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The Hot Strength of Industrial Cokes – Evaluation


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of Coke Properties that Affect Its High‐Temperature


Strength
Juho A. Haapakangas, Juha A. Uusitalo, Olli J. Mattila, Stanislav S. Gornostayev,
David A. Porter, and Timo M. J. Fabritius

The strength of coke at high temperatures is of major importance for efficient blast furnace
operation. Despite this, there is little information regarding the hot strength of coke. In this
research, the hot strength of three industrial European coke grades was studied using a
Gleeble thermomechanical simulator. The hot strength was analyzed at three different
temperatures: room temperature, 1600 and 1750 8C by measuring the compressive strength
of roughly 50 coke samples at each temperature. A significant decrease in strength was
observed for all three coke grades at high temperatures. Notable differences between the
coke grades in compressive strength were observed at room temperature. At high
temperatures, differences were observed in strength and deformation behavior; however,
the order of magnitude of strength remained the same. The deformation behavior at high
temperatures was also studied and discussed based on stress–strain curves. Several
structural properties of coke such as total porosity, pore size distribution, pore shape factor,
amount of inerts, and degree of graphitization were determined in order to explain the
obtained strength results. Both hot and room temperature compressive strength values
were compared to industrial strength tests and discussed. The reliability of the results was
evaluated with statistical analyses.

1. Introduction price is increasing, so coke manufacturers will have to


utilize coals of lower quality. One option could be the pre-
Coke as a raw material in the blast furnace provides fuel for pelletizing of weakly coking coals.[1] Also, the high price of
ironmaking, serves as a source of reductant gas, provides metallurgical coke is forcing companies to find alternative
structural support for the material bed and serves to fuels for the blast furnace. A common way to replace coke
carburize hot metal. Its role as structural support is vital is to increase the use of injectant fuels, commonly
and for this reason strength is one of the most important pulverized coal. When less coke is charged, greater
properties of coke. Poor coke strength can cause many chemical stresses are faced by individual lumps of coke.
operational problems, such as reduced permeability in the Coke also undergoes higher load due to thicker iron ore
shaft and hearth areas, undesirable gas and temperature layers and rise of average burden weight. Another issue
distribution, and the possibility of hanging of the burden. is the rising price of CO2 emissions. One possibility to
In the near future, steel manufacturers worldwide are reduce CO2 could be the addition of bio-material or
faced with challenges regarding the quality of coke. The waste plastics into the coking mix, which can negatively
availability of prime coking coals is decreasing and their affect the strength of the coke. All of these factors
increase the importance of coke quality and its analysis
methods.
[] J. A. Haapakangas, S. S. Gornostayev, Prof. T. M. Fabritius
Stresses inside a blast furnace include mechanical
Laboratory of Process Metallurgy, University of Oulu, P. O. Box 4300, stresses such as shattering and abrasion, solution loss
FI-90014 Oulu, Finland reactions, alkaline attack, high temperature, and impact
Email: juho.haapakangas@oulu.fi
J. A. Uusitalo, Prof. D. Porter
shock by the high-speed hot blast. In industry, coke
Materials Engineering Laboratory, University of Oulu, P. O. Box 4200, strength is characterized by drum indices (Micum, Irsid)
FI-90014 Oulu, Finland or drum strength after reaction (CSR). Although these
O. J. Mattila
Ruukki Metals Oy, Rautaruukintie 155, FI-92100 Raahe, Finland methods are useful in assessing coke quality, they do not
measure coke strength at operational temperatures. Blast
DOI: 10.1002/srin.201300450 furnace excavations made in Japan have shown that coke

