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178  Mineral Processing Technology (MPT 2007)

An Investigation into the use of Electric Arc Furnace Slag


as a Cementitious Material
Luckman Muhmood, Satish Vitta and D.Venkateswaran
Indian Institute of Technology, Indorama Cement Ltd.,
Bombay Bombay

ABSTRACT: Electric Arc Furnace Slag, which is highly crystalline and rich in iron content, does not find much
use as an additive in cements. For improving its cementitious properties, heat treatment was done. There was a
remarkable reduction in the iron content but the crystallinity was not much affected. Both untreated and treated
slag samples were then hydrated for 3,7,14 and 28 days. The pH of the pore water and the TGA/DTA curves
showed that the treated slag sample exhibited better hydraulic properties. The slag samples were then mixed with
30% Ground Granulated Blast Furnace Slag (GGBFS) and 50% Clinker for compressive strength measurements.
GGBFS was used to provide a reactive media for the slag to hydrate. It was seen that the 28-day strength of the
treated slag exceeded the corresponding strength of the control mix (50% GGBFS and 50% Clinker). This
substantiated the fact that the treated slag samples had better hydraulic properties compared to that of the
untreated slag.

1. INTRODUCTION The sample was crushed and powdered to pass


through # 200 sieve (< 75μm). A representative
Slag is a waste product of iron and steel making sample was taken and the chemical and phase
processes and it includes blast furnace slag, analysis was done.
electric arc furnace slag and steel slag. Among
these, blast furnace slag is used for cement
2.2 Experimental Work
production whereas electric arc furnace and steel
slags are currently being used as landfills, which 2.2.1 Phase and Composition Analysis
have very low value.
Though the components making up the The powder XRD analysis of the sample was
composition of the slag and clinker samples are done using PHILIPS X’pert Pro Diffractometer
the same, all the three show entirely different and the interpretation of the phases was analyzed
properties. by X’pert highscore plus software. The
GGBFS is highly glassy (93-97%) in nature. compositional analysis of the sample was
This makes it reactive when hydrated; hence it obtained from the X-ray Fluorescence analysis
finds much use as a cement additive. Clinker is using a PHILIPS PW 2404 spectrometer.
crystalline (70-80%), but hydrates to give
hardened cementitious phases. EAFS is highly 2.2.2 Treatment of EAFS
crystalline and also rich in iron content. This
makes it less reactive when hydrated. The slag was melted in an induction furnace
Experiments were conducted to improve the (INDUCTOTHERM, 25kg, 15kV) with a
hydraulic properties of EAFS so as to increase its graphite crucible, up to a temperature of 14500C
utilization in cements. and then quenched. It was expected that sudden
cooling would lead to a glassy phase rather than a
crystalline, which influences the reactivity of the
2. EXPERIMENTATION slag.
2.1 Raw Materials
2.2.3 Microstructure
The EAFS was obtained from M/S Ispat
Industries Ltd, located in the vicinity of Mumbai The slag samples were polished and etched with
(Bombay) in Western India. nital (1% concentrated HNO3 in 99% of ethanol).
Microstructures was captured using a reflected
179  Mineral Processing Technology (MPT 2007)
microscope OLUMPUS GX 51 with a numerical shows that the Untreated EAFS was rich in iron
camera Olympus DP12-2 and the study of the content.
different phases for each sample was done with
W - Wuestite
the help of the EDX information from the SEM

Intensity (Counts)
900 W M - Merwinite
(Hitachi S3400N)-EDX (Thermo Noran 800 M
G - Gehlenite
NSS200). 700
G
1
M - Magnesioferrite
L M1W W L - Larnite
600 M
1

