CME 458/459 Special Projects

DEPARTMENT OF CHEMICAL AND MATERIALS ENGINEERING

Course Objectives:

CME 458/459 are individual research projects under the supervision of an academic faculty
member, and may be taken by either a Chemical or Materials student. A list of topics for the 2012-
2013 Fall, Winter and Spring/Summer terms is given under the title labeled Project Descriptions.
The conditions and procedures for registering in CME 458/459 are given below. A final written
report will be required for each project. A CME 458/459 project may not be combined with a
Dean’s Research Award as the Award “can’t be concurrent with a project for which credit is
received.”

1. Only students with GPA  3.0 in the last two academic terms may register in CME 458/459.

2. Students who plan to register in CME 458/459 should select a project, usually from the list, and
discuss the selected project with the professor who proposed the project.

3. Students who would like to pursue a project not included in the list should discuss such a
project with the professor whom they consider best qualified as supervisor of the project. A
brief written project description must be prepared and the project must be approved by the CME
458/459 coordinator.

4. Complete the attached PROJECT Selection Form (2012-13) and return the completed form
(one form for each student registered in CME 458/459) to the course coordinator as soon as
possible.

5. Registration in CME 458/459 must be done for you by Heather Green (ECERF reception area).
A completed Project Selection Form (2012-13), given on the next page, signed by the project
supervisor and course coordinator will be required before you can register in CME 458/459.

6. Mark Distribution (Fall) Marks

Progress Report due by November 9, 2012 10% deducted from mark, if not submitted
Final Report due by December 5, 2012 100%

Mark Distribution (Winter) Marks

Progress Report due by March 15, 2013 10% deducted from mark, if not submitted
Final Report due by April 12, 2013 100%

7. The Progress Report should be 1-2 pages long, summarize the work done on the project and
tasks still to be performed.

All reports will be handed into the course coordinator; they will be distributed to the appropriate
supervisor(s).
Deadlines will be strictly enforced; late reports will be penalized 10% per working day unless
arrangements have previously made with the course coordinator.

Dr. Natalia Semagina

CME 458/459 Course Coordinator
 CME 458/459 Special Projects in Materials Engineering

DEPARTMENT OF CHEMICAL AND MATERIALS ENGINEERING

PROJECT SELECTION (REGISTRATION FORM)

Indicate which course you will be registering for:

CME458 _______ CME 459 ________

Term in which project is to be completed:

Fall Term (Sept-Dec) Winter Term (Jan-April) Spr/Sum Term (May-Aug)

Name of Student: _________________________________________

ID No. ________________
(Please print)
No. of Project in Listing: _______

Title of Project: __________________________________________________________________

Supervisor(s): ___________________________________________________________________
(Please print)

Signature of Supervisor(s): ________________________________________________________

Signature of Course Coordinator: __________________________________________________

Dr. Natalia Semagina

If your Project is not listed, please provide a short written description of the project to the Course
Coordinator.

** For CPC and Oilsands stream students only, approval required from appropriate advisor.

Please indicate program: Chemical CPC ________ Chemical Oilsands _________

Name: __________________________ Signature: _______________________________

(Please print) (Advisor)

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 CME 458-459 PROJECT DESCRIPTIONS, 2012-2013

Project 1: Behaviour of Solar Energy Harvesting Polymers

Supervisor: P. Choi
Type of Project: Theory and Computational
Number of Students: 2

Environmental issues related to energy production from fossil fuels and soaring crude oil
prices have been the main stimulants for the development of renewable energy resources. More
energy from sunlight strikes Earth in one hour than all of the energy consumed by mankind in an
entire year and finding a suitable way to capture this form of energy could definitely solve
energy concerns of the human race forever. Advent of organic semiconductors in the early 80s
made it possible to fabricate solar cells from polymers. The advantages of these so-called plastic
solar cells include lightweight, versatility of chemical structure, mechanical flexibility and ease
of processing (inexpensive). However, there are still two major hurdles that need to be overcome
and they are the power conversion efficiency (~ 8.3%) and durability (~ 1 year). It is expected
that efficiencies of 10% or higher and device lifetimes of around 10 years will make this
technology commercially viable.
The essence of the technology is that an electron donor polymer and an electron acceptor
polymer are mixed together in a small cell so that electrons liberated from the electron donor
polymer as a result of the impingement of sunlight would flow to the electron acceptor. To
facilitate the charge transport process between the two polymers in the cell, a nano-scale highly
interconnected structure is needed. The challenge of this technology is to identify the molecular
structures of the polymer pair that have the required electronic properties and at the same time
would thermodynamically form the desired interconnected morphology. In this project,
molecular dynamics (MD) simulation, Monte Carlo (MC) method and the rotational isomeric
state (RIS) model will be applied to study the miscibility of a selected pair of electron donor and
acceptor polymers to determine whether nano-scale highly interconnected morphology would
form.

