, over a cross-sectional area, Acs. The pressure p, is then counterbalanced by exerting an
equal pressure from a pressure pump on the fluid in the DWT reservoir until the weights freely
floats indicating an equilibrium of pressure throughout the hydraulic system.62,63 By connection to
the fittings on the DWT, the p generated is transferred to the transducer to be calibrated. p is given
by:
F  mi g
p  i (3-1)
Acs Acs
To ensure accurate measurements, the transferred p, is corrected for local gravity, gl, local
temperature, buoyancy of the stack of weights, thermal expansion of the instrument and static
pressure head as a result of the different height between the transducer and the piston. With the
incorporation of the corrections, equations 3-1 is transformed into:
 mi g   
1  air   g l  fluid h 
F
p  i
Ap Ap   mass 
, (3-2)
where
 
Ap  Ae 1   p   c T  Tref  , (3-3)
and
49

Ae  a0 1  bd p . (3-4)
a0 represents the effective area of the piston at ambient pressure and the reference temperature,
Tref, at which the properties of the deadweight piston were initially measured. The pressure
distortion coefficient, bd, in equation 3-4 is used to calculate the constant temperature effective
area, Ae, when a certain amount of pressure is loaded. Ae is then converted to the temperature-
corrected true effective area, Ap, through equation 3-3 for the temperature T, at the time of
calibration, using the coefficients of thermal expansion for the piston and cylinder, αp and αc,
respectively.62, 64 Once Ap has been determined, the buoyancy correction is applied to the pressure
equation using the ratio of air density, ρair, to the density of the weights, ρmass.62,64 The static
pressure head correction is also applied due to the height difference, Δh, between the transducer
and the bottom of the piston assembly using the local acceleration due to gravity, gl, and the density
of the hydraulic fluid, ρfluid.
3.2.2 Experimental Methods
A Pressurements Limited T 3800/4 Deadweight Apparatus and standard weights were used to
apply the reference equilibrium pressure to the Keller pressure transducer. The standard weights
were carefully cleaned and measured on a highly sensitive X26003L Mettler-Toledo mass
comparator to 3 decimal digits (0.001 g). Isopropyl alcohol was used as the hydraulic fluid instead
of a commercial hydraulic oil for ease of cleaning the transducer’s measurement chamber after the
calibration.
To generate pressures for the calibration, the following procedures were used (Figure 9). The
leveling feet J of the dead weight tester were adjusted to ensure balance while observing the bubble
50
level in the indicator “G”. The pressure valve “F” was opened and the capstan “D’’ (Figure 9a)
was turned fully out. With the use of the hand pump the hydraulic fluid transfer lines were pre-
pressurized and de-aerated to prime the system. Then, weights equivalent to the desired pressure
were placed on the weight stack “H” and the hand pump “A” was used to pressurize the system
until the desired pressure was nearly reached. The capstan was screwed-in until the weight stack
floated (Figure 9b). The weights were adjusted until the underside edge of the bottom weight was
on the mid reference mark of the indicator rod “I” (Figure 9a) to ensure proper alignment of the
weights. The weight stack was then spun in the clockwise direction between 40 to 100 rpm so as
to obtain a consistent pressure. The spinning helped to minimize error that may result from static
friction between the piston and the cylinder.63,64 At this point, the pressure readings on the
LabVIEW graphical indicator were observed to be constant, then the program was prompted to
save the pressure readings.
51
(a) (b)
Figure 9. (a) DWT without weight on the weight stack. (b) DWT with transducer and weight on
stack at equilibrium with pressurized fluid. Notations: A, de-aeration hand pump; B, pre-
pressurization hand pump; C, hydraulic fluid reservoir; D, fine-pressurization capstan; E,
connection fitting for pressure device to be calibrated; F, pressure-release valve; G, bubble level;
H, weight stack holder with base plate in place; I, base plate indication rod; J, adjustable foot for
levelling; K, Keller pressure transducer; L, floating loaded standard weight.
3.2.3 Results and Discussion
Correction parameters for gravity, buoyancy and pressure head unique to this instrument as
provided by the manufacturer were summarized in Table 2. Equations 3-2 through to 3-4 were
provided also by the manufacturer to calculate the theoretical pressure exerted by the associated
masses. Also, the required masses were obtained by the addition of all the weights used in exerting
the pressure. The corrected theoretical pressure from equation 3-1 and the respective pressure
measured by the pressure transducer are given in Table 3.
52
Table 2. Relevant parameters for deadweight calibration.64
Parameter Value
gl 9.8082 m·s-2
a0 4.06115 × 10-6 m2
bd 1.043 × 10-8 MPa-1
αp+αc 2 × 10-5 °C-1
T 21 °C
Tref 20 °C
ρair 1.22 kg·m-3
ρmass 7300 kg·m-3
ρfluid 785 kg·m-3
Δh 0.0635 m
pvac,21°C 0.0121 MPa
Table 3. The corrected theoretical pressures, the measured pressures, and uncertainties of the
measured pressures estimated using the standard deviation and a 95.5 % confidence intervals.
Ptheoretical / MPa Pmeasured / MPa δ / MPa
4.000 3.996 0.019

5.000 4.997 0.014
6.000 5.996 0.015
7.000 6.994 0.017
8.000 7.995 0.011
9.000 8.996 0.006
10.000 9.995 0.017
12.000 11.993 0.017
14.000 13.995 0.007
53
Table 3. Continued
Ptheoretical / MPa Pmeasured / MPa δ / MPa
15.000 14.994 0.010

