Effect Of Process Variables On Scale Formation

In Steel Reheating
R. C. ORMEROD IV‘, H. A. BECKER‘, E. W. GRANDMAISON’*, A. POLLARD2 and A. SOBIESIAK2

‘p2Centrefor Advanced Gas Combustion Technology, ‘Department of Chemical Engineering

and

2Department of Mechanical Engineering, Queen ’s University, Kingston, ON K7L 3N6, Canada

Variables affecting the high temperature oxidation of steel were investigated using an experimental design strategy.
The experimental methods included continuous mass-gain measurement to characterize the oxidation kinetics in terms
of parabolic rate constants. A Morris and Mitchell (1983) eleven-run experimental design was used to identify main
effects and interactions among seven independent variables (oxidation temperature, steel grade, steel surface condition,
sample history and gas composition: H,O, O2 and CO,). The levels of these variables were chosen to reflect industrial
steel reheat operations. The use of this type of strategy in assessing the effect of variables at an intermediate stage in an
experimental program is also demonstrated.
On a etudie les variables qui influent sur I’oxydation de I’acier a des temperatures elevees au moyen d’une strategie
de conception experimentale. Les methodes experimentales incluent la mesure continu du gain de masse afin de carac-
teriser la cinetique d’oxydation en termes de constantes de vitesse paraboliques. On a eu recours a une conception expiri-
mentale a onze essais de Morris et Mitchell (1983) afin de determiner les principaux effets et interactions parmi les sept
variables independantes(temperature d’oxydation, qualite de I’acier, condition de surface de I’acier, histoire de I’echan-
tillon et composition du gaz: H 2 0 , 0, et CO,). Les niveaux de ces variables ont ete choisis afin de refleter les operations
de rechauffement d’acier industrielles. On demontre egalement I’utilisation de ce type de strategie pour evaluer I’effet
de variables a un stade intermediaire dans un programme experimental.
Keywords: experimental design, steel oxidation. reheat furnaces.

identify the presence of interactions at an early stage of

R eheat furnaces are used to heat steel slabs prior to
olling and subsequent processing. These furnaces uti-
lize natural gas, coke-oven gas or oil as fuels in continuous
batch heating operations of 4 hours or more to raise slabs to
temperatures of 1215- 1300°C. Associated with the heating
is the growth of scale (iron oxides) on the surface of the
slabs. This scale typically amounts to 1 to 3% of the total
steel throughput; it requires removal prior to further pro-
cessing of the slab and constitutes a direct product loss.
Control of scale formation is complicated by the fact that the
oxidation reaction is exothermic, with the oxide products
acting as a thermally insulating barrier. Hence, a knowledge
of the scaling rates is also necessary for accurate energy bal-
ances on reheat furnaces. Without the introduction of a per-
meation barrier for the oxidation reactants, scale formation
is inevitable but the kinetics of the oxidation process can be
affected by operating variables in the reheating process
(Sachs and Tuck, 1968).
The objective of the present work was to investigate the
effect of process variables on the oxidation rate of low-car-
bon steel. The steel samples were supplied by the Ferrous
lndustry Energy Research Association (FERA) and repre-
sent grades and compositions of current industrial interest.
The methodology involved the use of an experimental
design strategy to reduce the number of runs required for a
screening study of the type here undertaken. Seven variables
were examined, including the oxidation temperature, the gas
and steel compositions, and the surface texture of the steel
samples. A Morris and Mitchell (1983) experimental design
was chosen for this screening study as it has the ability to
*Author to w h o m correspondence should be addressed. E-mail address:
grandmai@qucdn.queensu.ca
experimentation. The use of this experimental design as a
tool in assessing the effect of variables at intermediate
stages of the experimental program is also demonstrated.
The kinetics of scale formation was described in terms of
the mass gain and a corresponding parabolic oxidation rate.
The effect of the process variables and interactions between
variables on the parabolic oxidation rate were assessed from
the experiments.
Background
The oxidation of metals is of great interest in the nietal-
lurgical, electrochemical and process industries. Research
over the past 5 M O years ranges from fundamental studies
to ascertain/confirm reaction mechanisms through to
methodology for corrosion control. Review articles (Cabrera
and Mott, 1949; Smeltzer and Young, 1975; Rapp, 1984)
and textbooks by Evans (1960), Kubascgewski and Hopkins
(1962), Hauffe (1965) and Kofstad (1965) have resulted.
The peculiar problems of high temperature oxidation are
addressed in recent texts by Birks and Meier (1 983) and
Kofstad (1 988).
The oxidation reaction starts with an initial adsorption of
oxygen gas on the metal surface, possibly with some disso-
lution in the metal, to form a thin oxide film. If this film is
continuous, it physically separates the reactants and subse-
quent oxidation occurs by solid-state diffusion through the
oxide film. Porosity, cracks and poor adhesion at the
scale/metal interface may also lead to phase-boundary con-
trol mechanisms as the oxidation proceeds. Models for the
oxidation rate of metals and alloys have been developed and
validated for many test conditions. These include (Kofstad,
1988) logarithmic, linear and parabolic forms, normally

