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Department of Chemical Engineering

University of San Carlos Technological Center


Nasipit, Talamban, Cebu City

ChE 413N
Material Science and Engineering

A Case Study on Material Selection and Design

Submitted to:
Engr. May V. Tampus
Instructor, ChE 413N

Submitted by:
Magno, Antoniette Jane C.
Navalta, Carl John Louie G.
Omega, Jan Laurence O.
Salazar, Leanille Grace M.

INTRODUCTION
Ceramics are nonmetallic, inorganic solids. By far the most common of terrestrial
materials ceramics made of sand and clay have been used for many thousands of years
for brick, pottery, and artware. However, modern structural ceramics bear little
resemblance to these traditional materials; they are made from extremely pure,
microscopic powders that are consolidated at high temperatures to yield a dense and
durable structure.
Compared to metals, ceramics have superior high-temperature strength, higher
hardness, lower density, and lower thermal conductivity. The principal disadvantage of
using ceramics as structural materials is the sensitivity of their strength to extremely small
flaws, such as cracks, voids, and inclusions. Flaws as small as 10 to 50 m can reduce
the strength of a ceramic structure to a few percent of its theoretical strength. Because of
their small sizes, the strength-controlling flaws are usually very difficult to detect and
eliminate.
Ceramics are candidates for numerous applications in high temperature
environments with aggressive gases and possible corrosive deposits. High temperature
oxidation and corrosion of monolithic ceramics has been studied for many years.
DEFINITION OF THE PROBLEM
A ceramic is an inorganic non-metallic solid made up of either metal or non-metal
compounds that have been shaped and then hardened by heating to high temperatures.
It is typically hard and a chemically stable material. It is commonly used in structural
applications, refractories, whitewares and widely used in advanced and technical
engineering applications such as gas burner nozzles, coatings of jet engine turbine blades
and mechanical bearing. With these types of applications, ceramics are subjected to
mechanical strains and high temperature environments, and experience active oxidation
reaction that leads to a rapid degradation of the ceramic component.
Active oxidation is the most important high temperature corrosion reaction. This
type of oxidation takes place when ceramics are heated at an elevated temperature and
highly oxidizing environments, which is common in processes that includes combustion
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with excess air or oxygen (Lai, 2007). Ceramics coated with silicon carbide for example,
when heated sufficiently will have its coating oxidize with free oxygen, and the volatile
portions of the ceramic compounds break free and the available oxygen will attach to the
remaining material, forming oxides (Peterson, 2015).
During oxidation, single-phase scales form on top of the ceramic layer (Mrowec et
al., 1973). This single-phase layer is formed by the oxidized components, and the layer
continues to grow with time. Because metal oxides and sulfides are known to have defects
in one sub-lattice only, the growth of the compact single-phase scale is a result of the
diffusion of only one of the reactants.
Ceramic component A was selected for a structural application in a hightemperature oxygen environment. Recognizing the potential problems associated with an
active oxidation reaction, an experiment was performed in which oxide thickness was
measured as a function of time with the obtained data below.
Oxide thickness (m)
Time (h)

5
1

11
3

17
5

32
10

From the gathered data, it is determined whether the chosen ceramic component A is
suitable in the specified environment. If not, another alternative material is to be
recommended.
THEORETICAL BACKGROUND
High temperature corrosion is a type of corrosion that does not require a liquid
electrolyte to proceed its reaction with the host material. To prevent or resist corrosion
attacks such as sulfidation, carburization, and other forms of high temperature corrosion
attacks, materials such as alloys rely on oxidation reaction to develop an oxide protective
layer. The properties of this protective layer such as the thermodynamic stability, ionic
defect structure and detailed morphology play an important role in determining the metal
or alloys oxidation resistance in a specific environment (Roberge, 2000).
Oxidation is the most common type of high temperature corrosion. Many industrial
applications involve operations at high temperatures in air, and materials oxidation
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resistance is an important consideration (Belitskus, 1993). Most non-oxides materials will


oxidize at high temperatures in the presence of excess air or oxygen that is not used up
in the combustion process. When a metal is subjected to high temperature, reacts with
oxygen or other gases by initial absorption of oxygen and by oxide nucleation, a surface
oxide is formed which laterally grow into a continuous film that serves as a protection to
the underlying metal. This protective layer covers up the non-protective scale that also
developed which has various defects including cavities, microcracks and porosities
(Jones, 1996).
There are three basic corrosion kinetics laws have been used to characterize and
understand the growth of oxide scale with time. These include parabolic rate law,
logarithmic rate law and, linear rate law and catastrophic oxidation. There are a number
of factors that affect the kinetics of oxidation, and some of the important ones are shown
in Figure 1.

Fig. 1. Schematic representation of factors influencing corrosion kinetics.