2.2.4 Hydration and Differential Thermal


GG G
500 1
M W

Analysis 400

300

The slag samples were hydrated by taking a w/c 200


20 40 60 80 100

ratio of 0.5. These samples were then hydrated Position (2 Theta)


for 3, 7, 14 and 28 days keeping them in a tight
Fig. 3: XRD of Untreated EAFS
polyethylene jar to prevent carbonation. After the
required time period, the hydration was stopped
with acetone and dried. The pore water obtained Treatment of the EAFS was done in order to
was separated and the pH measured. improve its reactivity. During the melting the
slag foamed and chunks of iron were also
Later the dried pastes were crushed and the obtained. The graphite of the crucible reacted
DTA-TGA was done. This measured the extent of with the iron oxide of the slag to produce carbon
hydration taken place in the sample. A monoxide, which caused the foaming to occur.
PerkinElmer Diamond TG/DTA was used for the
analysis. C + (FeO) → [Fe] + {CO} ------------ (1)
Figure 4 shows the XRD pattern of the
treated slag. The pattern showed a better
2.2.5 Consistency, Setting time & development of the crystalline phases as
Compressive Strength compared to the pattern of the untreated EAFS.
Measurements Here merwinite (Ca3Mg(SiO4)2) was observed to
be the dominant phase. Also the larnite phase
The Consistency, Initial and Final Setting time
showed substantial growth.
measurements were done using a Vicat Appara-
tus with standard fittings. The experiments were M - Merwinite
Intensity (Counts)

1600 M

done in accordance to IS 4031 (Part 4) and IS 1400


L- Larnite
W - Wuestite
4031 (Part 5) respectively. 1200

EAFS samples were added along with 1000

GGBFS and Clinker in the proportion 2:3:5 800

600
L
M

respectively. Control mix of 50% Clinker and 400


MW
M
M

50% GGBFS was used. The compressive 200


M

strength measurements were done according to 0

IS 4031 (Part 6). 20 40 60 80 100

Position (2 Theta)

3. RESULTS AND DISCUSSION Fig. 4: XRD of Treated EAFS

The untreated EAFS was seen to have high iron The compositional analysis (Table 1) showed that
content. Figure 3 shows the XRD pattern of the there was a substantial reduction in the weight
slag sample. From the phase analysis, it was seen percentage of iron oxide in the slag. From the
that a majority of the phase was contributed by analysis of the XRD patterns it was also obvious
wuestite (FeO). Here the iron is in the Fe2+ state that the wuestite phase of the untreated slag
and hence forms crystalline compounds. Traces reduced to a considerable extent.
of larnite (Ca2SiO4) were also seen. Table 1 Table 1: Composition of Clinker and Slag
samples
An Investigation into the use of Electric Arc Furnace Slag as… 180
Others untreated slag. This substantiates the phenomena
Sample CaO SiO2 Al2O3 MgO FeO MnO SO3 P2O5 TiO2
* of iron oxide reduction during heat treatment.
Untreated
EAFS
30.8 23.3 6.1 12 24.1 1.5 0.4 0.6 0.9 0.4 Hydration of the slag samples was done. The pH
Treated
of the pore water that gives the extent of
30.6 26.4 5.9 33.6 0.3 1.4 0.1 0.5 0.7 0.6
EAFS hydration of the sample was measured. Figure 7
shows that the pH of the untreated slag was less
* Cr2O3, V2O5 compared to that of the treated slag.

Clinker
Figure 5 shows the microstructure of the 15.0 EAFS (Treated)
untreated slag sample. A predominant presence of 14.5 EAFS (Untreated)
14.0
wuestite and magnesioferrite was seen, both of 13.5
which contributed to the high reflectivity of the 13.0

microstructure. Elongated crystals present were

pH of pore water
12.5
12.0
observed to be Merwinite. Larnite was seen to 11.5

present in very small amount and was 11.0

characterized by its bluish striated grain 10.5


10.0
appearance. 9.5
9.0
8.5
8.0
0 5 10 15 20 25 30

Hydration Time (days)

Fig. 7: Variation of pH of pore water

To quantify the degree of hydration taking


place in both samples, TGA/DTA was done
(Ramachandran, 1969). The TGA curves of both
slag samples given in Figure 8 depicts that the
treated sample shows greater mass loss indicating
Fig. 5: Microstructure of Untreated EAFS greater degree of hydration taking place.