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size remains mostly unchanged in the upper parts, but graphitization. Only visibly crack-free samples were
significant degradation is observed in the lower parts when selected for strength testing. The method of sample
the temperature exceeds 1400 8C.[2] preparation is shown in Figure 1.
There are few published studies on the hot strength of During strength testing, the Gleeble samples were held
coke, possibly due to difficulties in experimental setup. for 30 s at their respective test temperatures to allow the
The reported hot strength results are somewhat contra- temperature to stabilize throughout the samples. After
dictory: increases in compressive coke strength have been heating, compressive forces were measured while the
reported at 1200,[3] 1300,[4] 1400,[5] and 1650 8C[6] while a samples were mechanically compressed 4 mm at the rate
decrease in coke strength was reported at 2000 8C.[4] It of 1 mm s1. The use of a Gleeble device for testing the hot
should be noted that most of the earlier results have not strength of coke has been described in detail earlier.[7,8]
been statistically reliable due to small sample sizes. The Industrial analyses provided by the coke manufacturers
properties of coke that define its hot strength are largely are displayed in Table 1 and 2.
unknown. The XRD tests were performed with a Siemens D5000
In this study, the study of compressive strength of X-ray diffractometer. The point counting of structural
coke was further expanded to include three industrially properties was performed with a Pelcon Automatic Point
produced European coke grades at room temperature and Counter.
at elevated temperatures of 1600 and 1750 8C. Also in
this study several coke properties, such as total porosity,
inerts, and degree of graphitization were analyzed in
order to study how they relate to the strength of coke 3. Results and Discussion
both and room temperature and at elevated temperatures.
Both the room temperature and hot strength measure- 3.1. Hot Strength
ments were conducted with a Gleeble 3800 thermo-
mechanical testing device. The obtained results were During previous work[7,8] coke hot strength was measured
intended to give information about the strength of for an individual coke grade and a significant decrease in
industrial coke in the lower part of a blast furnace, where strength was observed at 1600 8C in comparison to 1000 8C.
coke is the only solid material and its strength is vital for Afterwards an even further decrease in strength was
good permeability. observed at 1750 8C. Deformation of coke was also
reported to be partially plastic at 1600 8C and plasticity
further increased at 1750 8C. In this study, two new coke
grades were included in the testing.
2. Experimental
All of the coke samples used in the Gleeble experiments
were prepared beforehand and mixed in order to avoid
systematic errors caused by sample location. Coke lumps
were drilled with a hollow drill, cut to appropriate height
and polished to form cylindrical samples of 16 mm in
diameter and roughly 12 mm in height. This size and shape
has been found appropriate for use in the Gleeble device
using a standard sample holder. The largest coke lumps
were selected for sample preparation as small ones are
inadequate for producing a sufficient number of samples.
After machining, the coke samples were pre-graphitized
in a chamber furnace in order to speed up testing in the
Gleeble by reducing the required sample holding time. The
pre-graphitization was made at the sample temperature
that was subsequently used for testing in the Gleeble. It
was done in order to simulate the thermal stresses and
degree of coke graphitization brought about by the descent
of the coke in an actual blast furnace. The coke samples
were sealed in a graphite container and covered in graphite
powder to avoid gasification. In addition, the furnace was
operated in inert gas. The graphite container containing
the coke samples was placed in the furnace at 1200 8C after Figure 1. A) A coke cylinder after drilling, B) a prepared coke
which the temperature was raised up to the subsequent sample, C) the graphitization container, and D) coke sample
test temperature and held for 60 min to ensure complete during a Gleeble test.

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Irsid Irsid Micum Micum CRI CSR Volatiles


> 20 mm < 10 mm > 40 mm < 10 mm [%]

Coke 1 77.2 21.1 21.5 63.6 0.2


Coke 2 85.0 5.4 31.3 57.6 0.2
Coke 3 82.7 5.8 28.2 58.5 0.2

Table 1. Industrial analyses of the studied coke grades.

Total ash SiO2 Al2O3 CaO Fe MgO S K2O Ti Na2O3


[%]

Coke 1 10.6 59.90 26.70 2.45 3.91 0.72 0.76 1.28 0.88 0.38
Coke 2 8.69 44.88 29.92 4.37 7.02 2.30 0.53 2.42 0.81 1.61
Coke 3 9.20 47.83 31.52 3.48 5.65 1.74 0.52 2.28 0.87 1.52

Table 2. Ash component contents.