402 T H E CANADIAN JOURNAL OF CHEMICAL ENGINEERING, V O L U M E 75, APRIL, 1997

describing the mass gain or scale thickness developed on the
metal surface. Investigations of the low-temperature oxida-
tion of iron have included studies of oxide nucleation by
Ronnquist and Thomas (1965) and of oxidation rates; Gilroy
and Mayne (1965), for example, observed an inverse loga-
rithmic rate. The initial oxidation stages of iron have also
been investigated at higher temperatures by means of SEM
by Castle and Hunt (1976) and HSESEM by Matson et al.
(1 984) and Jungling and Rapp ( 1984). The linear rate equa-
tion is used to describe phase-boundary rate controlling
steps, while a parabolic form is applicable to cases of solid-
state diffusion in scale growth. At temperatures above
57OoC, iron oxidizes to form a multilayer scale of FeO
(wustite), Fe30, (magnetite) and Fe203(haematite) with the
wustite layer next to the metal surface, magnetite as an inter-
mediate layer, and haematite at the gas-solid interface. The
mass ratio of these oxide phases is around 95:4: 1 (Paidassi,
1958). At intermediate temperatures, up to 570°C, only the
haematite and magnetite layers form on iron and steel.
Wustite is a p-type semiconductor with a metal deficit; typ-
ically the stoichiometry approximates Fe,,9,0, but locally
the Fe/O atomic ratio may range from 0.95 to 0.88 with the
largest iron deficit occurring at the wustite-magnetite inter-
face (Engell, 1958). This level of cation vacancy promotes
high mobility of cations and electrons in wustite and the
overall mechanism for the oxidation is generally modelled
as a cation diffusion through the three scale layers, although
some early results suggested that anion diffusion occurs in
the haematite layer (several examples of these results are
noted in the text of Birks and Meier, 1983). In high-temper-
ature systems, the oxidation to wustite is dominant and the
rate is commonly described by a parabolic law relating the
cation flux to the metal vacancy concentration in the scale.
This approach was first proposed by Tammann ( 1 920) and
applied in early studies of iron oxidation by Davies, Simnad
and Birchenall (195 1) and Paidassi (1 958) in the form
d h -. k . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
dt h
where h is a measure of the scale thickness and t is time. At
constant rate coefficient, k, integration gives
h2 = k,,t + C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
where k,, = 2k is the parabolic rate constant and C i s the inte-
gration constant. In experimental studies, h is normally
expressed in terms either of a measured scale thickness or of
the mass gain of the test specimen per unit of its surface. It
is implied in these formulations that the scale thickness is
typically small compared to the local radius of curvature of
the surface. It should also be noted that, because it predicts
an infinite rate at t = 0, the parabolic law cannot apply at
t + 0. Typical oxidation curves and parabolic rate laws are
discussed by Logani and Smeltzer (1971) (e.g., see their
Figure 9).
The parabolic rate law is also developed in the quantita-
tive theory of Wagner (1933). Assumptions in the theory
require that the oxide layer be compact and perfectly adher-
ent to the metal surface, migration of ions or electrons is rate
controlling, the scale is thick compared with distances over
which space charge effects occur, thermodynamic equilibri-
um exists locally in the scale at both boundaries, there are
only small deviations from stoichiometric composition in
the scale, and oxygen solubility in the metal is negligible
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 75, APRIL, 1997
(Birks and Meier, 1983). The theory gives for the coefficient
of the parabolic oxidation rate
(3)
P' P"
where D is the diffusion coefficient for transport through the
scale and p is the chemical potential. The single and double
prime superscripts denote the values at the metal-scale and
scale-gas interfaces respectively. The subscripts "c" (for
cation) and "a" (for anion) refer to metal and nonmetal
properties, respectively.
Experimental confirmation of Wagner's theory has been
found by Himmel et al. (1953) and Engell (1958).
Experimental investigations have also demonstrated applic-
ability of the parabolic rate law for oxidation of iron in oxy-
gen (Paidassi, 1958; Davies et al., 195 1; Caplan and Cohen,
1963; Schmahl et al., 1958). Goursat and Smeltzer
(1973a,b) have shown that the reaction rate is independent
of the oxygen pressure in the range 0.04- 100 kPa.
Deviations from the parabolic law occur, for example,
when the rate controlling step is a phase boundary reaction
(Smeltzer, 1960; Pettit et al., 1960; Surman, 1973), a porous
scale is formed (Birchenall, 1956), or when adhesion of the
scale to the metal substrate fails (Engell and Wever, 1957;
Peters and Engell, 1959; Hussey and Cohen, 1971a,b). The
problems of discriminating between different kinetic models
are discussed by Smeltzer and Simnard (1957) and Kofstad
(1988). From their observations it may be concluded that con-
tinuous monitoring of scaling rates is the best route for correct
data interpretation.
Scale formation in steel reheat furnaces poses a situation
where many process variables may have synergistic influ-
ences. Sachs and Tuck (1968) review the potential impact
based on previous research in the field of high temperature
oxidation. Methods of reducing scale formation through
favourable control strategies are described by Cook and
(1) Rasmussen (1 970). The oxidizing gases in reheat furnaces
include oxygen, water vapour and carbon dioxide, presenting
a gas composition depending on the fuel type, excess air
level and other operating factors such as air infiltration. The
effects of gas composition on scaling rates are reported by
(2) Rahmel and Tobolski ( 1 965); the presence of water vapour
and carbon dioxide was found to increase the rate, with water
vapour having a larger effect at higher temperatures. Sachs
and Tuck (1970) studied the effect of oxidizing gases on the
high-temperature oxidation of iron and steel in an integrated
heating strategy for application to reheat furnaces. Kuhn and
Oeters (1975) and Selenz and Oeters ( 1 984) examined the
effect of several oxidizing species, providing data on coeffi-