18.000 17.993 0.012
20.000 19.992 0.016
22.000 21.991 0.018
22.997 22.983 0.015
24.997 24.983 0.017
29.996 29.982 0.011
31.996 31.980 0.020
39.995 39.976 0.020
The corrected, calculated pressures were plotted against the pressure measurements made using
the pressure transducer. The measured pressure also was corrected for atmosphere by measuring
and subtracting the temperature-dependent vacuum pressure reading. A linear regression was
completed on the plot to obtain the calibration and is shown in Figure 10. The resulting calibration
equation is given as:
Pcorr  1.000468 0.000036 Pmeas . (3-5)
54
45
40
35
30
pcorr / MPa
25
20
15
10
0
0 5 10 15 20 25 30 35 40 45
pmeas / MPa
Figure 10. Deadweight calibration plot of the calculated applied reference pressure (pcorr) against
their corresponding transducer measurements (pmeas).
Because errors in Table 3 (95 % confidence interval) were all greater than the error associated with
the calibration coefficient (0.0036%), the quoted error for each pressure measurement will
therefore be estimated using the standard deviation and the 95 % confidence interval.
3.3 Commissioning the MCR 302 Rheometer
The MCR302 is a modular rheometer in which different measuring geometry and temperature
devices could be coupled. The pressure cell geometry is the only suitable measuring system for
this study because for other geometries, sulfur vapour will continuously escape which would
55
impact experimental data and constitute a safety concern. Other factors that make other rheometry
measuring geometries unsuitable for this study have been discussed in chapter two.
3.3.1 Operation and Hardware of MCR 302 Rheometer
The instrument is equipped with an electric DC motor supported by two air bearings, where the
current supplied to the stator coils is proportional to the torque of the motor.65 The radial air bearing
centers and stabilises the shaft while the axial air bearing holds the weight of the rotating parts.
This instrument can operate with a torque (M) range from 1 nNm to 2 x 108 nNm.65 A magnetic
coupling, attached to the shaft of the motor, imparts a rotational motion on the sample sandwiched
between the pressure cup and a cylindrical magnet by rotating the cylindrical magnet (Figure 11).
The cylinderical magnet is suspended between two sapphire bearings which minimize the friction
at the contact points of the cylindrical magnet with the pressure cup. The pressure cell and the
cylindrical magnet are made of titanium for corrosion resistance. Heating of the pressure cell is
done resistively and is rated up to 300 °C. A 100 ohm platinum resistant thermometer (PRT) is
embedded in the cell for temperature measurement.
56
MCR 302 rheometer
Keller pressure Sulfur
transducer reservoir Electric
motor
Magnetic
coupling
Rotating
V1 cylinder
Sample
V2 V3 space
Pressure
High-pressure
cell
N2 cylinder
Sapphire
bearing
V4
Thermostated FT-IR cell
Figure 11. Schematic of the experimental set-up for measurements of the rheometric properties of
57
Figure 12. Picture of the experimental set-up for measurements of the rheometric properties of
3.3.2 Controls and Data Logging
Rheoplus 4.14 is the software from the manufacturer (Anton Paar) of the rheometer used to send
instructions to the instrument and log measurements from it to a computer system. Using this
software, the instrument can be operated in controlled shear (CS) mode - where the torque (M) is
set and the angular speed (ω) that is obtained as a result of the drag by the sample on the cylindrical
magnet is measured to obtain η, or the controlled rate (CR) modes - where the ω is set while the
58
M required by the electric motor to maintain the ω is measured to obtain the η. The temperature,
time, shear stress, shear rate, speed, and torque can all be varied or kept constant to obtain different
information from sample analyses (Figure 13).
Figure 13. User interface of Rheoplus 4.14 software used for controls and logging rheological data
from MCR 302 to the computer system showing some input variables.
3.3.3 Comparing Measured Results with Standards
To check the accuracy of the MCR 302 rheometer, two Newtonian standards and a non-Newtonian
standard were analyzed. The Newtonian standards included: a low viscosity standard – (Canon
Instrument Company N600) with a viscosity range from 1031 cP at 25 °C to 16.61cP at 135 °C
and a high viscosity standard - (Canon Instrument Company N450000) with a viscosity range from
1,539,000 cP at 25 °C to 2,509 cP at 135 °C. These standards are traceable to American Society
59
for Testing and Materials (ASTM) and National Institute of Standard and technology (NIST)
methods.66,67 The Newtonian standard was Standard Reference Material 2490 purchased from
NIST.68 The certified viscosity values for this standard are provided in Table 4.
Table 4. Certified values for NIST rheology standard-SRM 2490.
T / °C γ̇ / s-1 η / cP δ / cP
25 6.31 41440 270

25 10.00 33040 190
25 15.85 25610 140
25 25.12 19360 100
25 39.81 14260 80
25 63.10 10220 70
25 100.0 7220 60
50 6.31 23540 370
50 10.00 19950 320
50 15.85 16410 270
50 25.12 13140 220
50 39.81 10240 170
50 63.10 7750 130
50 100.0 5720 100
3.3.3.1 Experimental Method
The standard samples were stored and handled as suggested by the manufacturers to obtain
consistent results. To load these samples, the procedure described later in section 3.7 was followed
with the set-up temperature set-point (SP) set to the minimum temperature of analysis for each
60
standard respectively before loading them. Each standard was loaded and measured three times at
the temperatures and shear rate specified in the respective test certificates.66-68
3.3.3.2 Results and Discussions
The measurements made for the Newtonian standards are plotted in Figure 14. The comparison
between the measurements of N450000 and its certified values shows measurements within 10%
of the certified values at 101,500 cP, and within 3% at 2350 cP. Also for this standard, a higher
confidence interval of 99.7 % were calculated using the t-distribution and plotted instead of the
standard 95.5 % confidence interval.69 This is because the 95.5 % was difficult to observe on the
graph. The certified values are well within the plotted 99.7 % confidence interval of the
measurements. For N600, the measurement data were within 1 % of the certified values at 1031
cP and 2 % at 164 cP. A plot of 95.5 % confidence intervals shows the mean of the triplicate
measurements was in agreement with the standard (within the confidence interval) at η = 1031 cP
and 164 cP. While the measurement at η = 16 cP was just outside the 95.5 % confidence interval.
This viscosity value is however outside the range desired for this study and is not of concern.69
61
100000
10000
1000
ɳ / cP
100
10
1
20 40 60 80 100 120 140
T / °C
Figure 14. Comparison of viscosity measurements made using the MCR 302 rheometer and
certified values. ▲, certified values of N600; ∆, measurements of N600; ●, certified values of
N450000; and ○, measurements of N450000. Error bars on the experimental data are at a
confidence interval of 99.7 % for N45000 and 95.5% for N600.
The measurements of the non-Newtonian standard are shown in Figure 15. For these
measurements, the uncertainties ranged from 0.02 % at 6 s-1, to 9% at 100 s-1 of the certified values.
Again, the error bars are calculated with a higher confidence interval of 99.7 % using the
t-distribution instead of the standard 95.5 % confidence interval because the 95.5 % was hard to
observe on the graph.69 The certified values are within the 99.7 % confidence interval for each set
of measurements across the measured shear rate range.
62
50000
40000
30000
ɳ / cP
20000
10000
0
0 20 40 60 80 100 120
-1
γ̇ / s
Figure 15. Measurements of NIST’s SRM 2490: ●, certified values at 25 °C; ○, measurements at
25 °C; ▲, certified values at 50 °C; and ∆, measurements at 50 °C. Error bars on the experimental
data are at a confidence interval of 99.7 %.
3.4 Experimental Set-up
A negative-pressure bay equipped with automatic toxic gas detector was made available for these
studies. The set-up in the bay (Figure 12) comprises of a HP (high-pressure) nitrogen cylinder well
secured to the wall with steel chains. One-sixteenth inch tubing connects the high pressure cylinder
valve (V1) to the Keller pressure transducer. One-quarter inch HP tubing connects the transducer
into the first inlet port of a two-way valve (V2). The molten sulfur reservoir is a 100 mL, 316L
stainless steel cylinder, which fits into the second of the two inlet ports on the two-way valve (V3).
The dual valve outlet, through one-quarter inch HP tubing is connected to the tee-fitting under the
MCR 302 rheometer. With HP quarter-inch tubing, the upper port of the tee directly connects to
63
the HP cell, while the lower port connects to a vent/waste valve (V4). As shown in Figure 11 and
12, the molten sulfur reservoir, the HP tubing and the valves were all heat traced and insulated for
temperature control. All dimensions of tubing used were made of the 316L alloy. The temperature
controllers use the PID (Proportional Integral Differential) feedback-loop control mechanism to
continuously minimize the difference between the Process Variable (PV) which is the actual
temperature, and the set point (SP) which is the desired temperature. The SP is set to ca.140 °C to
ensure that the temperature in the molten sulfur reservoir, HP tubings, and valves, do not rise to
160 °C or fall below the melting point of sulfur at approximately 120 °C.
3.5 Materials
Oxygen-free, nitrogen gas (99.998% as per certificate of analysis) was purchased from Praxair
Technology, Inc. ACS grade, 99.5% toluene was supplied by BHD through VWR Analytical. The
sulfur prills used for this study were supplied by Keyera Energy. The total analysis of these sulfur
prills was performed by Alberta Sulfur Research Limited as shown in Table 5.
Table 5. Result of the total analysis of Keyera air prilled sulfur.70
Moisture content Purity Ash Content H .C. Content H2S Content