The strength of three coke grades was measured at room 4 mm (33.3%) compression. In some cases, this was
temperature and at elevated temperatures of 1600 and obtained in the beginning of compression and in some
1750 8C. Originally 50 coke samples were tested for each at the very end.
grade at each temperature in order to obtain statistically The mean strength and strain values at room tempera-
reliable results, however some of the results had to be ture were similar to those reported elsewhere: Kim and
discarded due to equipment malfunction. The strength Sasaki[9] reported compressive strength of coke to vary
results are listed in Table 3. In Table 3 the superscript between 19.4 and 28.6 MPa, while strain at fracture ranged
numbers 7 and 8 represent results obtained during from 2.2 to 3.0%. As observed in Table 3, there were notable
previous work. In the table, the term “ultimate strength” differences in the compressive strength of the coke grades
refers to the highest obtained strength value during the at room temperature; coke 2 was clearly the strongest and

Temperature Number of Mean Strain Standard Effect of heating


samples ultimate [%] deviation on the ultimate
strength [MPa] [MPa] strength [%]

Coke 1
Room 50 16.67) 2.5 7.57)
1600 8C 50 12.17) 3.67) 27.0
1750 8C 50 10.78) 3.38) 35.5
Coke 2
Room 50 23.8 3.0 8.1
1600 8C 40 15.8 5.2 33.6
1750 8C 50 17.5 6.2 26.5
Coke 3
Room 49 13.3 2.5 6.7
1600 8C 50 9.1 3.2 31.5
1750 8C 50 9.7 3.3 27.1

Table 3. Room temperature and hot strength values.

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coke 3 the weakest. The difference in the reported drum be the softening of bonding between carbon layers as a
strength between cokes 2 and 3 in the Micum test, given in result of increased heat energy, which would allow re-
Table 1, was much less pronounced. Unfortunately, only organization of the carbon matrix during compression.
Irsid values were available for coke 1. It is noteworthy that none of the three coke grades
At 1600 8C, the ultimate strength was significantly tested during this study suffered a catastrophic fall in
decreased for all coke grades compared to room tempera- strength as a result of high temperatures. This result was
ture. The decrease in strength was similar for all three expected since all three cokes are used industrially and
coke grades. An increase in test temperature had a varying known to function in actual blast furnace operation. The
effect depending on the coke grade; the strength of significant fall in the strength of coke at high temperatures
coke 1 suffered a further significant drop when heated is contradictory to some of the previous reports by other
to 1750 8C. The ultimate strength of cokes 2 and 3, on the researchers.[3,5,6] A possible explanation for this could be
other hand, seemed to slightly recover as a result of the differences in the coke grades that were analyzed,
increasing the temperature, however, as will be shown different methods of sample preparation (pre-graphitiza-
in Table 4 this result was without statistical significance. tion) or the use of different testing equipment. Some of the
The possible recovery in strength could be explained by studies were also conducted at temperatures below the
the increasing plasticity of the coke at higher temper- melting point of cokes ash components, therefore not
atures. As a result, the density and surface area of coke taking into account their effect. The reported significant
resisting the compressive force are increased during fall in strength at 2000 8C and above, and the observed
deformation resulting in a higher force required for plastic deformation behavior,[4] however, are congruent
further deformation. Plastic deformation behavior of with results of this study.
coke at high temperatures has also been reported in a Statistical reliability of the hot strength results was
previous study.[4] The results indicate that the develop- analyzed using a two-sample t-test assuming unequal
ment of coke hot strength as a function of temperature variances (Welch’s t-test). A two-tailed test with p ¼ 0.05
may be material dependent. Despite the varying effects was chosen as the level of significance. The following
of temperature, the relative strengths of the various coke hypotheses were set and evaluated:
grades remained constant independent of temperature
(2 > 1 > 3). H0: There is no statistical difference in coke hot strength
The reason behind plastic deformation behavior of between the studied temperatures.
coke at high temperatures is unknown. It is the belief of H1: There is a significant difference in the hot strength of
the authors that melting of cokes ash components is not coke at the studied temperatures.
responsible, since it has been shown that in tuyere coke the
melted ash has migrated into pores, therefore it should When the calculated value of t exceeds the critical value
not affect deformation behavior.[10] One explanation could of t and p is below the chosen significance level of 0.05, the