Project 2: Simulation of Solid Particle Motion in Shear Flow

Supervisor: J. Derksen
Type of Project: Numerical
Number of Students: 1-2

Solid particles suspended in liquid is a common situation in nature (e.g. sediment

transport in rivers) and engineering (oil sands process streams, liquid fluidized beds). The
dynamics of solids and liquid are tightly linked: The solids are moved by the flowing liquid, and
the solids motion has impact on the behavior of the liquid. Numerical simulations can be used to
enhance our understanding of this coupling. In such simulations the equations of motion of solid
and liquid are solved by taking small, discrete time steps. As a first, simple case a spherical
particle in a shear flow will be considered. We will study the motion (translation and rotation) of
the particle, and see how it affects the liquid surrounding it.

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Project 3: Fitting Imperfect, but Rare and Valuable, Data
Supervisors: J. A. W. Elliott and V. Prasad (in collaboration with Locksley McGann, Lab.
Medicine and Pathology)
Type of Project: Numerical
Number of Students: 1 (Sep-Dec 2012 OR Jan-April 2013)

When an engineer encounters a data set that cannot be accurately fit to equations to
obtain the best values of coefficients that the experiment was meant to deliver, the usual thing to
do is to design a new experiment to deliver better data. But what if the experiment cannot be
repeated? Such a problem is encountered in practice with space experiments or biological
experiments on endangered or extinct species.
Cryobiology is the study of life at low temperatures with an important application of
preservation of reproductive cells for the maintenance of genetic diversity in small or isolated
populations such as of endangered animals in zoos or wild-life preserves. Osmotic parameters
(such as cell membrane water permeability) are important parameters that can be used to develop
cryopreservation protocols for cells. These parameters are obtained by measuring cell volume
response to anisotonic solutions and fitting to known equations. Experimental data on osmotic
responses of spermatozoa from endangered clouded leopards were collected in 1999 on a project
led by Dr. Budhan Pukazhenthi of the Smithsonian Conservation Biology Institute, Front Royal,
Virginia, USA. This data set has some problems and so it has not been used to obtain the cell
parameters by fitting to equations.
In this project, the student will use statistical data analysis techniques to attempt to fit this
data (and other similar data sets) to obtain the best conclusions possible from the limited data
available.

Project 4: Solidification of an aluminum bulk amorphous alloy

Supervisor: H. Henein
Type of Project: Experimental
Number of Students: contact

Bulk amorphous metals are a new class of materials characterized by their amorphous
structure under low cooling rates of solidification. The resultant alloy has high hardness and low
ductility. Some of these new classes of alloys are incorporated into new designs of golf clubs. A
new Al based bulk amorphous alloy will be atomized and the structure characterized using x-ray,
and microscopy techniques. The hardness of the alloy will also be measured. A model of droplet
cooling will be used to estimate the droplet cooling rate prior to solidification. The resultant
structure and properties will be related to the droplet cooling rate.
Engineering objectives:
•Develop experimental testing strategy.
•Carry out atomization experiments.
•Use of various microscopy techniques to characterize the steel microstructure.
•Carry out x-ray diffraction analysis of powders.
•Use hardness measurements to estimate the mechanical properties of the warm rolled steel.
•Relate mechanical properties to the evolution of microstructure as described by quantitative
methods developed.