Sample
(wt %) (wt. %) (ppmw) (ppmw) (ppmw)
A 0.02 99.992 4 0.6 0.4
B 0.09 99.991 14 0.6 0.3
64
3.6 Experimental Procedure
To prepare the apparatus for the measurements of rheology of liquid elemental sulfur, the viscosity
standards were fully drained out of the pressure cell and the entire set-up. Pure toluene was loaded
into the system overnight to dissolve possible remnants of the standards before being emptied and
disposed-off into the appropriate organic waste station. This was repeated three times to ensure
that no impurities were left in the system.
200 g of high purity sulfur prill (99.992%) was placed in oven overnight at 135 °C. Before the
MCR 302 was powered on, it was ensured that air valve connected to run the air bearing of the
rheometer was opened and at the required pressure of 6 bar. The set points of the temperature
controllers were set to ca. 140 °C. After the molten sulfur reservoir, HP tubing, fittings and valves
had reached the set temperature; about 80 mL of molten elemental sulfur was carefully poured into
the reservoir from its top while all the valves were closed. With all other valves closed, the plug
on the pressure cell was unscrewed, then V3 (the sulfur reservoir valve, Figure 10) was opened to
allow molten sulfur flow by gravity into the pressure cell until some liquid sulfur had escaped from
the top of the pressure cell. The molten sulfur was allowed to remain in the system overnight. No
data were recorded during this time in other to further clean the system. To empty the sample from
the pressure cell, V3 was closed, then, V4 (the vent valve) was opened and the plug on the pressure
cell was removed to allow the sample to flow out under gravity into waste container. This cleaning
procedure was repeated three times before finally retaining the molten sulfur sample for viscosity
measurements.
65
To finally measure and record the data from this study, fresh molten sulfur was loaded into the
apparatus as described above, the plug on the pressure cell was returned and the gland nut was
tightened. The desired temperature and shear rate were programmed using the Rheoplus software
interface, then the instrument was prompted to start analysis. Each time a fresh molten sulfur
sample was loaded into the pressure cell, the temperature of the sample was held for an
equilibration time of two hours at 5 °C intervals from 120 °C to 280 °C while step-wisely heating
and then, step-wisely cooling the sample. Measurements were made after equilibration at each
temperature interval. For this study, while several viscosity measurements were being made at
constant temperatures, the shear rates were varied. The instrument was programmed to
continuously increase the shear rate on the molten sulfur sample in the pressure cell by increasing
the speed of rotation of the magnetic cylinder which makes the instrument also increase the torque
(M) necessary to sustain this speed. The instrument has an operational M range from 1 nNm to 2
x 108 nNm. The instrument had also been programmed from factory to automatically stop the
increment of γ̇ once the maximum M is closely approached to protect the instrument from being
overloaded.
The entire procedure of equilibrating a fresh liquid sulfur sample at different temperatures while
heating and cooling, as well as making measurements on this same sample before finally draining
out for FTIR spectroscopy analysis is referred to as one charge of experiment.
66
3.7 FT-IR Analysis
Both the fresh sulfur loaded into the apparatus and the analysed molten sulfur drained from the
pressure cell were analysed for impurities using Nicolet iS10 FT-IR spectrometer. This instrument
was calibrated up to 200 ppm by measuring the absorbance of several standard solutions of H2S
dissolved in pure molten sulfur, and then purging before quantifying the total H2S evolved from
the same solution using an ion chromatography technique.24 The FT-IR instrument contains a
thermostated cell maintained at T = 135 °C to keep elemental sulfur sample molten. The cell
window is made of KCl and it has a path length of 5 cm. This FT-IR cell is manufactured at Alberta
Sulfur Research Limited and is widely used in industry.24
67
Chapter Four: RESULTS AND DISUSSION
4.1 Measured Newtonian Viscosity Data of Liquid Elemental Sulfur
The measured Newtonian viscosities were averaged across a shear rate range of 1 to 3500 s-1 at
each temperature. The data obtained for the first four charges of sulfur into the apparatus are given
in the Tables 6, 7, 8 and 9 respectively. The stated uncertainties in η, δ, are estimated using the
standard deviation and a 95.5 % confidence interval, while the uncertainties in T were estimated
to be ± 0.1 °C at 95.5 % confidence interval for the entire measurements.
temperatures for the 1st charge of sulfur into the apparatus.
T / °C η / cP δ / cP
165.0 5600.4 86.3

170.0 17470.7 253.8
175.0 24794.4 88.2
180.0 30134.5 156.7
185.0 32049.4 82.0
190.0 30138.8 76.8
195.0 25157.8 57.0
200.0 20106.2 24.5
205.0 16088.0 21.5
210.0 11975.5 28.3
210.0 8670.4 40.7
205.0 7131.7 57.2
200.0 5620.2 50.1
68
Table 6. Continued
195.0 4105.5 66.9

190.0 2647.3 51.9
185.0 1463.8 63.6
180.0 659.8 50.4
175.0 198.3 1.2
170.0 101.7 1.5
165.0 21.8 0.7
temperatures for the 2nd charge of sulfur into the apparatus.
150.0 4.7 0.7

155.0 4.0 0.8
160.0 11.7 0.2
165.0 6392.4 186.7
170.0 24176.6 305.7
175.0 40290.9 446.6
180.0 50579.6 223.5
185.0 55782.3 242.6
190.0 56363.5 207.0
195.0 53747.5 191.3
200.0 49121.7 135.9
205.0 43341.6 121.3
210.0 37360.9 70.5
69
Table 7. Continued.
215.0 31299.2 73.5