Temperature Degrees of t Critical t p-Value Statistically


freedom significant

Coke 1
Room vs. 1600 8C 70 3.790 1.994 0.000 Yes
Room vs. 1750 8C 67 5.043 1.996 0.000 Yes
1600 vs. 1750 8C 97 2.019 1.985 0.046 Yes
Coke 2
Room vs. 1600 8C 84 5.648 1.989 0.000 Yes
Room vs. 1750 8C 91 4.328 1.986 0.000 Yes
1600 vs. 1750 8C 87 1.443 1.988 0.153 No
Coke 3
Room vs. 1600 8C 68 3.955 1.995 0.000 Yes
Room vs. 1750 8C 70 3.394 1.994 0.001 Yes
1600 vs. 1750 8C 97 0.872 1.985 0.386 No

Table 4. Statistical reliability analysis of the hot strength values.

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difference in strength is concluded to be significant. Based stress–strain curves were identified during the tests and
on the results presented in Table 4, the hypothesis H0 they are presented in Figure 2. For clearer representation,
was accepted in two cases: both for cokes 2 and 3 when the actual stress–strain curves obtained from the
comparing the hot strength between temperatures 1600 Gleeble experiments were re-calculated based on moving
and 1750 8C. Therefore, the differences in strength between average of 30 measurement points (one measurement
these temperatures are statistically insignificant. In all of every 0.01 s). It should be noted that the strain values
the other cases, hypothesis H0 was rejected and the in Figure 2 do not always precisely reflect the true strain
alternative hypothesis H1 was accepted; the difference in values since the graphs were re-calculated based on
the other studied temperatures is statistically significant. moving average. The difference can be up to roughly 2%
Digital stress–strain curves were obtained during the during the linear elastic phase. These stress–strain type
strength tests both at room temperature and at high categories were found to represent the vast majority of all
temperatures. The curves can be used for analyzing the strength experiments both at room temperature and at
deformation behavior of the cokes. Six general types of high temperatures.

Figure 2. General stress–strain curve types (A–F) observed during the compressive strength tests for coke (see text for further details).

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The distribution of all stress–strain curves to the six was also regularly observed at room temperature, which
general types is presented in Table 5. As observed from the could be a sign of layered crushing as reported in a
table, each coke grade was unique in terms of the shape of previous study.[11]
the stress–strain curves at high temperatures. At room The type D curve, like type C, had a steep linear rise in
temperature, only curve types A and C were observed. the stress curve followed by fracture and a decrease in the
Meanwhile, types B, D, E, and F, which indicated plastic stress curve, however, at high temperatures toward the end
deformation, were only found at high temperatures. of compression the stress started to strongly increase.
At room temperature, the ultimate strength values were Types E and F both had a very gentle rise in stress curve
obtained at the very beginning of deformation for all three during the linear elastic phase. Based on the shape of
grades. On a stress–strain curve this is reflected by an the curve, this was followed by fracture half way through
initial almost linear rise in compressive force until fragile the compression, i.e., about roughly 15% strain and a
fracture occurs at 0–4% strain (mean 2.5–3.0%) and in most decrease in stress required for further deformation. Type F
cases followed by a significant decrease in force required showed a second increase in the stress curve toward the
for further deformation. This type of a stress–strain curve is end of indicating plastic deformation during compression
type A in Figure 2. Therefore, it can be stated that and often the highest force value was obtained at the very
deformation behavior was brittle in all room temperature end. Plastic deformation behavior (types B, D, and F) could
cases and the obtained stress–strain curves resembled be considered beneficial for blast furnace performance,
the deformation of a ceramic material, a result, which has since the strength of coke would increase under compres-
been reported in previous studies. sion at high temperatures.
The type B curve was observed at high temperatures and As was reported in Table 3, the standard deviation of
can be considered to indicate plastic deformation during strength showed a strong decrease at high temperatures.
compression: as the coke sample is compressed, its density This can also be observed from the distribution of all
and surface area are increased and force required for results to specific strength regions, which are depicted in
deformation is increased. For type B curves, the ultimate Figure 3.
strength value was obtained at the very end of the 4 mm The distribution of coke strength becomes increasingly
compression. This type was observed for cokes 1 and 2 at narrower as the temperature is increased. This result
high temperatures. was especially pronounced for coke grades 1 and 3. For
Type C curve is similar to type A with a steep linear rise coke 2, the standard deviation decreased at 1600 8C but
in strength, but unlike for type A, there is no dramatic fall was slightly higher at 1750 8C compared to 1600 8C.
in the force required for further deformation, instead This result could be explained by the grades possibly
significant force is still required all the way up to 33% stronger tendency toward plastic deformation as indicated
compression. This type of a curve was common at by the mean strength values. It can be considered that
higher temperatures for coke 1 and especially coke 3. It a narrow strength distribution would be desirable, since