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Project 5: The Effect of Warm Rolling on the Morphology of Cementite in Low alloy Steels
Supervisor: H. Henein
Type of Project: Experimental
Number of Students: 2

Low alloy steels are used for down hole applications in the oil and gas sector. As down
hole conditions of oil and natural gas extraction are worsening, producers encounter the presence
of hydrogen sulfide with consequences such as sulfide stress cracking (SSC) instigated by
hydrogen. There is increasing evidence that the morphology of cementite in these quench and
tempered steels plays a role in the SSC behaviour. The objective of this project is to explore the
use of warm rolling as a processing strategy to modify the morphology of cementite. The project
will involve carrying out a literature review on the subject, plan and execute an experimental
warm rolling test matrix, followed by the quantitative characterization of the microstructure
using Optical and SEM microscopy, X-ray diffraction. In addition, other characterization
techniques such as hardness measurements may be used as needed. An analysis of the
experimental and characterization results will be carried out.

Project 6: Mn Oxide-based Supercapacitors

Supervisor: D. G. Ivey
Type of Project: Experimental Study
Number of Students: 1

Electrochemical capacitors or supercapacitors are energy storage devices capable of

delivering high power densities. Electrochemical capacitors are promising devices for back up
power storage, peak power sources and hybrid electric and fuel cell vehicles, due to their high
specific capacitances, high charge/discharge rates, long cycle life and excellent reversibility. The
energy stored in supercapacitors is either capacitive (non-Faradaic) or pseudocapacitive
(Faradaic) in nature. The non-Faradaic process relies on charge separation at the interface
between the electrode and the electrolyte giving rise to an electrical double layer (EDL) (e.g.,
activated carbon and carbon nanotubes), while the Faradaic process consists of redox reactions
occurring within the active electrode materials or at their surfaces (e.g., conducting polymers,
noble metal oxides such as RuO2 and IrO2 and transition metal oxides such as MnO2, NiO, V2O5
and MoO).
The primary challenges for supercapacitor technology that hinder market development
are low energy density and high cost. Hence, increased energy density and lower cost must be
achieved without sacrificing high power density and long life cycle. Because energy density is
directly proportional to capacitance, high surface area materials are very desirable for boosting
energy density. Furthermore, incorporating pseudocapacitive materials at the surface of high
surface area materials, or fabricating such materials directly to achieve a high surface area, will
increase the utilization of the active materials and significantly enhance supercapacitor
performance. This work will focus on developing thin film deposition techniques, which can be
used to fabricate nano-structured electrodes consisting of low cost Mn oxides.

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Project 7: Diffusion Barriers for Microelectronic and MEMS Applications
Supervisor: D. G. Ivey
Type of Project: Experimental
Number of Students: 1
The increasing effort to achieve smaller and faster microelectronic devices has resulted in
higher resistance in metal lines and larger RC-time delay. Low-resistance Cu interconnects,
therefore, have replaced Al interconnect technology in current Si-based microelectronics
technology. Copper offers a lower bulk resistivity compared to Al, i.e., 1-1.7 µΩcm for Cu vs 3-
3.5 µΩcm for Al, and a 400% reduction in RC-time constant can be achieved by using Cu
combined with a low dielectric constant material instead of Al/SiO 2. Furthermore, the activation
energy for electromigration in Cu (0.8-0.9 eV) is larger than that in Al (0.4-0.8 eV). Copper also
offers better resistance to stress voiding and, hence, provides better performance as a
metallization material under ultralarge scale integration device schemes. This material shift,
however, has the inherent problem of Cu interaction and diffusion through Si and SiO 2 layers
followed by early device failure. A diffusion barrier layer is, therefore, needed between the active
region of the device and Cu layer to prevent diffusion/drift under thermal/thermoelectrical
stresses. An ideal diffusion barrier must be conductive and also nonreactive with both Si and Cu
at the device operation temperature. Moreover, an amorphous structure with minimum defect
density and a high melting temperature can provide excellent performance in preventing
diffusion and intermixing. The main objective of project is to find a promising diffusion barrier
material that successfully prevents diffusion of Cu into Si and SiO 2 under severe operating
conditions.