cients of the linear rate behaviour that occurs in the initial
stage of oxidation. Minaev et al. ( 1983) studied the effect of
fuel type and temperature on scale formation for five grades
of steel. The fuel with the lowest oxidizing potential (as mea-
sured by the sum of oxygen, water vapour and carbon diox-
ide partial pressure) gave the least scale at the higher tem-
peratures, but this effect was less marked at the lower tem-
peratures. Importance of surface preparation on the oxida-
tion rate of metals has been documented in the literature. The
effect of cold working on the oxidation of iron was studied
by Caplan and Cohen (1966) and Caplan et al. (1970). At
temperatures up to 55OoC, cold worked iron exhibits higher
oxidation rates than annealed samples; this was partly attrib-
uted to poor scale contact for the annealed specimens.
403
 As noted above, the problem of oxidation of metals, and TABLE1
of iron in particular, has been well researched with mecha- Seven-variable Morris and Mitchell (1983) design
nisms documented for different experimental and process Variables
conditions. The bulk of the previous measurements of scal- Run 1 2 3 4 5 h 7
ing rates on iron and steel have been obtained by one-factor
at-a-time assessment of the effect of independent variables. I -1 -1 -1 -I -1 -I -1
2 +I +I +I +I +I +I +I
While this background serves to suggest useful guidelines 3 -1 -1 -1 -I +I +I +I
for scale control and methodologies to be employed for lab- 4 +I +I +I +I -1 -I I
oratory and plant investigations, measurements with well 5 -1 -1 +I +I -I -1 +I
planned experimental strategies can also provide useful 6 +I +I -1 -1 +I +I -1
information for improving scale control for particular steel 7 +I -1 -1 +I +I -I -I
grades in the process industries. 8 -1 +I -1 +I -1 +I -1
The main objective of the present work was to perform a 9 +I +I -I -1 -I -1 +I
series of screening experiments to assess the effects of inde- 10 +I -1 +I -1 -1 +I -1
pendent variables on the parabolic scale growth coefficient I1 -1 +1 +I -1 +I -1 ~~I
in the high temperature oxidation of steel:
TABLE2
log,o(k,,) =f(independent variables) . . . . . . . . . . . . . (4) First four runs of Morris and Mitchell (1983) design showing
alias structure denoted as A and B arouDings
where kp is assessed in a consistent manner for all experi-
mental runs. The logarithm of k,, is employed as the depen- Variables
dent variable in anticipation of Arrhenius temperature A B
dependence. The steel samples were prepared from slab Run 1 2 3 4 5 6 7
material supplied by Dofasco Inc. (Hamilton, ON), and the 1 -1 -1 -1 -I -I -I -1
independent variables of interest were chosen to include 2 +I +I +I +I +I +I +I
those most commonly associated with industrial reheat fir- 3 -1 -1 -1 -1 +I +I +I
naces, namely steel grade/finish, oxidation atmosphere and 4 +I +I +I +I -I -1 -1
temperature. The simplest model form for the effects of the
independent variables is the linear model
required to assess interaction effects, for example, additional
runs up to and including a complete fold-over fractional fac-
torial design can be employed (Myers and Montgomery,
1995). The effects of response surface curvature or higher
order terms also require additional experimentation, typically
with x, = 1, or, in standard vector notation, at the mid-point level for continuous or quantitative vari-
ables. In all the cases mentioned above, it is assumed that
Y = X P + E............................... (6) additional runs are also performed to obtain an estimate of
the system variance; mid-point experiments or replicate runs
where Y is an (n x 1) vector of observations, X is the ( n x p ) at design levels are frequently preferred if the variance is a
matrix of independent variables, p is a 0, x 1 ) vector of function of the level of the independent variables.
coefficients to be estimated and E is the 0, x 1) vector of Morris and Mitchell (1983) have proposed another
random errors (each having a zero mean and a variance a2). method of constructing experimental designs suitable for
The least squares estimate of p then is screening experiments. A feature of these is that they are
suitable for detecting the effect of interactions at an early
p= (XT X)-1 XT Y. . . . . . . . . . . . . . . . . . . . . . . . . . . (7) stage of experimentation. If we write the model for Y to
include interactions, then
One criteria for constructing experimental designs, the D-
optimality criterion, involves choosing the X matrix such Y = x , p , + X , p , + &. . . . . . . . . . . . . . . . . . . . . . . (8)
that the determinant of (XTX) is maximized (Smith, 1918).
The benefits of this are described by Box and Draper ( 1 97 1). with a corresponding lack-of-fit matrix
In screening designs, the main objective is often the esti-
mation of the relative importance of independent variables L = x,T(I - x l ( x ; XI)-, XT)X,. . . . . . . . . . . . . . . . (9)
with the assumption that interactions and higher order terms
are negligible or can best be explored in later experimenta- where pzis a vector consisting of thep@ - 1)/2 interactions
tion. Suitable forms of such experimental designs, including and I is the identity matrix. Morris and Mitchell (1983) note
those proposed by Plackett and Burman (1946) and fraction- that the proposed designs maximize the trace of L and satisfy
al factorial designs (Box and Hunter, 1961) have been the D-optimality criterion.
described in the statistics literature. Applications to industri- In the present study, seven variables were chosen for
al problems have been described, for example, by Williams investigation, as described in detail later. The seven-variable
(1963), Stowe and Mayer (1966), Hunter and Hoff (1967), design of Morris and Mitchell (1983, from their Table 6) is
Grandmaison et al. (1984) and Hamada and Wu (1992). shown in Table 1. This type of design permits intermediate
These designs require careful analysis to yield information analysis of some of the effects under study. In particular, the
regarding interactions between variables, for example, first four runs can be placed in two groups, A and B, as
Hamada and Wu (1992) discuss use of Plackett and Burman shown in Table 2. The structure of the first four runs is a 2 ,
designs in this regard. In other cases, additional runs may be factorial design with variables 1-4 assigned to a set of lev-