220.0 25824.3 394.7
220.0 20521.0 65.7
215.0 20733.3 62.7
210.0 20582.9 59.1
205.0 19597.5 46.6
200.0 18508.9 103.3
195.0 14854.0 117.9
190.0 10766.9 93.0
185.0 6772.9 74.1
180.0 3379.6 34.5
175.0 1221.3 19.2
170.0 289.1 4.7
165.0 45.8 0.9
160.0 8.6 0.3
155.0 4.8 0.6
150.0 5.0 0.6
70
temperatures for the 3rd charge of sulfur into the apparatus.
120.0 11.7 0.4

125.0 10.3 0.3
130.0 9.0 0.1
135.0 7.9 0.3
140.0 6.8 0.2
145.0 5.8 0.2
150.0 5.0 0.2
155.0 4.3 0.2
160.0 5.1 0.2
165.0 8750.7 154.0
170.0 33130.0 481.8
175.0 56918.3 622.4
180.0 73086.8 688.3
185.0 81452.1 537.9
189.8 82793.3 735.7
195.0 79104.5 382.4
200.0 72593.8 538.2
205.0 65071.8 558.8
210.0 55928.5 636.7
215.0 46370.9 672.0
220.0 38693.4 100.3
225.0 32255.6 78.7
230.0 26428.6 105.0
235.0 21366.7 81.5
240.0 13009.4 89.5
71
Table 8. Continued.
245.0 13687.3 88.6

240.0 13009.4 89.5
235.0 12796.3 31.3
230.0 13164.3 76.4
225.0 11518.1 72.7
220.0 11058.3 20.8
215.0 9548.4 15.9
210.0 8667.3 12.8
205.0 7484.5 25.9
200.0 6100.1 35.8
195.0 4552.4 55.5
190.0 3070.0 46.6
185.0 1765.0 23.6
180.0 794.6 21.8
175.0 261.3 11.0
170.0 76.3 3.9
165.0 24.3 1.4
160.0 10.7 0.8
155.0 7.3 0.5
150.0 6.7 0.5
145.0 6.9 0.5
140.0 7.6 0.5
135.0 8.4 0.4
130.0 9.5 0.5
125.0 10.8 0.5
120.0 12.1 0.7
72
temperatures for the 4th charge of sulfur into the apparatus.
120.0 11.1 0.7

125.0 9.6 0.5
130.0 8.5 0.7
135.0 7.4 0.5
140.0 6.4 0.6
145.0 5.5 0.5
150.0 4.7 0.8
155.0 4.1 0.5
160.0 33.5 14.1
165.0 16702.7 323.1
170.0 45578.5 465.2
175.0 70435.2 634.0
180.0 85771.8 967.3
185.0 92354.8 793.1
190.0 92142.1 699.9
195.0 87065.1 851.7
200.0 79533.3 473.5
205.0 70865.3 1088.5
210.0 61907.3 513.0
215.0 53083.0 955.7
220.0 45091.8 3082.0
225.0 38754.7 548.1
230.0 32509.3 153.2
235.0 27310.1 189.7
235.0 26110.9 181.0
73
Table 9. Continued.
230.0 30019.1 351.3

225.0 34215.0 234.0
220.0 38568.5 230.6
215.0 42990.3 216.8
210.0 47119.1 229.9
205.0 50406.3 270.8
200.0 52455.3 260.0
195.0 52386.1 234.0
190.0 49260.2 283.3
185.0 42638.0 218.6
180.0 32484.6 161.6
175.0 19785.3 275.2
170.0 7101.2 166.6
165.0 826.2 26.6
160.0 10.6 1.0
155.0 4.8 0.8
150.0 5.0 0.7
135.0 7.4 0.7
130.0 8.6 0.4
125.0 9.7 0.5
120.0 11.1 0.5
74
The probability distribution characterized by this measurements’ results and their standard
uncertainties, were assumed to be normal. Therefore, the δ of each set of measurements was
estimated to be twice the standard deviation in agreement with the NIST’s convention for coverage
factor, c = 2 ( i.e. 2 x standard deviation), equivalent to 95 % confidence interval.69 However,
because the number of data points per measurement at each temperature varied from five to thirty,
depending on the shear rate at which molten sulfur becomes non-Newtonian, c was therefore
obtained individually for each measurement based on the t-distribution, which takes the degrees
of freedom, v into consideration.
The maximum viscosity, ηmax, of molten sulfur obtained for the 1st, 2nd and 3rd charges charges of
sulfur into the apparatus were approximately 32,000 cP; 56,000 cP and 83,000 cP respectively.
These values are not consistent and are significantly lower than the ηmax value of 93,000 cP
reported by Bacon & Fanelli.2 Finally, for the 4th charge, the heating run matched the data of Bacon
& Fanelli, while the cooling measurements still showed lower ηmax value than the heating
measurements as presented in Figure 16.
75
100000
4th Charge
80000
Bacon & 3rd Charge
Fanelli
Heating
η / cP
60000
2nd Charge
40000 1st Charge
20000
0
140 160 180 200 220 240 260 280
T/°C
Figure 16. Average measured Newtonian viscosity data of molten sulfur as a function of
temperature for the first four charges. ●, heating run of the 1st charge; ○, cooling run of the 1st
charge; ♦, heating run of the 2nd charge; ◊, cooling run of 2nd charge; ■, heating run of the 3rd
charge; □, cooling run of the 3rd charge; ▲, heating run of the 4th charge; ∆, cooling run of 4th
charge ✲, data of Bacon & Fanelli.
4.1.1 The FT-IR Spectroscopy Results
The FT-IR spectroscopy analysis (Figure 17) for the first, second, third and fourth charges shows
total H2S (H2S + H2Sx) contents of 36.1 ppm, 30.7 ppm, 152.0 ppm and 81.0 ppm respectively.
This H2S is believed to be the product of reactions of • Sn• with the hydrocarbons (HCs) of which
the viscosity and rheology standards are made as illustrated in reaction 1 - 2.13 As a result there
was a larger modification of viscosities for the 1st charge where more HCs were available in the
76
pressure cell than the 2nd charge. For this reason, the 1st charge had a higher dissolved total H2S
compared to the 2nd charge. However for the 3rd charge, the maximum temperature of
measurements was increased from 220 °C of the 2nd charge to 250 °C, to further react away
possible impurities in the pressure cell. This produced 152.0 ppm of total H2S in the sample as
shown in Figure 17. It appeared that much of the available HCs reacted away during the 3rd charge
as evident by the lack of a visual peak in the 2900 cm-1 HC region of the IR spectrum for the 4th
charge, making the heating run of 4th charge match the data of Bacon & Fanelli (Figure 16).
2.0
4th Charge;
81.4 ppm (H2S + H2Sx)
1.5
3rd Charge;
152.0 ppm (H2S + H2Sx) 2nd Charge;
30.7 ppm (H2S + H2Sx)
A. U.
1.0
1st Charge;
36.1 ppm (H2S + H2Sx) 0.5
H2Sx
RH
H2S
0.0
3000 2900 2800 2700 2600 2500 2400 2300 2200 2100 2000
Wavenumber / cm-1
Figure 17. FT-IR spectra of the 1st, 2nd, 3rd and 4th charges showing the total H2S (H2S + H2Sx)
content and peaks.
77
The hysteresis between the heating and cooling curves of each charge and the examination of the
FT-IR analysis results led to the thought that trace amounts HCs, which might be present in the
loaded molten sulfur (99.992%) could react at T > 200 °C to produce H2S that modified the
viscosity of the cooling curves.13 Note that the only measurement of Bacon & Fanelli from which
both the heating and cooling experimental data matched using their purified sulfur were carried
out up to a maximum T of 210 °C.2,6 Another possibility is that the equilibration time of two hours
at each T might not be sufficient to establish a dynamic equilibration between all sulfur species
present. To test the validity of the first hypotheses, before further measurements were made, the
pressure cell was loaded with fresh molten sulfur and its temperature held at 295 °C for four days
to ensure that possible remnant of HCs in the pressure cell were reacted away. Subsequent
measurements which were the 5th, 6th, 7th and 8th charges are plotted in Figure 18, while the data
are presented in Appendix B; Tables 12, 13, 14 and 15.
It must be noted however, that the instrument developed electrical faults and could not hold the T
long enough for equilibration on many occasions during the course of measurements for the 5th to
the 8th charge. During this period, the electrical contact points of the pressure cell resistive heating
were modified, by placing contact points outside the heated zone. Corrosion issues were evident
with the manufacturer using brass and silver within the base of the heating mantle. Sulfur vapour
also corroded the electronics of the instrument above the pressure cell and the instrument was
eventually sent back to the manufacturer for repairs. This accounted for the missing data points for
some cooling measurements in Figure 18. The ηmax recorded for all these measurements were
≈ 104,000 cP, which is 10 % higher than ηmax for the 4th charge and the literature value of
Bacon & Fanelli. This could be as a result of a systematic effect in the instrument as it began to
78
fail. Nevertheless, the heating plots of the 5th, 6th, 7th and 8th charges have a good agreement. Even
though, the heating curves still did match the cooling curves for each of these charges, the ηmax of
the cooling run consistently increased. This is attributed to the pressure cell kept getting cleaner of
HCs with each passing charge evident in the total H2S becoming significantly low, reaching a
concentration of 3.8 ppm for the 7th charge and 3.0 ppm for the 8th charge (Table 10).
100000
7th Charge
8th Charge
80000
Bacon &
Fanelli
60000
η / cP
6th Charge
40000
5th Charge
20000
0
140 160 180 200 220 240 260 280
T/°C
Figure 18. Measurements data of average Newtonian viscosity of molten sulfur as a function of
temperature for different charges. ●, heating run of the 5th charge; ○, cooling run of the 5th charge;
♦, heating run of the 6st charge; ◊, cooling run of 6st charge; ■, heating run of the 7th charge; □,
cooling run of the 7th charge; ▲, heating run of the 8th charge; ∆, cooling run of 8th charge ✲,
data of Bacon & Fanelli.
79
Table 10. Total H2S (H2S+H2Sx) content from FTIR analysis of each charge.
Charge Tmax / °C H2S / ppm H2Sx / ppm Total / ppm
1 210.0 9.2 26.8 36.0