Type A Type B Type C Type D Type E Type F


[%] [%] [%] [%] [%] [%]

Room temperature
Coke 1 76.0 24.0
Coke 2 88.0 12.0
Coke 3 72.0 28.0
1600 8C
Coke 1 2.0 40.0 22.0 22.0 14.0
Coke 2 15.0 67.5 17.5
Coke 3 18.0 46.0 16.0 16.0 4.0
1750 8C
Coke 1 42.0 18.0 4.0 30.0 6.0
Coke 2 4.0 10.0 4.0 62.0 20.0
Coke 3 4.0 56.0 12.0 22.0 6.0

Table 5. Distribution of stress–strain curves among the six general types.

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blast furnace operators value consistent quality and


predictability. Strength of coke 3 is, however, clearly the
highest at all temperatures with a low number of weak
samples. Therefore, out of the tested cokes, the distribu-
tion of coke 3 can be considered the most desirable.
The industrial CSR (coke strength after reaction) test is
often called a hot strength test despite the fact that the
actual drum strength is measured at room temperature
after 2-h gasification at 1100 8C in 100% CO2 gas. Based on
the industrial tests for coke depicted in Table 1, coke 1 had
by far the highest CSR value, likely a direct result of its
lower chemical reactivity (CRI). The high CSR value is
usually interpreted as indicating good performance in a
blast furnace. However, it has been discussed that the
conditions during the CSR test are intensive and the
reaction mechanism differs from an actual blast furnace:
during the CSR test coke is gasified throughout the coke
whereas in a blast furnace reactions occur mainly on the
surface.[12] Despite the usefulness of CRI and CSR tests,
they do not include testing coke at blast furnace temper-
atures. Since no single analysis method is capable of
simulating blast furnace conditions, multiple different
tests are required. The use of a Gleeble could be a useful
addition to the coke testing protocol.
The most authentic strength test could be testing pre-
gasified coke in a thermomechanical simulator, such as
the Gleeble. The pre-gasification could be performed in a
blast furnace gas phase simulator, such as presented in
literature.[13] The tested coke could be also taken from a
dissected blast furnace or an experimental blast furnace,
in which case it would also include the presence of
circulating elements. Including coke gasification to hot
strength testing, however, could not be fit to this article
and deserves a separate investigation.

3.2. The Effect of Heat Treatment on the Room


Temperature Strength

Heat treatment above the temperature of the coking


furnace is expected to have a twofold influence on the
strength of coke: (i) it promotes further graphitization,
which changes the atomic structure of coke into a more
highly ordered one and (ii) it causes significant weight loss
as displayed in Table 6.

Grade 1600 8C 1750 8C


[%] [%]

Coke 1 7.2 10.1


Coke 2 4.9 7.6
Coke 3 6.2 8.7

Table 6. Weight loss of coke as a result of 1 h pre-graphitization in


Figure 3. Distribution of coke strengths. a chamber furnace.