404 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 75. APRIL, 1997
 TABLE 3 TABLE 4
First six runs of Morris and Mitchell (1983) design showing Chemical composition (mass%) of steel samples; low CI and low
decoupling of alias structure from Table 2 C2 refer to low carbon content, high C I and high C2 refer to high
carbon content samples
A B
Al A2 BI B2 LowCI LowC2 HighCI HighC2
-
Run 1 2 3 4 5 6 7
Carbon 0.002 0.003 0.203 0.2 14
~~ ~
~~
Sulphur 0.008 0.005 0.007 0.007
1 -1 -1 -1 -1 -1 -1 -1 Nickel 0.006 0.007 0.006 0.005
2 +I +1 +I +1 +I +I +I Aluminum 0.028 0.056 0.036 0.035
3 -1 -1 -1 -1 +I +I +1 Cobalt 0.022 0.027 0.00 1 0.000
4 +I +1 +I +1 -1 -1 -1 Titanium 0.026 0.041 0.003 0.002
5 -1 -1 +1 +I -1 -1 +1 Manganese 0.139 0.157 0.356 0.352
6 +I +I -1 -I +I +I -1 Silicon 0.008 0.015 0.008 0.007
Chromium 0.018 0.022 0.024 0.026
Molybdenum 0.003 0.004 0.003 0.003
els A and variables >7 assigned to levels B. This subset of Zirconium 0.000 0.001 0.001 0.000
experiments provides an estimate of the sum of the main Phosphorus 0.005 0.005 0.005 0.007
effects due to variables 1, 2, 3 and 4, estimated from PA,and Copper 0.008 0.009 0.008 0.005
variables 5, 6 and-7, estimated from &. The interaction Tin 0.002 0.005 0.003 0.002
between A and B, pAB,provides an estimate of the sum of Vanadium 0.000 0.00 1 0.000 0.000
interactions b e p e e n any variable in groups A and B, i.e., Nitrogen 0.002 0.002 0.003 0.004
p15,p16, . . . . , p47.The interactions betweep va*riableswjth-
in a group A or B, i.e. R2,R3,.. . ,h4and p45,& . . . , k7,
are biased with the overall mean for the model, Several properties or attribute variables associated with the
Runs 5 and 6 in Table 1 provide an additiona decoupling 4
of the alias structure as shown in Table 3. This set of runs
steel samples were of interest. These included surface condi-
tion, pre-oxidation history and carbon content of the steel.
provides an estimate of main effects confounded only with The steel as received was in the form of bars cut from cast
one other main effect, plus fractional amounts of all other slabs, preserving on one face the original cast surface. Two
main effects, except for variable 7. The variables in group types of samples for study were prepared from these bars. The
A are decoupled into the groups A1 and A2, while those first were 22.2 x 22.2 x 44.4mm blocks milled and polished
from group B decouple as groups B1 and B2. The estimates on all sides, weighing 160 g. The second type were similar
of the interactions are biased in three groups of six interac- except that one 22.2 mm square face was in the original cast
tions plus another group consisting of the overall mean surface, unaltered. It was expected that this contrast would
aliased with three interactions. The interactions are not allow a significant gauging of the effects of surface condition,
biased by any main effect but these groups of interactions comparing natural cast surfaces with highly machined sur-
are also biased by fractional amounts of all other two-fac- faces. The sample shape and size were chosen to promote
tor interactions. Moms and Mitchell note that this design good metal/oxide contact (poor contact would tend to occur
has an 80% chance of detecting interactions at a 90% con- in cylindrical samples, for example) and to provide a rela-
fidence level. tively high specific area of 0.031 m2/kg (to reduce the effect
The full 1 1-run design shown in Table 1 provides esti- of sample superheating due to reaction exothermicity).
mates of the main effects of each variable biased only by The elemental analysis of the steel samples is shown in
small amounts of other main effects and interactions. This Table 4. The primary component of interest for this work is
type of design thus offers a compromise with other alterna- the carbon content. Those samples with a low carbon con-
tive designs (e.g. a 12-run Plackett and Burman (1946) design tent (0.003 mass%) are designated as low C1 and low C2
or a 2’“ fractional factorial design) with the advantage of and those with a high content (0.2 1 mass%) as high C 1 and
indicating the presence of interactions and an intermediate high C2, where the designation “Cl” and “C2” denote the
analysis during the course of the experimental programme. variations in other components at each carbon level as noted
Additional runs are required to estimate experimental error; in Table 4.
in the present study a total of 20 runs was performed for the The effect, if any, of pre-oxidation history was gauged by
complete programme. One of the main objectives in the pre- storing the steel samples at either dry or ambient room con-
sent work was to demonstrate an experimental design strate- ditions prior to oxidation tests. For this purpose, samples
gy which would permit assessment of the effects of variables/ were stored at room temperature either in a vacuum desic-
interactions at an intermediate stage in the experimental pro- cator as one experimental level or under atmospheric condi-
gram. Such information would be of interest, for example, to tions (nominally 50% R.H.) as the other level. This variable
industrial users of such statistical methods where progress was intended to demonstrate any effects like those of sub-
reports on experimental programs are important. stantial time delays between casting and reheating steel in
normal plant operation as well as providing guidance for
Experimental procedures future preparation techniques in our laboratory.
The furnace used to oxidize the samples was a Sola Basic
The variables chosen for investigation were set at two lev- Lindberg electrical resistance tube furnace. A schematic
els according to the experimental design discussed above. diagram of the heating, gas preparation and data acquisition
The primary dependent variable was the kinetic behaviour systems is shown in Figure 1. Additional details are given
of the steel samples undergoing oxidation in a laboratory by Ormerod (1991). The firnace housing was 0.6 m x 0.6 m
furnace. From mass-gain data for the samples, the parabolic x 0.8 m in outside dimensions. The heating cavity was
rate constant, kp, was estimated and the logarithm of kp was cylindrical in shape, 80 mm in diameter, 0.7 m long and
used as a dependent variable for statistical analysis. open at both ends. The temperature within the furnace could