2 220.0 6.0 24.7 30.7
3 240.0 82.6 69.4 152.0
4 240.0 1.9 79.5 81.4
5 220.0 0.2 0.5 0.7
6 280.0 1.7 39.2 40.9
7 280.0 0.1 3.7 3.8
8 280.0 0.1 2.9 3.0
9 280.0 0.2 0.7 0.9
10 280.0 0.2 0.7 0.9
It became important to also look at the equilibration time of the molten sulfur and possibility of
trace impurities still present being responsible for the modification of the viscosity of molten sulfur
at high T. Because the equilibration time was two hours at each T before measurements were made,
further measurements were made with equilibration time of four, and six and eight hours while
cooling the sample to check the possibility of recovery of the viscosity within these time durations.
There was no significant effect of increased equilibration time up to eight hours on the cooling
viscosities of molten sulfur. However, for the same sample, repeating the heating run immediately
leads to lower viscosity measurements values for both the heating and the cooling run. By keeping
the sample at 155 °C for 96 hours or more the heating curve was reproduced while the cooling
curve consistently showed increased maximum viscosity. Because smaller amount of HCs were
available to react to modify the viscosity of sulfur at high T as sequential measurements were made
80
on the same sample, leading to smaller viscosity modifications. Whereas for a freshly loaded
molten sulfur, approximately the same concentration of HCs were available to react to modify the
viscosity of molten sulfur. From this, it can be concluded that the equilibration time was not
responsible for the anisotropy of the cooling curve and the small amount of hydrocarbon impurity
in the initial sulfur could be responsible for the anisotropy. The FT-IR analysis of the 9th, 10th and
subsequent charges showed no significant H2S while the total carbon content analysis on the
sample showed the samples having the same total HCs of 50 ± 10 ppm before and after measuring
the sample in the pressure cell of the MCR 302 rheometer. This anisotropy observed can therefore
be attributed to trace amount of HCs that are present in the molten sulfur reacting with sulfur
diradicals to produce H2S which further react to modify the viscosity of the molten sulfur at
T > 210 °C.10,13
4.1.2 Average Measured Newtonian Viscosity Data of Liquid Elemental Sulfur
After the instrument was repaired, important temperatures were selected and programed into the
instrument for measurements. The following temperatures: 120, 155, 175, 187, 200, 240 and
280 °C were chosen because of the abrupt changes to the viscosity of liquid elemental sulfur
observed at these temperatures during the previous eight charges. This would allow the completion
of a number of charges within a shorter time. Also, a shear rate range of 1 - 1500 s-1 was chosen
instead of the 1 - 3500 s-1 used for the previous measurements. This was based on the fact that no
significant changes in the flow behaviour of molten sulfur were observed between 1500 - 3500 s-
1
from the results of the previous charges.
81
The heating runs of the measurements obtained for the 9th - 14th charges were averaged and
presented Table 11. Also, the heating runs measurements data of these charges are plotted in
Figure 19 just like many previous authors.2,29,49 It appears from this study that this was as a result
of the difficulty they encountered in their attempt to reproduce a similar η measurement while
cooling the sample.
temperatures, averaged for the 9th - 14th charges of sulfur into the apparatus.
120.0 11.1 0.7