Project 8: Improved Interconnects (IC) for Solid Oxide Fuel Cells

Supervisor: D. G. Ivey
Type of Project: Experimental
Number of Students: 1
Anode-supported, planar solid oxide fuel cells (SOFCs) have electrolytes which are
typically less than 20mm thick, and in many cases less than 10mm thick, permitting operation at
temperatures less than 800°C. Multiple planar SOFCs are stacked in series, to achieve sufficient
voltages for practical applications, necessitating the use of interconnects to electronically connect
anodes and cathodes to one another. In addition to being electronically conducting, interconnects
must be easily fabricated, be stable at operating temperatures, have similar thermal expansion
coefficients to other fuel cell components, have low ionic conductivity and be impermeable to
fuel and oxidizing gases. Candidate interconnect materials consist of two major types,
electronically conductive oxides, such as LaCrO3 and related ceramics, and oxidation resistant
metallic alloys, such as ferritic stainless steels. Ferritic stainless steels have many advantages
compared with their ceramic counterparts, including reasonable mechanical stability, much
higher thermal and electronic conductivities, little porosity, ease of fabrication and significantly
lower cost. Although not suitable for high temperature fuel cells (900-1000°C), they may be
used for lower temperature anode-supported cells. Long-term reliability in fuel cell environments
remains a concern; however, as the temperatures employed are pushing the limits of the steel.
The proposed research focuses on the development of reliable and cost-effective
techniques for producing fuel cell interconnects with satisfactory oxidation/corrosion resistance,
lower area specific resistances and lower susceptibility to cracking and spalling during fuel cell
thermal cycling. The approach taken will be to develop conductive and oxidation resistant
coatings using electrochemical deposition techniques.

Projects 9, 10.
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Supervisors: J. L. Luo and A. Afacan
Type of Project: Experimental
Number of Students:1 or 2

Fluid-to-solid and liquid-to-vapor mass transfer under flow-boiling and two-phase flow
are important to a range of phenomena currently relevant to the nuclear industry, e.g., materials
degradation of wide range of components, fouling of heat exchangers and steam generators,
radioisotope partitioning in low-level nuclear waste disposal sites, fate of chemical species under
accident conditions. Recent open literature indicates that the experimental data on materials
degradation and mass transfer under two-phase flow boiling are scarce. The lack of data can be
attributed to the experimental difficulties-the system capable of the preferred measurements
under two-phase flow boiling are rare and the interpretation of the data is challenging compared
to the single-phase equivalents. Since mass transfer measurements under two-phase flow boiling
are too complicated, we will first measure the mass transfer under single-phase and no boiling
condition and then we will investigate liquid solid mass transfer behavior at static boiling
condition.

Part I (Project 9): Mass Transfer Measurements under no Boiling Condition

Under no boiling condition, the liquid solid mass transfer rate has close relation to
diffusion- controlled corrosion. In many cases, the diffusion of dissolved oxygen to the corroding
metal surface such as copper and steel is the rate-determining step of the diffusion-controlled
corrosion. Many factors could influence this diffusion process, such as oxygen concentration
inside the liquid, temperature, liquid flow rate etc. An existing experimental method of rotating
disc electrode will be used to investigate the mass transfer controlled corrosion. The objectives of
this project are to complete extensive literature survey and to study the effects of dissolved
oxygen concentration inside the liquid, liquid temperature and liquid flow rate on diffusion-
controlled corrosion. The liquid solid mass transfer rate will be measured using limiting current
technology.

Part II (Project 10): Mass Transfer measurements at Boiling Condition and without flow
This part of the project is involved in measuring the liquid solid mass transfer under
boiling and without flow condition using electrochemical methods. A novel experimental set-up
is currently under construction to investigate the liquid solid mass transfer rate under boiling
without flow condition using limiting current technology. The objectives of this project are to
trouble-shout the experimental set up, to complete literature survey and to study the effects of
dissolved oxygen concentration inside the liquid, liquid temperature as well as at boiling point.
This study would be very significant because it provide the fundamental understanding of mass
transfer behavior at boiling condition i.e. gas bubbling at the solid surface and this is essential for
the next stage which involve a gas liquid two phase flow at boiling condition.