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 75, APRIL, 1997 405

Temperature
Controller
i Digital Storage
Oscilloscope
71
water
Vapourlzer
II
Heater n
Balance
Gas Supply supply
be controlled at temperatures up to 1200°C (f 2"C), with
three separate heating zones located along the 700 mm heat-
ing section. Each heating section was normally set at the
desired design temperature for a run, at the low level of
800°C or the high level of 1 150°C. A 57 mm i.d. quartz tube
was inserted into the furnace cavity to provide a reaction
containment for the oxidizing gas and the steel sample. The
gas-feed end of the tube had a contraction terminating in a
ground-glass joint through which it was connected to the
feed system. The gas discharge end of the tube was open to
the atmosphere. The steel sample was introduced through
the discharge end, suspended from a quartz rod rigidly
attached to the platform of a Mettler PM6100 electronic bal-
ance (6 kg range, 10 mg resolution). The gas flow-rate was
adjusted to provide a linear velocity of 0.13 m/s at the sam-
ple position at 1150°C. A study by Tomlinson and
Catchpole (1968) showed no effect of gas velocity on oxi-
dation between 0.002 and 0.9 m/s at temperatures ranging
from 600 - 1000°C. The serial output of the balance was
connected to a microcomputer for data logging (normal
sampling rate of 1 datum per minute). The furnace and bal-
ance system were located in a shielded fume hood to mini-
mize external drafts and exhaust the gas discharged from the
oxidation process. A thermocouple was placed adjacent to
the sample within the furnace to provide an estimate of the
sample temperature. This thermocouple did indeed indicate
a temperature rise at the onset of the sample oxidation (an
exothermic reaction), but these readings could not be used to
provide accurate estimates of this phenomena.
An additional set of independent variables of interest in
this work was defined upon the oxidizing gas atmosphere.
In order to simulate conditions present in reheat furnaces,
gas mixtures consisting of nitrogen, oxygen, carbon dioxide
and water vapour were prepared to simulate combustion
products of both natural gas and coke oven gas. Oxygen lev-
els were chosen to simulate relatively low excess air condi-
tions as a low level (nominally 2 mol%) and possible air
infiltration situations as a high level (nominally 12 mol%).
The corresponding low and high target concentrations for
carbon dioxide were 4 and 12 mol%, respectively. The gas
streams were prepared from dry oxygen, carbon dioxide and
nitrogen mixtures humidified in a gas preparation system. A
similar procedure has been described by Miner and
Nagarajan ( 1 98 I). The bubbling-gas humidification cham-
ber consisted of a standard pipe tee, 76.2 mm in diameter
406 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 7 5 , APRIL, 1997
and 254 mm in length, with a capacity of 400 mL of distilled
water. The chamber was heated within f 0.4"C with an
on/off controller to maintain the desired dew point tempera-
ture. The gas stream leaving was heated with a 400 W heat-
ing tape to prevent condensation. The temperature in the
humidification system was continuously monitored during
runs and recorded for later analysis. The average value of
the dew point (the total amount of water evaporated during
each run was recorded for this purpose) was used for the
water vapour content in each run. The dew-point data also
allowed estimation of the variation in the water vapour con-
tent during each run; the maximum of the standard deviation
of this variation about the low level for the water vapour
content (a target value of 16 mol% H 2 0 ) was 0.20%, while
the worst case for the high level for water vapour (a target
value of 26 mol% H 2 0 ) was 0.52%. The steel samples were
mounted in the furnace at room temperature with a nitrogen
purge and then heated to the desired temperature over a
period of 2-3 hours. During the experimental programme,
the 1 I-run experimental design discussed above was used
with replicates of runs 1 to 7 along with additional replicates
of runs 1 and 3, yielding a total of 20 runs. The experimen-
tal run conditions are shown in Table 5 with the independent
variables shown in natural units and Table 6 with these vari-
ables shown in coded units. The coded levels for the quanti-
tative variables (gas compositions and temperature) were
calculated from the average low (-1 level) and high ( + I
level) values used in each experiment. The independent
variables are also denoted with the symbols x , , . . . , x7 cor-
responding to the seven variables from oxygen level to sur-
face condition in Table 6. The parameter estimates dis-
cussed later are denoted by the symbols fi,for the main
effects of variable i and for interactions between vari-
ables i andj.
Experimental results
The gas compositions could not always be set at the pre-
cise target levels noted above. This was primarily due to the
problem of controlling the water vapour content and to small
variations in the original bottled gas supplies. The largest
deviations from the design levels occurred for the water
vapour content but these errors were not considered large
enough to affect the benefits gained from the overall experi-
mental strategy. The furnace temperature was preset to the
desired level by a control system which gave consistent tem-
peratures within the furnace to *2"C. Compensation for sam-
ple overheating due to reaction exothermicity was not
employed (the effect of this phenomena is discussed later).
The variable for sample history was set at fixed levels o f f 1
as discussed above and sample grade levels were set to * I
based on the carbon content and the steel composition noted
in Table 4. For the purposes of statistical analysis, the vari-
able levels were range-scaled and centred with the range
being the average upper bound and average lower bound in
each variable as shown in Table 5.
Runs 1 to 1 1 (original experimental design) and IX to 7X
(replicates of runs 1 to 7) were initially performed in a ran-
domized fashion. Additional replicate runs, IXX and 3XX,
were performed later to check the previous observations.
The mass gain data, expressed in terms of the square of the
mass gain per average unit area, are shown in Figure 2.
These results were obtained at a sampling rate of one datum
per 60 s. To distinguish between the different curves in these
 TABLE 5
Experimental run conditions expressed in natural units.
Independent Variables
1 2 3 4 5 6 7
co,, Temperature,
mol% "C History Grade Surface
Run 1 2.16 17.2 4.03 800 Laboratory Low c2 Smooth
Run 2 12.0 25.7 11.9 1150 Dessiccator High CI Cast
Run 3 2.20 15.8 4.09 800 Dessiccator High C I Cast
Run 4 11.9 26.3 11.8 I I50 Laboratory Low C I Smooth
Run 5 2.06 15.4 11.9 1 I50 Laboratory Low c2 Cast
Run 6 12.0 25.6 4.05 800 Dessiccator High C2 Smooth
Run 7 12.1 15.7 4.04 1 I50 Dessiccator Low C I Smooth
Run 8 1.79 25.7 4.17 1150 Laboratory High CI Smooth
Run 9 12.0 25.4 4.06 800 Laboratory Low c 2 Cast
Run 10 12.4 16.5 12.4 800 Laboratory High C I Smooth
Run 1 1 1.97 25.3 12.2 800 Dessiccator Low CI Smooth
Run I X 2.2 I 15.3 4.12 800 Laboratory Low CI Smooth
Run 2X 12.1 25.2 12.0 1150 Dessiccator High CI Cast
Run 3X 2.20 15.9 4.09 800 Dessiccator High C I Cast
Run 4X 12.0 25.8 11.9 1150 Laboratory Low C I Smooth
Run 5X 2.05 15.8 11.9 1 I50 Laboratory Low c2 Cast
Run 6X 12.0 25.5 4.05 800 Dessiccator High C2 Smooth
Run 7X 12.1 15.4 4.05 1 I50 Dessiccator Low c 2 Smooth
Run IXX 2.19 16.0 4.08 800 Laboratory Low CI Smooth
Run 3XX 2.19 16.2 4.07 800 Dessiccator High C2 Cast
Aver age 2.10 15.9 4.08 800 Laboratory Low c 1lC2 Smooth
Low Level
Aver age 12.1 25.6 12.0 1 I50 Dessiccator High C 1lC2 Cast
High Level

TABLE6
Experimental runs conditions expressed in coded units
XI x2 x3 x4 X5 X6 .r7
0, H2O co2 Temperature History Grade Surface
Run 1 4.988 4.737 -1.01 -1 -1 -1 -I
Run 2 +0.988 +1.02 +0.975 +I +I +I +I
Run 3 4.980 -1.03 -1 .oo -1 +I +I +I
Run 4 +0.968 +1.14 +0.950 +I -I -1 -1
Run 5 -1.01 -1.11 +0.975 +I -1 -1 +I
Run 6 +0.988 +0.998 -1.01 -1 +I +I -I
Run 7 +1.01 -1.05 -1.01 +I +I -I -I
Run 8 -1.06 +1.02 4.976 +I -1 +I -1
Run 9 +0.988 +0.956 -1 .oo -1 -1 -I +I
Run 10 +1.07 4.882 +1.10 -I -1 +I -1
Run I 1 -I .03 +0.936 +1.05 -1 +I -1 -1
Run IX 4.978 -1.13 4.989 -1 -I -I -I
Run 2X +1.01 +0.9 15 + I .oo +I +I +I +I
Run 3X 4.980 -1 .o I -0.996 -1 +I +I +I
Run 4X +0.988 + I .04 +0.975 +I -1 -I -I
Run 5X -1.01 -1.03 +0.975 +I -1 -1 +I
Run 6X +0.988 +0.977 -1.01 -1 +I +I -1
Run 7X +1.01 -1.11 -1.01 +I +I -I -I
Run IXX 4.982 -0.985 -0.999 -1 -1 -1 -1
Run 3XX 4.982 4.944 -1 .oo -1 +I +I +I