125.0 9.6 0.5
130.0 8.5 0.7
135.0 7.4 0.5
140.0 6.4 0.6
145.0 5.5 0.5
150.0 4.7 0.8
155.0 2.8 1.2
160.0 2.0 0.2
165.1 5415.4 653.4
170.1 30236.2 816.1
175.1 59445.6 950.8
180.1 80551.3 886.4
185.0 91662.4 698.6
187.0 92689.8 489.8
190.1 92864.8 1631.0
82
Table 11. Continued.
195.0 91896.6 671.6

200.0 85089.1 936.5
205.0 76695.4 1289.6
210.0 67942.7 88.3
215.0 59163.6 580.0
220.0 51123.5 676.2
225.0 43546.3 618.8
230.0 36573.3 493.9
235.0 31044.0 155.9
240.0 25802.7 570.6
245.1 21535.7 112.5
250.1 17936.2 282.1
255.0 15092.4 246.8
260.1 12454.7 401.3
265.0 10389.4 99.1
270.0 8600.6 230.1
275.1 6983.9 323.6
280.1 6008.0 330.6
83
100000
80000
60000
η / cP
40000
20000
0
140 160 180 200 220 240 260 280
T/°C
Figure 19. Experimental Newtonian viscosity data and models of molten sulfur as a function of T.
✲, experimental data of Bacon & Fanelli;6 –, fittings of Shuai & Meisen;9 □, average experimental
Newtonian viscosity from this study; –, calibrated reptation model of Cates.55
4.1.2.1 Re-Optimising the Modified Reptation Model
There are discrepancies in the literature values of B in equation 2-24. The original value of B by
Cates was therefore kept, while parameters A, C and λ of equations 2-21 to 2-24 were optimised
by minimising the sum of squares using generalized non-linear algorithm. The experimental data
of Ruiz Garcia et. al., Bacon & Fanelli and those obtained from this study were all fitted, the non-
linear algorithm did not converge well.2,29 However, when all four parameters were optimised, a
good fit was found as
84
k  17960 
 7.31013 exp  , (4-1)
 2
 T 
And was plotted in Figure 19. Also, this equation is more sensitive to B than A, and A than C, while
λ was close to unity for each of the fitting attempts in agreement with equation 2-24. The sum of
squares due to error (SSE) between the experimental data and equation 2-24 is 2.5 x 1011, while
the SSE after optimization (equation 4-1) gives 2.8 x 108.
4.2 Non-Newtonian Viscosity Measurements Results of Liquid Elemental Sulfur
4.2.1 Rheology of Sulfur in Mid-Shear Rate Range
During the injection of molten sulfur into underground reservoirs, different γ̇ regimes will be
encountered. Pumping and pipe flow are two important processes with established γ̇ regimes that
are usually encountered during most sulfur transport operations. The mid-shear rate range which
spans from 1 to 1000 s-1, is encountered during pumping processes and pipe flow operations.71,72
The rheology of molten sulfur between 1 to 100 s-1, and 1 to 1000 s-1 at constant T intervals
bounded by 120 °C to 280 °C are summarized in Figure 20 and 21 respectively. The data plotted
are from the 9th - 14th charges of sulfur into the apparatus. Some of the isotherms are omitted for
the sake of clarity.
4.2.1.1 Rheology of Liquid Elemental Sulfur during Pipe Flow
When a sample in the pressure cell thickens and the M of rotation approaches 2 x 108 nNm, the
instrument continues to make measurements without further increment in γ̇ to maintain the
85
viscosity within a safe limit for the instrument. Figure 20 shows the flow behavior of molten sulfur
in shear rate range up to 100 s-1. The γ̇ at which molten sulfur undergoes shear thickening varied
as a function of temperature as can be seen in Figure 20 by the clustering of the red legends. Many
fluids comprise of molecules with irregular shapes and sizes, as shear rate increases, the relative
motion between fluid molecules increases causing them to align and easily move past one another
while reducing the viscosity of the fluids.33 This is the case for Shear thinning and Bingham fluids.
However, for shear thickening fluids, increasing shear rate causes densely packed fluid molecules
to be forced against one another, thereby filling the void spaces in the fluid and leading to increased
viscosity. In molten sulfur, as the average chain length increased, the molecules become more
closely packed causing more entanglements while making the slithering motion between sulfur’s
molecules slower.53,55,60 For each temperature, a shear rate is reached at which the molecules begin
to jam.55 At this point, further shearing at an increased rate would lead to a large resistance to shear
force as observed in the abrupt rise in η of isotherms represented by the red legends of Figure 20
and 21 before the instrument stops the increment of γ̇ in the shear thickening region to prevent
overloading.
86
100000 200 °C
205 °C
Shear thickening region
80000
175 °C
60000 220 °C
η / cP
230 °C
40000
170 °C
245 °C
20000
255 °C
275 °C
165 °C
0
0 20 40 60 80 100
-1
γ̇ / s
Figure 20. Measurement data of the η of molten sulfur as a function of γ̇ up to 100 s-1 at constant T.
□, Newtonian isotherms up to 1000 s-1; ∆, Newtonian isotherms up to 100 s-1 ; ○, shear thickening
isotherms at γ̇ ˂ 100 s-1. Some isotherms are intentionally omitted for clarity.
4.2.1.2 Rheology of Liquid Elemental Sulfur during Pump Operations
Most sulfur pumps operations are within the upper mid shear range which is up to 1000 s-1. The
viscosity measurements data of molten sulfur in this region are presented as a function of shear
rate in Figure 21.
87
100000
165 °C ˂ T ˂ 240 °C
80000
60000 Shear thickening region