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As was shown in Table 2, coke 1 contained the highest
amount of SiO2, therefore its ash had the highest potential
to react with the carbon matrix (forming SiC and CO) and
to induce weight loss. The weight loss is a result of
chemical reactions, vaporization, and re-organization of
mineral matter in the coke (i.e., decarbonation and
desulphurization[14]). Another issue is the plastic defor-
mation at elevated temperatures. For this reason, a test
was made to study how much merely the preceding
heat treatment affects the room temperature strength
of coke in comparison to it being in a hot state. This
study was done for coke 2 by testing the strength at
room temperature of 50 non-graphitized samples and
50 samples pre-graphitized at 1750 8C. The obtained
strength values are displayed in Table 7. Young’s modulus
was determined from the angular coefficient of linear
elastic part of the stress–strain curves.
As can be seen from Table 7, the mean room
temperature strength of coke is significantly decreased Figure 4. Distribution of strength of coke 2 samples before and
by pre-graphitization. As with strength tests at elevated after heat treatment at 1750 8C.
temperatures, the standard deviation of strength is
much lower. From Figure 4, it can be concluded that
the structure of coke undergoes a process of homo- 3.3. Graphitization Degree of Coke
genization during heat treatment. In particular, samples
showing high strengths are absent after graphitization. Graphite is a crystalline structure of carbon that consists of
The result of a decreased strength is likely a combina- regular, vertical stacking of hexagonal aromatic layers.
tion of several factors including weight loss and a When coke is heated to a sufficiently high temperature,
resultant increase in porosity, as well as changes in the it begins to become more ordered and approach the
crystalline structure of the coke. It has been stated structure of graphite. Further graphitization of coke begins
that as the crystalline structure approaches that of to occur when its temperature exceeds the original coking
graphitic carbon, the cross-linking between carbon temperature; generally above 1100 8C. Graphitization is
layers is decreased and the coke matrix weakened.[15] made possible by the plastic phase of coking, during which
The above results support this theory, however the carbon layers are organized near parallel. As the tempera-
weight of each factor is unknown and deserves separate ture of coke is increased, it enables the continuous
investigations. rearrangement of the layer-planes to take place by small
For both graphitized and non-graphitized samples stages.[16]
tested at room temperature, the breakage mechanism In the structure of graphite, each C atom within an
was the following: a short elastic phase followed by fragile aromatic layer is linked through covalent bonds to three C
fracture. Heat treatment at 1750 8C did not have any atoms. However, bonding between aromatic layers is
noticeable effect on the shape of stress–strain curves, weak, easily broken by external forces. Non-graphitic
except for the angular coefficient of the elastic phase carbon, however, contains cross-linking between the
(Young’s modulus). There was little to no change in the aromatic layers and much higher force is required to
strain value following heat treatment. Therefore, it is dissociate them.[15,17] During heat treatment, non-orga-
expected that the plasticity of coke observed at high nized carbon is presumably attached to the edge atoms
temperatures is purely a result of the temperature during of the graphite like layers, which enables the growth of
the compression, not the preceding heat treatment. organized layers but decreases the cross-linking between

Mean Standard Strain Young’s Change in


strength deviation [%] modulus strength
[MPa] [MPa] [MPa] [%]

Non-graphitized 23.75 8.09 3.0 1337.1


Pre-graphitized (1750 8C) 15.32 5.42 3.1 724.3 35.5%

Table 7. Compressive strength values of coke 2 before and after heat treatment at 1750 8C.

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the layers. After heat treatment between temperatures of


1000 and 2000 8C non-graphitizing carbons become harder
and graphitizing carbons become softer.[16] Therefore, it is
important to know the degree of coke ordering, which is
unique for different coke grades.[18]
Some coals are easily graphitized, others are non-
graphitizing and some, such as anthracite, begin to
graphitize at extremely high temperatures (above
2000 8C). Graphitization is inhibited by random orientation
of the graphite like layers as well as strong cross-linking
between the layers.[16] Coke grades have also been
observed to have varying degrees of graphitization even
in similar annealing temperatures.[18]
The size of graphite crystallites in coke can be
represented by the height of carbon net layer (Lc) and
the spread of carbon net plane (La). The growth of Lc during
graphitization is linear as a function of temperature and
is independent of the gas atmosphere and gasification
reaction. La also increases during heating, but is decreased
during gasification.[19] The graphitization degree of coke
can be evaluated by X-ray diffraction method. In this
work, graphitization degree was evaluated by calculating
the Lc values based on the 002 carbon peaks from the
XRD patterns. Calculating the La values is also possible,
but more difficult due to its smaller intensity in the
XRD spectra. The Lc value can be calculated from X-ray
diffraction profiles using Scherrer’s equation:[17,19]