graphs, appropriate graphical symbols are shown at every
600 s with a continuous line for the intermediate points.
Hence the data for the high mass-gain runs (bottom graph in
Figure 2) display smoother curves than those from the low
gain tests (top graph in Figure 2), due to the mass resolution
of the data acquisition system and balance employed. The
results in Figures 2 generally exhibit a parabolic behaviour
except for the initial stage of run 1. Similar data for the
replicate tests are shown in Figure 3. The first replicate of
run 1, run IX,shows better parabolic behaviour with sam-
ple grade low CI as compared to the low C2 grade used in
run I . The observed differences between these two runs
prompted an additional replicate, run IXX, using sample
grade low CI (there was insufficient sample material to per-
form an additional test with the low C2 grade). In general,
the results in Figures 2 and 3 give a linear relationship, par-
ticularly at longer times. The slopes of these curves for the
final 6000 s of each run were used for estimates of the par-

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 75, APRIL, 1997 407
 TABLE7
Experimental results for the parabolic rate constant
Run Parabolic rate constant,
number kp, g2/m4 s log I " kJJ
I , IX, IXX 2.83,4.25, 6.17 0.452,0.628,0.790
2,2x 507,488 2.70, 2.69
3,3x, 3 x x 4.20, 4.63, 3.98 0.623,0.665,0.600
4,4x 615,453 2.79, 2.66
5,5x 248, 198 2.40, 2.30
6, 6X 4.88, 6.28 0.689. 0.798
7, 7 x 543,465 2.74, 2.67
8 423 2.63
9 2.22 0.346
10 2.93 0.467
11 4.55 0.658

\
t
N
m
Y

N !
.-c TABLE8
tu Ranking of factors in descending order after 4 runs
m
cn Factor Effect on log,, k,,
cn
3
v
bo + PI2 ' k 4 + 656 'bI.4 + + I .64
6 7 + & 3 + & 4 +&7

Pl+&+&+b4 +1.10
0 5 10 15
-0.0638
Time, ks bL7 + k h + P45 + 617 + &5 + P46 +

Figure 2 - Square of the mass gain as a function of time for the 615 +&6 ' k 7 'pi6 +bZS +b47
low temperature runs (800°C. top graph) and high temperature runs &+p6+& +0.02 I7
( 1 1 5OoC,bottom graph).

0 5 10 15 0 5 10 15 0 5 10 15 0 5 10 15 Figure 3 - Square of the mass gain as a

function of time for the replicate runs (run
Time, ks 1 -run 7).

abolic rate constant. The oxidation rates at longer times, typ-
ically up to 15000 s, are of particular interest in applications
for reheat furnaces. The estimates of the parabolic rate con-
Fp
stants k and log,o are shown in Table 7.
As aieady mentioned, a thermocouple was used to moni-
tor the temperature adjacent to the steel samples (thermocou-
ples inserted in the samples were usually destroyed during
runs and hence the procedure of placing a thermocouple out-
side but near the sample was adopted). While this tempera-
ture reading is only indicative of the sample temperature, the
results show good agreement with estimates from a mathe-
matical model (Ormerod, 199 1). The observed temperature
rise is typically 10 - 40°C for the high temperature runs and
2 - 8°C for the low temperature runs. The peak temperature
values lasted for about 10 minutes before decreasing to the
target values for each run. No compensation was made for
this exothermic effect and hence in the present work (and
many other experiments reported in the literature) the
reported temperature represents an under-estimate of the
true reaction temperature.
The phased approach to estimating the parameters or the
influence of variables and interactions can be applied to the

408 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 75, APRIL. 1997
 TABLE
m
9
Ranking of factors in descending order after 6 runs
99
Factor Effect on log,, k ,

0
0
-
0
0-
-
-
.4--Xl

17
’‘
x2

XlX2

10 ----X7

A+& 4.203 0- x5
I I I
TABLE
10
1
Ranking of factors in descending order after eleven runs 0 5 10 15
Factor Effect on log,, k, Normalized effect
Figure 4 - Normal probability plot of the normalized effects.
Po + 1.569 Interaction effects are identified by one term from biased groups of
+a734 three terms noted in Table 10.
64

p15 + 6 2 h + 6 3 7 +0.3 12
the overall average biased with a group of interactions and
616 + 625 +647 -0.217 the main effects associated with the gas compositions and
temperature. On the other hand, the effect of steel history,
63 +0.204
grade and surface condition along with the group of two-fac-
614+&3+667 +O. 107 tor interactions in (3) above are relatively small. The signs
associated with the effects in these results indicate whether
612 + 6 3 4 + A 6
4.104 an increase in a variablehnteraction increases (positive
effect) or decreases (negative effect) the dependent variable.
62 +0.088
The results after the first six runs are shown in Table 9
627 + (336 + 645 -0.084 with the relative ranking of the factors affecting the depen-
dent variables. These effects were estimated by applying a
61 +0.078 singular value decomposition (SVD) to Equation ( 7 ) to
4.074 solve for eight factors in the vector p shown in Table 9. At
817 + 6 3 5 +b46
this point the influence of temperature and interactions
813 + 6 2 4 + A 7 +0.070 between variables are more evident. After eleven runs the
results, Table 10. obtained by SVD for fifteen factors, show
67 +0.052
that the highest-ranking main effect is temperature with
66 -0.034 other main effects and groups of interactions interspersed
through the remaining rankings. An interaction effect is
ps +0.004 strongly indicated.
The data for the full twenty experiments were analyzed
using unweighted, weighted and stepwise regression proce-
experiments involving 4, 6 and 11 runs. For this intermedi- dures. Model adequacy was checked by comparing the ratio,
ate analysis, it was necessary to employ the target values for F,, of the mean square lack of fit and the mean square pure
the levels of the quantitative variables to maintain the error to the appropriate Fa. ,,2 value with a significance
required number of degrees of freedom for such an analysis. level of a = 0.05. The mean square pure error, estimated
The results after four runs are summarized in Table 8 as esti- from the replicate runs, was 0.00902 with 9 degrees of free-
mates of four pieces of information: dom. Additional tools in this analysis included assessment
(I) 6,+~2+A4+A6+P]4+b23+P57+~3+8?4+PS7.
of normal probability plots of the residuals, 0,- j ) , and plots
of the residuals as a function of? and the independent vari-
(2) PI + b2 + + 64’ ables and interactions.
A normal probability plot of the normalized effects is
(3) b 2 7 + ~ 6 + b 4 ~ + ~ 7 + ~ ~ + 8 4 6 + 8 ] 5 + ~ 6 + ~ 7 8 ~ 6 in Figure 4. These effects are the average of the
+shown
k5+ b47,and
+
“low” and “high” values of each effect divided by their
respective standard deviations. Those effects that are negli-
(4) ps +& +I$ gible fall along a straight line while significant factors or
interactions (or groups of interactions in this case) will devi-
as shown in the “factor” column in Table 8. These results ate from the straight line. The results shown in Figure 4
show that the factors in ( I ) and (2) have the largest effect; i.e., include the fourteen main effects and interactions (shown in