η / cP
40000
T ≤ 165 °C
T ≥ 240 °C
20000 T ≤ 165 °C
T ≥ 275 °C
0
0 100 200 300 400 500 600 700 800 900 1000
γ̇ / s-1
constant T. □, Newtonian isotherms up to 1000 s-1; ∆, Newtonian isotherms up to 100 s-1 ; ○, shear
thickening isotherms at γ̇ ˂ 100 s-1. Some isotherms are intentionally omitted for clarity.
The following observations can be made from both Figures 20 and 21. Isotherms of liquid sulfur
at T ≤ 165 °C and T ≥ 275 °C are Newtonian for the entire mid-shear rate range i.e. up to 1000 s-1.
In addition to the relatively low η, ≈ 10,000 cP in this region, this flow behavior implies that molten
sulfur can be handled without the challenge of shear thickening. Likewise in considering the shear
rate range up to 100 s-1, isotherms T ≤ 165 °C and T ≥ 240 °C are Newtonian, making 240 °C to
275 °C a suitable temperature range for shear operations up to 100 s-1.
88
Unlike the flow behaviours discussed above, liquid sulfur becomes shear thickening at different γ̇
known as the critical rate of shear thickening, γ̇ cr, below 100 s-1 within the temperature range
165 °C ˂ T ˂ 240 °C as seen in the sharp increase of η in Figures 21 and 22. A plot of η and γ̇ cr as
a function of T is presented in Figure 22.
100000 400
350
80000
300
250
60000
γ̇ cr / s-1
η / cP
200
40000
150
100
20000
50
0 0
140 160 180 200 220 240 260 280
T/°C
Figure 22. Newtonian viscosity data and critical rate of shear thickening of molten sulfur as
functions of T. □, average experimental Newtonian viscosity from this study; –, calibrated
reptation model of Cates;55 ○, average critical rate of shear thickening from this study.
89
The γ̇ cr of liquid sulfur decreases from the on-set of its λ-transition at T ≈ 160 °C as η rise and T
increases up to 187 °C. The minimum γ̇ cr for the entire sulfur’s liquid temperature range is 30 s-1,
observed at T = 187 °C and η ≈ 92,300 cP. This coincides with the T at which molten sulfur
possesses the longest average chain lengths.52,73 From this point, the γ̇ cr of liquid sulfur begins to
increase as the T increases and η decreases.
90
Chapter Five: CONCLUSIONS AND FUTURE DIRECTIONS
The difficulty many authors encountered in establishing the viscosity data of liquid elemental
sulfur has been a result of the impurities in the sulfur.5,10,11 Bacon & Fanelli established a rigorous
procedure with which they eliminated most of these impurities before making viscosity
measurements, which even today are highly acceptable in the literature. However, it has been over
seventy years since their data were published. A new Anton-Paar MCR 302 rheometer was
commissioned and set up to validate the viscosity data of molten sulfur and for the first time,
investigate its rheometric properties. Viscosity and rheology standards were measured using this
instrument with certified values found well within the 99.7 % confidence interval for all the
standards except the low viscosity N600, with measurements within 99.5 % confidence interval of
certified values for the viscosity range of interest. The sulfur prill used for this study has a purity
of 99.992 % in order to get reliable results. However, the measured standards were difficult to
clean out of the pressure cell and therefore contaminated it. The hydrocarbons of which these
standards were made reacted to produce H2S which modified the viscosity of the measured molten
sulfur samples until the 4th charge where the pressure cell was clean enough that the measurements
matched viscosity data of Bacon & Fanelli.2 Despite this breakthrough for the 4th charge, the
viscosity measurements data for the cooling run were still lower than those for the heating run,
possibly as a result of equilibration or reactions at high temperature.
This anisotropy persisted even after the next four charges of loading fresh molten sulfur samples
into the system, while the sequential heating measurements still showed a good repeatability. The
equilibration time was varied from two to eight hours while cooling the liquid sulfur samples to
91
check the possibility of recovery of the viscosity within these time durations. There was no
significant effect of increased equilibration time up to eight hours on the cooling viscosities of
molten sulfur. The FT-IR analysis of 9th to the 14th charges showed that no significant H2S was
produced in the sample while the total carbon content analysis on the sample also showed the
samples having the same total carbon content of 50 ± 10 ppm before and after measuring the
samples in the pressure cell of the MCR 302 rheometer. The anisotropy observed in each charge
even after the pressure cell appeared to be clean of impurities can therefore be attributed to trace
amount of HCs in the molten sulfur reacting at T > 210 °C. The Newtonian sulfur viscosity data
reported in this study is the average viscosity measurements for the heating runs of the 9th - 14th
charges. The uncertainty in the viscosities were reported at 95.5% confidence interval.
In this study it was also established that liquid sulfur is not Newtonian over its entire liquid range.
The shear rate at which molten sulfur becomes shear thickening varies from ≈ 30 to 100 s-1 with
the minimum shear rate of ≈ 30 s-1 at 187 ° C. Even though, the shear rates applicable for molten
sulfur injection cannot be fully established in this study, two important processes with established
shear rate ranges, and relevant to most molten sulfur transport processes were examined. These
processes fall within the mid-shear rate range: the liquid pipeline transportation (1 to 100 s-1) and
liquid pumping processes (1 to 1000 s-1). The following conclusions can be drawn from the study
of the rheology of molten sulfur in the mid-shear rate range:
(1) Isotherms at T ≤ 165 °C and T ≥ 275 °C appeared to be Newtonian up to 1000 s-1.
(2) Isotherms at T ≤ 165 °C and T ≥ 240 °C appeared to be Newtonian up to 100 s-1.
92
(3) Isotherms between 165 °C ˂ T ˂ 240 °C appeared to be shear thickening at different γ̇ below
100 s-1.
The immediate follow-up work is to obtain sulfur better than 99.992 % to confirm that trace HCs
were entirely responsible for the anisotropy observed in this study. Note that Bacon & Fanelli
reported a reversible viscosity profile with their purified sulfur at 210 °C.6 With even higher purity,
we may be able to show isotropic profiles at higher temperatures.
Once it can be demonstrated that the low-shear viscosities are not anisotropic due to reaction of
impurities, it will be important to revisit the modifying effect of dissolved H2S and H2Sx.
Fanelli (1946), in his work on modifying the viscosity of sulfur, reported the modifying effect of
the viscosity of liquid sulfur as a function of the head pressure of H2S on the molten sulfur. Rubero
(1964), believed Fanelli’s work under-predicted the modifying effect of H2S on the viscosity of
molten sulfur because some of the H2S was lost during the sealing process of the viscometer used
for Fanelli’s measurements.58 He therefore used a different capillary viscometer in a closed system
to measure the modifying effect of H2S on the viscosity of molten sulfur. As he predicted, there
was an increase in the modifying effect of the viscosity of molten sulfur from the same head
pressure of H2S put on molten sulfur compared to Fanelli’s data. However, none of these authors
looked into how much of H2S was actually dissolved into the molten sulfur causing the
modification. It will be desirable to measure these effects using the established FT-IR spectroscopy
technique to analyze the molten sulfur after it is put under a known head pressure of the impurities
and to correlate the lowering of the viscosity that results with known concentrations of the
H2S.24,59,60 It would be interesting to determine if there is still a shear thickening when the H2S has
93
modified low-shear viscosity, i.e., is the shear thickening limit predictable from the low-shear
viscosity? Finally, the previously discussed theoretical models can be tested for H2S modified
elemental sulfur, which should have shorter chain lengths.
Other impurities that have also been suggested but are yet to be studied for their effects on the
viscosity of molten are SO2 and amines (MEA, DEA and MDEA) , which can be present in a Claus
plant where molten sulfur is produced. In addition, the rheology of the sulfur modified by these
impurities will be useful to optimize many flow processes involving molten sulfur.
94
Figure 23. Block diagram of the the VI used to log on pressure measurements from the Keller
pressure transducer to a computer system.
95
Figure 23. Continued.
96
Figure 23. continued.
97
150.0 52.2 2.3