These factors lead to different types of oxidation product behavior (Nickel, 1993). A scale
growing by diffusion may develop cracks because of volume differences after a critical
thickness is reached, which will follow either a linear rate law the cracks give direct
access to the surface or, when the cracks are closed by the newly growing oxidation
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product until a critical thickness is again reached, a paralinear behavior. A layer which is
crystallizing may grow and follow a logarithmic law and after the layer is completely
crystallized, it follows a parabolic rate law.
Typically, oxidation at high temperatures follows a parabolic rate law, in which the
rate is obtained by plotting oxide thickness versus the square root of time or the parabolic
kinetics. Parabolic kinetics occurs when the mass gain or oxide growth indicated by a
layer formed on a sample ceramic is proportional to the square root of time. In general,
this implies that the diffusion of reactants such as Fe, O, or electrons in the reaction
product through a growing oxide scales is rate-determining step during the formation of
these scales (Kofstad, 1996).
The rate-determining step is derived from Ficks first law of diffusion (Roberge,
2000). At the oxide-metal and oxide-gas interfaces, the diffusing species concentrations
are assumed to be constant, and the diffusivity of the oxide layer is also assumed to be
invariant. With these assumptions, it is implied the the oxide layer formed is uniform and
continuous, and is a single phase type. The parabolic rate law is an Arrhenius type of
equation where the diffusion rate constant, kp, varies with temperature:
# = & + *

(Equation 1)

where:
x oxide film thickness, or mass gain due to oxidation
t time
kp diffusion rate constant
xo - constant

ANALYSIS AND EVALUATION


Ceramic component A for structural application in a high-temperature oxygen
environment was tested and the oxide thickness data as a function of time were obtained
shown in the table below.
Table 1. Oxide Thickness of Ceramic Component A
5
11
17
Oxide thickness (m)
Time (h)
1
3
5

32
10

Since oxidation follows a parabolic rate law, the rate is best obtained by plotting
oxide thickness versus the square root of time. Shown in figure 2 is a plot of oxide
thickness vs. the square root of time, which will give an equation of the line, and the slope
is the parabolic rate constant.

Oxide Thickness vs. t1/2


35

Oxide Thickness, m

30
Ceramic Component
A

25
20
15

Linear (Ceramic
Component A)

10

y = 12.586x - 9.3322
R = 0.97311

5
0
0

t1/2, h

Fig. 2. Oxide thickness of ceramic component A vs. t1/2.


The parabolic rate constant of the ceramic component, which is the slope of the
line, is 12. 586

+,.

or 125.86 m of oxidation product in 1000 hours. According to

Engineering Property Limitations of Structural Ceramics and Ceramic Composites, above


1600oC the acceptable parabolic rate constant is 10

+,.

or 100 m of oxidation product

in 1000 hours.
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CONCLUSION
Most ceramic components such as carbides, borides, and nitrides oxidize at very
high rates to be useful for long term structural applications at 1600oC. But at lower
temperatures, these composites are suitable.
Since the parabolic rate constant of the ceramic component A is a bit larger than
the acceptable rate constant, the ceramic will be ineffective when the maximum
temperature of stability of the material is exceeded.
RECOMMENDATIONS
It is recommended that ceramic component A will be used in a temperature not
exceeding its maximum temperature of stability to prevent further active oxidation. With
this, the component will be effective in its working environment and will provide satisfying
service.
If the working condition really exceeds the maximum stability temperature of the
ceramic component, first, other ceramic component is recommended with lower oxidation
rate. One component suitable for high temperature and is very adaptive to service
conditions is silicon carbide, where when it is subjected to high temperature it will oxidize
and form a protective layer, although it also produces gaseous products which is
dangerous. Second, ceramics at higher temperature tend to oxidize and cracks from at
the surface due to its relatively low toughness. It is recommended that the material used
for structures at high temperature environment is a metal coated with ceramics, in a sense
that the ceramics are reinforced by the metal. Third, further innovations on ceramic
components are highly recommended.

REFERENCES
Albina, D. (2005). Theory and experience on corrosion of waterwall and superheater
tubes of waste-to-energy facilities. Retrieved from www.seas.columbia.edu
Belitskus, D. (1993). Fiber and whisker reinforced ceramics for structural applications.
New York: Marcel Dekker, Inc. Retrieved from https://books.google.com.ph
Courtright, E.L. (1991). Engineering property limitations of structural ceramics and
ceramic composites above 1600C. Ceramic Engineering and Science Proceedings
12(910):17251744. doi:10.1002/9780470313848.ch9
Jones, D.A. (1996). Principles and prevention of corrosion. 2nd Edition. Upper Saddle
River, NJ Prentice Hall
Mileiko, S.T. (1997). Metal and ceramic based composites. Volume 12 of Composite
Materials Series. Retrieved from https://books.google.com.ph
Mrowec, S. & Stoklosa, A. (1974). Calculations of parabolic rate constants for metal
oxidation. Oxidation of Metals,8(6), 379-391. doi:10.1007/BF00603388
Nickel, G. (1994). Corrosion of advanced ceramics. Germany: Kluwer Academic
Publishers. Retrieved from https://books.google.com.ph
Roberge, P.R. (2000). Handbook of corrosion engineering. New York: Mc Graw Hill.