 0:9l
Lc ðA Þ ¼ ð1Þ
B cos uB


where l is the wavelength of X-ray (A ), B is the angular
width in radians at half-maximum intensity of [002] peak,
and uB: is the reflection angle of [002] peak.
The calculation is based on the assumption that
crystallites are ideal with no strain or distortion. The
results can be considered precise only for ordered
materials. Images of the 002 peak in the XRD spectra
are displayed in Figure 5.
The Lc value illustrates the average height of graphite
crystals in coke, hence a high value indicates a high degree
of graphitization. The Lc values of the studied coke grades
are presented in Table 8.
The calculated Lc values indicate further graphitization
as a result of heat treatment for all three coke grades.
Similar observations have been made in previous studies.
The coke grades also showed similar Lc values at a given
temperature, therefore they are expected to be similar in
terms of graphitization behavior brought about by high
temperatures.
Strength and degree of graphitization of coke may Figure 5. Shapes of the 002 peaks from the XRD spectra of the
indeed be strongly linked: for all three coke grades strength studied coke grades. The background intensities of each curve are
was significantly decreased at high temperatures as the scaled for clearer recognition of the shapes.
degree of graphitization was increased. This observation is
also supported by the fact that the room temperature
strength was significantly lower for coke heat-treated at
1750 8C. However, the significant weight loss and following

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Coke 1 Coke 2 Coke 3 Porosity Inerts Reactive
  
[A ] [A ] [A ] [%] [%] texture
[%]
Untreated 21.8 20.0 16.9
Coke 1 49.0 17.4 33.6
1600 8C 59.8 62.5 62.8
Coke 2 46.0 17.6 36.5
1750 8C 93.2 81.9 88.9
Coke 3 48.1 16.8 35.2
Table 8. Lc values of coke after heat treatment.
Table 9. Total porosity, contents of inert, and reactive texture.

increase of porosity during heat treatment should also be counting method by counting at least 1000 points from
kept in mind as a weakening factor. In this study, all of the five polished sections for each coke grade. Structural data
coke grades proved to be graphitizing and very close in obtained by these analyses is displayed in Table 9.
terms of degree of graphitization at each temperature. Differences in the content of inert material between the
Therefore, their differences in strength at a given coke grades proved to be small. The high strength of coke 2
temperature are probably decided by other factors. reported in Table 3 could be at least partially explained by
its slightly lower total porosity. However, all of the studied
cokes were fairly close in measured structural character-
3.4. Effect of Coke Properties on Their Physical Strength istics and due to the heterogeneous nature of coke
substantial amounts of polished sections would have to
The strength of coke can be divided into two factors: the be analyzed in order to draw certain conclusions.
adhesive strength of the solid matrix and the pore Pore size distribution and pore shape factors were
structure. Lower total porosity is beneficial for coke determined with a MATLAB-based image analysis soft-
strength since high porosity indicates a reduction in the ware[24] using the same polished sections used for point
amount of solid material. This result has been observed in counting. Five images of size 3.5 mm  2.6 mm were taken
previous publications.[5] According to results of 3D from each five polished sections per grade under 4
modeling, total porosity is dominant compared to carbon magnification. The pore shape factor was determined by
matrix bonding strength regarding the mechanical identifying pore edges from LOM images by subsequent
strength of coke.[9] Pore size distribution is also considered thresholding and filtering methods causing the smallest
important, since it affects the distribution of stresses. It has pores to be excluded from the analysis as they could not be
been concluded that small pore size and high density of separated reliably from the darker areas of the coke matrix
pores produce higher strength compared to a small itself. After the pore edge detection, the measured pore
number of large pores.[5,20] Thick coke cell walls in theory surface area was used to determine round-equivalent edge
should be beneficial for strength, however in practice a length, which was divided by measured real edge length on
high density of small pores tends to produce a thin cell each pore. The software was programmed to ignore any
wall. Regular distribution of pores has also been suggested pore connected to the edge of an image in the calculations.
to be beneficial for good strength as cracks can propagate According to the image analysis results shown in
more easily through connected pores.[9,21] Table 10, there was practically no difference in the pore
A high amount of inerts in coke is another factor that has shape factors in any size range. It can be concluded that in
been linked with good strength.[20] High amounts of inerts this study no direct correlation was obtained between coke
have also been reported to decrease the mean pore size, strength and pore shape factors of pores below 1 mm in
which may partially explain their positive effect on diameter. It is thought by the authors that the effects of
strength.[20] A decrease of inert size can improve coke pore shapes on coke strength are caused by flaws,
drum strength up to a certain limit.[22] Inert macerals also connected pores, and pores of larger size than the ones
have higher hardness than reactive macerals. The hardness measured during this study.
of reactive macerals decreases with increasing mosaic
size.[20] Differences exist in the hardness of various coke
textures.[20] However, despite some attempts to link coke
texture with mechanical strength, correlations between the 4. Conclusions
two have been poor and it is possible that the effects of
texture distribution are overshadowed by other factors.[23] The compressive hot strength of three industrially
In order to explain the differences in strength between produced coke grades was analyzed by testing 50 coke
coke grades, total porosity and the contents of inert and samples at room temperature, 1600 and 1750 8C. Statistical
reactive texture were determined. The distribution of these reliability of the obtained strength results was analyzed.
structural parameters was done by a standard point The strength testing was performed with a Gleeble 3800