155.0 50.1 1.8
160.0 61.9 1.4
165.0 16972.5 723.2
170.0 49559.4 1237.5
175.0 78084.7 2443.4
180.0 96649.0 2529.6
185.0 104461.1 2376.2
190.0 104699.9 513.0
195.0 99383.3 977.0
200.0 91505.8 1214.9
205.0 81723.3 958.7
210.0 71910.6 941.5
215.0 61958.3 828.0
220.0 53373.2 152.0
220.0 51469.8 905.5
220.0 51540.0 441.9
220.0 51327.1 444.3
215.0 58588.6 389.7
210.0 66329.3 610.5
205.0 73938.3 1517.4
200.0 80142.0 1962.8
195.0 84580.1 2224.8
98
190.0 84566.7 2625.0

185.0 78623.5 1805.6
180.0 64997.1 755.3
175.0 44438.2 682.2
170.0 20470.4 117.7
165.0 3104.1 79.0
160.0 61.4 83.1
155.0 54.5 58.5
150.0 54.5 65.5
155.0 3.8 1.1

160.0 2.3 0.9
165.0 4234.3 519.5
170.0 31444.9 1441.2
175.0 66831.3 1254.1
180.0 86898.6 465.1
185.0 99477.0 1546.1
190.0 103096.9 2182.3
194.9 101333.0 952.5
200.0 94049.2 1947.0
205.0 85744.7 530.1
99
210.0 77243.7 548.4

215.0 65489.5 116.9
220.0 56269.8 815.0
225.0 48075.5 130.8
230.0 40566.6 473.0
235.0 33818.9 557.6
240.0 28721.7 186.5
245.0 23289.9 914.3
250.0 19202.3 601.8
255.0 16146.7 582.8
260.0 13486.5 604.6
265.0 11259.5 212.0
270.0 9136.5 506.2
275.0 7718.7 274.4
280.0 6466.1 256.6
280.0 6390.1 10.6
275.0 7348.3 393.8
270.0 8556.1 283.2
265.0 9751.1 474.1
260.0 11450.1 10.6
255.0 13219.6 143.0
250.0 15284.3 331.4
245.0 17440.8 473.9
240.0 19829.5 478.7
235.0 22577.1 506.2
230.0 24967.1 1060.1
100
225.0 27553.9 1237.2

220.0 29203.4 549.6
215.0 30750.0 385.8
210.0 31267.6 636.1
205.0 30964.8 464.4
200.0 28563.6 322.0
195.0 24868.2 1327.0
190.0 19384.8 936.5
185.1 12908.7 978.3
180.0 6546.0 241.9
175.1 2544.5 946.9
120.0 7.3 4.3

160.0 2.7 0.4
180.0 85636.5 2404.1
185.0 98942.6 4154.2
190.0 102506.7 2103.4
195.0 100007.4 1524.3
200.0 93351.0 1871.1
240.0 29191.9 835.8
280.0 6886.1 357.1
101
280.0 6950.6 91.7

240.0 23643.6 417.0
200.0 47681.5 671.9
195.0 44675.0 391.0
190.0 38953.5 779.1
185.0 29380.0 1242.3
180.0 18638.0 1760.0
160.0 2.6 1.5
140.0 3.4 6.1
120.0 10.2 1.1

160.0 2.6 0.8
175.0 69916.1 1932.5
180.0 90775.9 1013.2
185.1 102723.1 276.6
190.1 105658.5 245.3
195.0 103298.8 3415.8
200.1 93967.8 736.3
240.0 29083.2 574.4
240.0 28263.7 183.1
280.0 6836.5 90.8
102
280.0 6739.6 94.7

240.0 25046.4 452.5
200.0 55844.9 420.6
195.0 53183.7 201.4
190.1 47027.4 95.8
185.1 37424.3 489.2
180.0 24458.5 601.9
175.0 10921.4 156.7
160.0 3.7 476.5
120.0 2.9 1.0
103
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UNIVERSITY OF CALGARY

Rheometric Properties of Pure Liquid Elemental Sulfur

Gabriel Oluwaseyi Sofekun

SUBMITTED TO THE FACULTY OF GRADUATE STUDIES

IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE

DEGREE OF MASTER OF SCIENCE

GRADUATE PROGRAM IN CHEMISTRY

© Gabriel Oluwaseyi Sofekun 2017

region. Sulfur’s viscosity increases from ≈ 10 cP upon melting at T = 115 °C to ≥ 90 000 cP at

and their insightful questions during the committee meetings.

rheometer whenever it developed electronics faults.

support they offered me throughout my studies.

in Applied Sulfur Chemistry University of Calgary, Department of Chemistry Graduate

Gbenga and IBK for all their support.

Uncle Nat Sofekun

CHAPTER ONE: INTRODUCTION ..................................................................................1

CHAPTER TWO: REVIEW OF LITERATURE DATA, EXPERIMENTAL TECHNIQUE

CHAPTER THREE: EXPERIMENTAL METHOD AND PROCEDURE ......................47

CHAPTER FOUR: RESULTS AND DISUSSION...........................................................68

CHAPTER FIVE: CONCLUSIONS AND FUTURE DIRECTIONS ..............................91

Table 1. Advantages and disadvantages of different rheometers. ................................................ 28

Table 2. Relevant parameters for deadweight calibration ............................................................ 53

Table 4. Certified values for NIST rheology standard-SRM 2490. ............................................. 60

Figure 4. Common fluids flow behaviours. ................................................................................. 17

Figure 7. Experimental literature data of sulfur’s viscosity. ........................................................ 35

Figure 8. Front panel of the VI to log pressure from the transducer............................................ 48

Figure 15. Measurements of NIST’s SRM 2490: ........................................................................ 63

Acs Specific area

as Entropy (S) term due to end effects

A.U. Arbitrary unit

bd Pressure distortion coefficient

bs Entropy (S) term due to chain lengths

CEN European Committee for Standardization

COM Data communication line

CR Shear rate controlled

CS Shear stress controlled

DWT Dead weight tester

d1 Width of suspension at the top of a lever system

d2 Width of suspension at the bottom of a lever system

dh Thickness of a body under shear stress

FT-IR Fourier Transform Infra-red

g Acceleration due to gravity

gl Local acceleration due to gravity

kT Temperature dependent constant

Kx Equilibrium constant for sulfur radical formation reaction

Kp Equilibrium constant for sulfur radical propagation reaction

LabVIEW Laboratory Virtual Instrument Engineering Workbench

l Length of suspension in a pulley system

L Depth of inner cylinder in a concentric cylinder geometry rheometer

Lc Length of capillary viscometer

Mav Average molecular weight

MCR Modular Compact Rheometer

mp Mass of a suspended body in a pulley system

Mx Ratio of halogen atoms to sulfur atoms

m Flow index or power law viscosity index

NIST National Institute of Science and Technology

pcorr Corrected deadweight pressure

PRT Platinum resistant thermometer

PID Proportional, integral and differential control action

Q Volumetric flow rate

𝑟̅ 2 Root-mean-square end-to-end average chain length of a polymer

R Ideal gas constant

Ro Radius of the outer cylinder of a concentric cylinder rheometer