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 75, APRIL, 1997 409
Table 10) with the latter denoted by one interaction member
from an aliased group, for example, x I 5denotes an effect
from the group x , +~ x2, + x37. These results, as expected,
clearly indicate the importance of temperature (x,) and the
relatively minor influence of other factors. In many experi-
mental design studies, it is assumed that only a small num-
ber of effects are important; this has been called effect spur-
sity by Hamada and Wu ( 1 992). These authors have also
noted that when a two-factor interaction is significant, it is
highly likely that at least one of the corresponding main
effects is also significant; Hamada and Wu (1992) refer to
this as effect heredity.
A model based only on temperature as a main effect gives
6 = 1.62 and p4= 1.OO.This model exhibits lack of fit with
F, = 3.98 compared with F,,,, 9, = 3.18. Stepwise regres-
sion procedures indicate that the significant effects include
temperature (x4), a positive interaction from the group (x,,
+ x2, + x ~ ~grade
) , (x,) and surface condition (x7). It is like-
ly that only one term from the interaction group (xI4+ x2, +
x67) is important in this analysis. The interaction between
water vapour (x2) and carbon dioxide (x,) concentrations is
an unlikely candidate because neither main effect is signifi-
cant. A positive interaction between oxygen concentration
(xI)and temperature (x,) would imply that (i) at the low
temperature, the oxidation rate is higher at the low oxygen
concentration and (ii) at high temperatures the oxidation rate
is higher at high oxygen concentrations. Both of these con-
ditions make this interaction term unlikely on physical
grounds. This leaves the interaction term between grade (x6)
and surface condition (x7) as the most plausible candidate
among these interaction terms. This conclusion is also sup-
ported by the significant main effect of each variable in this
interaction term. A positive interaction between grade and
surface condition implies that at the +I grade level, surface
condition has little effect on the oxidation rate but at the -1
grade level, the cast surface has a lower oxidation rate. This
conclusion leads to the model,
j = 1.58 + 1.03x4 + 0 . 0 8 3 8 + ~ 0~ .~0 ~7 6 3 ~ ~
- 0 . 0 8 2 8 ~ ~. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
and this model is statistically adequate with F, = 1.1 1 com-
pared with Fo,05,, ? = 3.37. The effect of grade and surface
condition on the oxidation rate at low and high temperature
conditions is shown in Figure 5.
There are other variables and interactions that might
appear more important or rank higher than the interaction
term x6x7 in Table 10 and Figure 4. For example, the vari-
ables x,, x2 and x3 and interactions x,xs and x,x7 are the next
higher ranking effects in Figure 4 following the inclusion of
temperature (x,) in the model. However, each of these vari-
ables had a small to moderate correlation with the large
effect of temperature in the regression analysis. Interactions
from the group (xIx4+ xp3 + x,x7), on the other hand, had
a very low correlation with temperature and from this group,
the interaction x,x7 appears to offer the most plausible
explanation.
The residuals from the model in Equation (10) exhibited
a larger dispersion at the low surface condition and hence a
weighted least squares procedure was also examined.
Pooled estimates of the pure error variance at the two sur-
face conditions for the replicate runs were obtained and used
in estimating weights for all the experimental test condi-
tions. The results of this analysis gave improved residual
410
103 I I I
h
Temperature = 115OoC
- - -C- - - -1 Grade
1 I I
102
L I I I
4
Temperature = 8OO0C
1
I--+-- -1 Grade I
I 1 1 I
-1 0 1
Surface condition
Figure 5 - Scatter plots showing the effect of the interaction
between grade and surface condition; top graph is for 1 150°C and
bottom graph is for 800°C.
behaviour with only modest changes in the parameter-esti-
mates noted in Equation (lo), p0 = + I .58, f3, = + I .02, ph7 =
a
+0.0838, pS = +0.0757 and = 4 . 0 8 2 4 .
The parabolic rate constants obtained here can be com-
pared to values found by others. For example, Davies et al.
(1951) and Schmahl et al. (1958) studied the oxidation of
iron in pure oxygen over a wide temperature range. Rahmel
and Engell (1959) studied the oxidation rate of iron in
(10) atmospheres with oxygen concentrations in the range 1 to
100% for three temperatures that overlap the results
obtained in the present work. Sachs and Tuck ( 1 970) also
report parabolic oxidation rates for iron in pure oxygen, air
and synthetic gases simulating combustion products. Data
from these investigations and the present data are shown in
the left graph of Figure 6 in an Arrhenius plot in the tem-
perature range of 600 to 1200°C. Sachs and Tuck ( 1 970)
also studied the high-temperature oxidation of mild steel in
oxygen, air and synthetic combustion product gases. These
results and data from the present study are shown in the right
graph of Figure 6.
Discussion
The present work demonstrates an experimental screen-
ing study of a problem with important industrial applica-
tions. The variables chosen for investigation are consistent
with those of interest for industrial control of scale, namely
the oxidizing gas composition, temperature, and steel com-
position. The oxidation tests were performed with an expo-
sure time of 4 hours, a time scale typical of that employed in
steel reheat furnaces for the batch heating of steel slabs. The
phased approach suggested in this work, based on the exper-
imental design strategy of Moms and Mitchell (1983), func-
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING. VOLUME 75, APRIL, 1997
 10-2
Schmahl et al (1958) A
10.3 Rahmel and Engell(l959) C
P
'? i0-4
E
w
'
0 10-5
Y
Y"
10-7
108
0.6
' I
0.8
1
1.o 1.2 0.6 0.8
in,K - ~ X I O - ~ in,K - ~ X I O - ~
tions well in providing significant intermediate information
about possible effects of interactions during the study. This
approach thus has merit in allowing for an interim reporting
and/or assessment of project objectives at an intermediate
stage. It should also be noted that the effects of the qualita-
tive variables (steel history, grade and surface condition)
were small in the initial stage of experimentation and the
potential significance of some of these variables only
became apparent after the completion of the full pro-
gramme. Hence, one should also be aware of the potential
need for changes in conclusions drawn from early stages of
experimentation. While a significant temperature effect
might have been anticipated in this work, based on the lev-