ß 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim steel research int. 85 (2014) No. 12 1617
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Pore edge Number of pores Pore shape factor


length [mm]
Coke 1 Coke 2 Coke 3 Coke 1 Coke 2 Coke 3

0.20–0.41 51.52 65.12 72.08 0.97 0.97 0.98


0.41–0.82 22.44 30.12 32.44 0.85 0.84 0.86
0.82–1.22 6.20 8.12 7.24 0.72 0.73 0.73
1.22–1.63 3.39 3.72 4.32 0.67 0.66 0.66
1.63 5.64 6.12 5.56 0.55 0.54 0.55

Table 10. Pore size distribution and pore shape factors obtained by image analysis.

thermomechanical simulator. Properties of coke, such as force was required after the initial fracture, although on
total porosity, content of inerts, and reactive macerals as some occasions significant force had to be applied all
well as degree of graphitization were determined in order the way up to the 33% deformation, which may indicate
to explain the observed strengths. The measured strengths layered crushing.
were also compared to industrially obtained strength 6. At temperatures of 1600 and 1750 8C, all three coke
analyses. grades showed unique distributions of stress–strain
The following conclusions can be drawn: curve types. Although the stress–strain curves at high
temperatures were complex, certain general types were
1. Significant differences were observed in the compres- found for each grade. The shape of the stress–strain
sive strength at room temperature. A large statistically curves at high temperatures also indicated plastic
significant drop in ultimate strength (roughly 30%) was deformation.
observed for all three grades when tested at 1600 8C.
Coke 1 suffered a further statistically significant fall
in strength at 1750 8C. Despite differences in the hot Acknowledgments
strength properties between the coke grades, the order This research is a part of the Energy Efficiency & Lifecycle
of strength (2 > 1 > 3) remained the same at high Efficient Metal Processes (ELEMET) research program
temperatures. coordinated by the Finnish Metals and Engineering
2. The standard deviation of strength was significantly Competence Cluster (FIMECC). The Finnish Funding
decreased at high temperatures indicating homogeni- Agency for Technology and Innovation (TEKES) is
zation of coke strength as a result of heating. acknowledged for funding this work. The authors would
3. Differences in contents of inert material and reactive also like to thank Mr. Tommi Kokkonen for assisting with
macerals between the studied coke grades proved to be sample preparation and experimental work.
small. Likewise, the graphitization behavior of all three
grades as a result of heat treatment proved to be similar Received: December 4, 2013;
at the test temperatures. Therefore, the difference in Published online: April 28, 2014
strength was likely governed by other factors such as
pore structure, flaws, or the adhesive strength of the Keywords: blast furnace; coke; high temperature;
carbon matrix. No direct correlation was obtained strength; Gleeble
between coke strength and pore shape factors of pores
below 1 mm in diameter. It is thought by the authors
that the effects of pore shapes on coke strength are References
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1618 steel research int. 85 (2014) No. 12 ß 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.steel-research.de

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