Project 11: Optimum Refining of C5 Naphtha

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Supervisor: A. de Klerk
Type of Project: Numerical
Number of Students: 1or 2

The refining pathway of C5 naphtha in a refinery is somewhat dependent on the

configuration of the other refinery units. The easiest strategy is to blend the C 5 naphtha directly
into the motor-gasoline. This has two drawbacks. Firstly, the C 5 naphtha has a high vapour
pressure and by including it directly into the motor-gasoline, it limits blending of butanes into the
motor-gasoline. The second drawback is related to the olefin content of the C 5 naphtha, since the
maximum olefin content in motor-gasoline is regulated. Olefins have a higher octane value than
paraffins, but in an olefin-rich refinery it is generally better to include heavier olefins into the
motor-gasoline, since the octane difference between olefins and paraffins increases with
increasing carbon number. The situation is even more complicated if one considers oxygenated
motor-gasoline. At present no guidelines exist for a priori recommending a C5 naphtha refining
strategy for refineries rich in olefins and oxygenates. The aim of this project is to provide such a
guideline.

Project 12: Study of the Dynamics of Reacting Systems using Extent-based Methods and
Computational Singular Perturbation
Supervisors: V. Prasad and A. de Klerk
Type of Project: Computational
Number of Students: 1

In systems with a large number of chemical reactions, it is often difficult to understand

the time scales at which different reactions and modes operate, and to find conditions that
activate specific subsystems of reactions. It is even more challenging to obtain this information
in open systems such as flow reactors, and when mass transfer effects are also present.
There are two techniques that can be used to solve this problem: the transformation of the
equations describing the reactions and mass transfer into extents of each reaction and mass
transfer process. This decouples each of the reaction and mass transfer affects. Once this
transformation is performed, computational singular perturbation (CSP) may be used to break up
the model of the chemical reaction system into sub-systems of reactions that operate at different
time scales. Once this is done, input manipulations can be designed in order to activate desired
reaction subsystems and suppress undesirable reactions.
In this project, the objective is use the extent-based methods and CSP together study the
dynamic behaviour of ammonia decomposition and Fischer-Tropsch synthesis, and to use the
understanding of the behaviour to devise dynamic operating strategies that optimize objectives
such as conversion, selectivity or product profiles. The work involves combining existing Matlab
code for the extent-based transformation and CSP, and for ammonia decomposition and Fischer-
Tropsch chemistry, and conducting simulations to understand and optimize operating conditions.

Project 13: Dynamic Scaling Laws for Chemical Systems

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Supervisor: V. Prasad and P. Mendez
Type of Project: Computational
Number of Students: 1

Scaling laws, leading to power law based models, have been used to describe and explain
the behavior of many chemical, physical and biological systems. Scaling laws may be derived
from statistical data on a particular class of systems through an implementation of dimensional
analysis. Imposing the condition of dimensional correctness leads to a constrained regression
problem, and enables us to identify the most relevant (dimensionless) groups of parameters that
affect the system and rank them.
Currently, methods exist for the generation of scaling laws with dimensional correctness
for static (steady-state) systems, and for the generation of scaling laws for dynamic systems
without the imposition of dimensional correctness. In this project, the student will extend and
couple the methods to develop a class of scaling laws for dynamic systems with the constraint of
dimensional correctness. This approach will be extended to solving the problem of identifying
the structure, and not just the parameters, of the model that describes the system. The work
involves extending existing Matlab code for building scaling law based models to dynamic
systems, studying chemical processes with flow, reaction and mass transfer, and analyzing and
generating dynamic scaling laws for these systems.

Project 14: Inclusion of Intuition and Prior Knowledge into Empirical and Fundamental
Process Models
Supervisor: V. Prasad
Type of Project: Computational
Number of Students: 1