EAFS (Untreated)
EAFS (Treated)
9

8
Weight gain (%)

Fig. 6: Microstructure of Treated EAFS 0 5 10 15 20 25 30

Hydration time (days)


The treated slag (Figure 6) shows the presence of
merwinite but with grains of smaller size. This Fig. 8: TGA curves of slag samples
was due to the sudden quenching of the heated The DTA curves, shown in Figures 10 and
slag. The presence of wuestite was also identified 11 depicts that the slag samples show two weak
but the amount was less compared to that of the endothermic peaks at 200ºC and 670-700ºC
respectively. The treated sample showed
181  Mineral Processing Technology (MPT 2007)

Microvolt Endo Down


significant endothermic peaks in these tempera-
28 DAY
ture ranges compared to the untreated slag. The
endothermic peak corresponding to 200ºC was
due to dehydration and the peak at 670-700ºC
was due to the formation of CaCO3.
14 DAY
EAFS was added along with GGBFS and
Clinker in the proportion 2:3:5 respectively
(Venkateswaran, 2006) for the compressive
strength measurement. The GGBFS was used in 7 DAY
order to provide a reactive media for the EAFS
to hydrate. A control mix of 50% Clinker and
50% GGBFS was taken. The results are given in
Table 2. 3 DAY
Microvolt Endo Down

28 DAY

0 200 400 600 800 1000

Temperature (degree celcius)


14 DAY
Figure 11. DTA curve of hydrated treated EAFS

Table 2: Strength characteristics of slag cement


mortar with EAF slag
7 DAY
Contro EAFS EAFS
Composition
l mix Untreated Treated

OPC % (Including
50 50 50
Gypsum)
3 DAY
GGBFS % 50 30 30
EAFS % 0 20 20
Std. Consistency 29.5 26.5 26.5
0 200 400 600 800 1000
Setting Time (min)
Temperature (degree celcius)
Initial 120 130 120
Fig. 10: DTA curve of hydrated untreated EAFS Final 210 220 220
Compressive
One of the striking features of the steel slag Strength (Mpa)
@27°C
incorporation was the noticeable reduction in
water demand for the standard consistency. No 1-Day 14.1 13.8 14.1
significant change in setting time was observed 3-Day 32.2 28 31
with respect to control sample. Though there was 7-Day 47 45 44.8
a marginal reduction in the early age strength up 28-Day 58.6 58 61
to 7 days, the strength became equal at 28-days.
The sample containing treated EAFS superseded
the control mix at 28 days. This is due to the 4. CONCLUSIONS
presence of the dicalcium slicate, which shows From the experiments conducted, it is clearly
later strength. visible that the treated EAFS was more hydraulic
than the untreated slag. The increase of the
hydraulicity of the treated slag may be due to the
reduction in iron, which is one of the major
hindrances to the reactivity of the slag. The
An Investigation into the use of Electric Arc Furnace Slag as… 182
refinement of the crystalline phase enhanced the REFERENCES
formation of dicalcium silicate that contributed to
the strength after 28 days of hydration. One of [1] D. Venkateswaran, D. Sharma, L. Muhmood,
S.Vitta, “Treatment and Characterization of
the striking features of the steel slag
Electric Arc Furnace Slag for its Effective
incorporation was the noticeable reduction in Utilization in Cementitious Products”,
water demand for the standard consistency. The Proceedings of the Second Global Slag
study confirms that EAFS when suitably treated Conference, Bangkok, November 2006.
could be used as an additive in cements. [2] V.S. Ramachandran, “Applications of Differential
Thermal Analysis in Cement Chemistry”, 1969,
Chemical Publishing Company, New York.