els chosen for this variable, the fact that interactions could
also be ranked high in relative importance demonstrates the
utility of the experimental strategy. The parabolic oxidation
mechanism here employed is consistent with the observa-
tions for all runs except the early stages of the low-temper-
ature runs. The results for run 1, in particular, did not indi-
cate a parabolic behaviour for the first 6000 s. However, the
parabolic rate constants were estimated from the present
data based on results for the last 6000 s where a distinct par-
abolic form was evident. This also corresponds to the time
when a larger scale growth develops on steel slabs in the
soak zone of reheat furnaces. Within this region a parabol-
ic model provides an adequate description of the data for all
test conditions, including those for run 1.
The effect of temperature is shown to be of greatest impor-
tance in the present study while a two-factor interaction
between surface condition and grade is also important at a
5% significance level. The effect of temperature is an expect-
ed result. The interaction term between surface condition and
grade coupled with the main effects of these variables indi-
cates that for the low carbon grade, the cast surface has a
lower oxidation rate or a more protective coating against oxi-
dation than the machined surface condition. This observation
is important for experimental tests and indicates the impor-
tance of surface preparation in studies of oxidation kinetics.
The parabolic rate constants in the present work are sim-
ilar in magnitude to those observed in previous studies of
high temperature oxidation of iron and steel. A comparison
between the present data and previous results for the oxida-
tion of iron indicates that the parabolic rate constant is typi-
cally lower for mild steel, as shown in Figure 6. The scatter
in the data sets shown in Figure 6 is attributable to the effect
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 75, APRIL, 1997
Figure 6 - Arrhenius graphs of the para-
1.o 1.2
bolic rate constant for scale formation on
mild steel (present work) and iron (other
references) on the left graph and for scale
formation on mild steel on the right graph.
of other variables (for example, the oxygen or gas concen-
tration for the work of Rahmel and Engell(l959) and Sachs
and Tuck (1 970) and the significant variables found in the
present work) and experimental error.
The fact that other variables/interactions appeared to rank
higher than the interaction between grade and surface con-
dition was due to the biased nature of the results from this
Morris and Mitchell design (1983). Traditional alternatives
for the investigation of seven variables include the 27-3 frac-
tional factorial design involving 16 runs (plus replicates).
This design will provide unbiased estimates of main effects
(an improvement over the present case) plus interactions in
seven groups of three (similar to the present case). Hence,
there is a penalty incurred in our implementation of the
Morris and Mitchell design ( 1 983). but in the present work,
plausible results have been obtained and hrther tests could be
performed to confirm or reject these hypotheses. Computer
generated experimental designs (Myers and Montgomery,
1995) could be used for this task and with better hindsight
might have been used at the outset in the present work, but
it was felt that the Morris and Mitchell design (1983) would
indicate the presence of significant effects at an early stage
in the experimental program. The present results do indicate
these benefits and also point out some of the problems that
can arise in the final analysis of the results.
Conclusion
Variables affecting the high temperature oxidation of low
carbon steel samples have been examined in a laboratory-
scale apparatus using a Morris and Mitchell ( 1 983) experi-
mental screening design. The experimental program includ-
ed eleven runs for the basic design and nine replicate runs to
obtain an estimate of the pure error variance. This type of
design allows for an assessment of the effect of variables
and interactions between variables at an intermediate stage
of the experimental program. The independent variables
investigated included those commonly encountered in
reheat furnace operation: gas composition, temperature,
steel grade and surface preparation. The dependent variable
was the parabolic rate constant estimated from the mass
gained by the steel samples during the oxidation process.
From the results, the following conclusions can be drawn:
I . The phased approach using the Morris and Mitchell
(1983) screening design performed well in this study.
The intermediate results after four and six runs indicated
41 I
 the importance of both main effects and two-factor inter-
actions between variables. The early knowledge gained
from this information served to guide the development
of the process model.
2 . The complete eleven run design confirmed that within
the range o f the variables examined, the most significant
factor was the oxidation temperature. The relative
importance of this variable was indicated at the interme-
diate stages of the experimental program. An interaction
between the qualitative variables, surface condition and
steel grade, w a s also significant. For the lower carbon
grade, a lower scaling rate was observed on samples hav-
ing a partially cast surface while a machined surface
gave higher rates.
Acknowledgements
We acknowledge financial support by the Natural Sciences and
Engineering Research Council of Canada in the form of a CRD
grant. The cooperation of the Ferrous Industry Energy Research
Association (FERA), the assistance of Sue Olynyk and Ted Kerr of
Dofasco, Inc. and useful suggestions by Dr. D.W. Bacon and Dr.
P.J. McLellan of Queen’s University in the project are gratefully
noted.
Nomenclature
integration constant, g2/m4
diffusivity, m2/s
ratio of mean square lack of fit to mean square pure
error
test statistic with a level of significance a and
degrees of freedom vI and v2
identity matrix
112 kp, g2/m4.s
parabolic rate constant, g2/m4.s
lack of fit matrix
gas constant, 8.3 144 J/mol.s
time, s
temperature, K
independent variable
vector of independent variables
dependent variable
predicted value of dependent variable
vector of observations
Greek letters
significance level
regression parameter
parameter estimate
vector of regression parameters
random error
vector of random errors
scale thickness (mass), g
chemical potential, J/mol
degrees of freedom
reference to variable i
reference to interaction between variables i a n d j
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413