In building process models for any system, there are two approaches that are used
traditionally - the development of fundamental models based on first principles, or the
development of empirical models purely from experimental data based on statistical principles
and optimization. However, with the current focus in many research areas on complex, large and
multiscale systems, there are many systems for which a complete first-principles description is
impossible to construct with our current knowledge of the system. While empirical methods may
be used in this case, the large number of variables in these systems provides significant
computational challenges; more importantly, no insight on physical, chemical and biological
processes occurring in the system can be obtained from these empirical models. Thus, these
systems require a hybrid modeling approach, where all the first principles knowledge available
on the system in somehow placed in a composite model along with empirical sub-models. The
focus in this project is to develop a framework to build such hybrid models, and to test the hybrid
models in various application areas.
The approach that will be used to build statistical models with intuition and knowledge
built into them is based on the so-called 'knowledge-based support vector machines'. Support
vector machines (SVMs) are supervised learning models based on specific learning algorithms
that can be used for classification and regression; thus, they are the empirical, statistical
modeling framework that will be used. Since SVMs are developed based on optimization
methods, the idea is that for systems where data is available and we have some physical intuition
about the system but full models cannot be developed, the physical intuition will be encoded into
constraints which will be respected when the optimization problem is being solved. There are
two areas of focus in this - the first relates to the best method to transform different types of
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process intuition into constraints, and the second relates to obtaining physical insight about the
system from the knowledge-based SVM model. The project is primarily simulation-based, and
requires the student to modify and develop algorithms, and to code them in Matlab.

Project 15: Identifying and Characterizing State-Space models for Macroeconomic Systems
Supervisor: V. Prasad
Type of Project: Computational
Number of Students: 1

State-space models are often used to characterize the behaviour of dynamic process
systems. These models consist of differential and/or algebraic equations, and may be built based
on first-principles modeling, or constructed empirically from process data. As new data is
gathered over time, the developed state-space models are often updated in a recursive fashion so
that they are better able to represent the process behaviour.
One difficulty in the application of empirical identification methods to generate state-
space models is in the case of large-scale systems, which have a large number of variables. The
high system dimension creates difficulty in the implementation of the identification algorithms.
Macroeconomic systems are such large-scale systems; however, there has been some success in
modeling these systems using empirically identified state space models of the same kind as the
models used in process control. Examples of macroeconomic variables include gross national
and domestic products, industrial production, manufacturing and trade sales, payroll employment
and money supply. In this project, the main aim is to build a case study for state space model
identification on a macroeconomic system, and to analyze the properties and behaviour of the
identified model. The project is primarily simulation-based, and will require the student to
develop and run simulations in Matlab.

Project 16: Advanced Metal Nanostructures for Catalysis: Decoupling Mass Transfer and
Reaction Kinetics
Supervisors: N. Semagina and V. Prasad
Type of Project: Computational based on available experimental data from catalytic reactions
Number of Students: 1

Advanced metal nanostructures, such as cubic, size-controlled spherical and other

nanoparticles, are at the cutting edge of modern catalysis research with enormous potential for
energy, environment applications and fine chemicals synthesis. In our laboratory, we
accumulated data on the performance of Pd nanocubes and nanospheres in three-phase
hydrogenation reactions for vitamins A and E production and showed significant increase in the
product yield over the Pd cubes. However, to conclude on the importance of the nanoparticle
shape control, it is necessary to decouple mass transfer and intrinsic reaction kinetics, which can
be done by modeling. Using the available experimental data, a student will model the process
(mass transfer + surface reaction) to derive the intrinsic kinetic parameters and will then estimate
the intrinsic activity of the shape-controlled Pd nanoparticles. The work will involve running
simulations in Matlab to obtain solutions to the model equations.

Project 17: CFD simulation and optimization of a bioreactor

Supervisors: S. Kresta, Machado, and D. Sauvageau
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Type of Project: Numerical

A recent study was conducted at Permolex Ltd. - a grain processing facility located in
Red Deer, AB - to evaluate the efficiency of their by-products of grain feedstock to bio-fuel
fermentation process. Permolex operates fermenters with capacities up to 400,000L. At such a
scale, issues of mixing quality and temperature profiles are suspected to have a significant
impact on productivity. Consequently, small improvements to bio-fuel yields and energy
requirements lead to significant savings.
In the preliminary study, data collected throughout the fermentation process was used to
build a model describing the hydrodynamics and heat exchange behaviour in the fermenter under
one set of conditions. The proposed project will focus on evaluating different scenarios
corresponding to different stages in the fermentation process. This will be done by modifying the
current model using parameters such as fluid density, viscosity, heat of fermentation, cell
densities, temperatures, etc. In addition, strategies to improve the temperature profile and
minimize energy requirements (pumping, cooling) will be developed and evaluated.
Students considering an MSc or graduate studies should note that this project has the
potential to be expanded into a full thesis project.

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