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178
 
Mineral Processing Technology (MPT 2007)
An Investigation into the use of Electric Arc Furnace Slagas a Cementitious Material
Luckman Muhmood, Satish Vitta and D.Venkateswaran
Indian Institute of Technology, Indorama Cement Ltd.,BombayBombay
ABSTRACT:
Electric Arc Furnace Slag, which is highly crystalline and rich in iron content, does not find muchuse as an additive in cements. For improving its cementitious properties, heat treatment was done. There was aremarkable reduction in the iron content but the crystallinity was not much affected. Both untreated and treatedslag samples were then hydrated for 3,7,14 and 28 days. The pH of the pore water and the TGA/DTA curvesshowed that the treated slag sample exhibited better hydraulic properties. The slag samples were then mixed with30% 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 thetreated slag exceeded the corresponding strength of the control mix (50% GGBFS and 50% Clinker). Thissubstantiated the fact that the treated slag samples had better hydraulic properties compared to that of theuntreated slag.
1. INTRODUCTION
Slag is a waste product of iron and steel making processes and it includes blast furnace slag,electric arc furnace slag and steel slag. Amongthese, blast furnace slag is used for cement production whereas electric arc furnace and steelslags are currently being used as landfills, whichhave very low value.Though the components making up thecomposition of the slag and clinker samples arethe same, all the three show entirely different properties.GGBFS is highly glassy (93-97%) in nature.This makes it reactive when hydrated; hence itfinds much use as a cement additive. Clinker iscrystalline (70-80%), but hydrates to givehardened cementitious phases. EAFS is highlycrystalline and also rich in iron content. Thismakes it less reactive when hydrated.Experiments were conducted to improve thehydraulic properties of EAFS so as to increase itsutilization in cements.
2. EXPERIMENTATION2.1 Raw Materials
The EAFS was obtained from M/S IspatIndustries Ltd, located in the vicinity of Mumbai(Bombay) in Western India.The sample was crushed and powdered to passthrough # 200 sieve (< 75μm). A representativesample was taken and the chemical and phaseanalysis was done.
2.2 Experimental Work
2.2.1 Phase and Composition Analysis
The powder XRD analysis of the sample wasdone using PHILIPS X’pert Pro Diffractometer and the interpretation of the phases was analyzed by X’pert highscore plus software. Thecompositional analysis of the sample wasobtained from the X-ray Fluorescence analysisusing a PHILIPS PW 2404 spectrometer.
2.2.2 Treatment of EAFS 
The slag was melted in an induction furnace(INDUCTOTHERM, 25kg, 15kV) with agraphite crucible, up to a temperature of 1450
0
Cand then quenched. It was expected that suddencooling would lead to a glassy phase rather than acrystalline, which influences the reactivity of theslag.
2.2.3 Microstructure
The slag samples were polished and etched withnital (1% concentrated HNO
3
in 99% of ethanol).Microstructures was captured using a reflected
 
179
 
Mineral Processing Technology (MPT 2007)
microscope OLUMPUS GX 51 with a numericalcamera Olympus DP12-2 and the study of thedifferent phases for each sample was done withthe help of the EDX information from the SEM(Hitachi S3400N)-EDX (Thermo Noran NSS200).
2.2.4 Hydration and Differential Thermal  Analysis
The slag samples were hydrated by taking a w/cratio of 0.5. These samples were then hydratedfor 3, 7, 14 and 28 days keeping them in a tight polyethylene jar to prevent carbonation. After therequired time period, the hydration was stoppedwith acetone and dried. The pore water obtainedwas separated and the pH measured.Later the dried pastes were crushed and theDTA-TGA was done. This measured the extent of hydration taken place in the sample. APerkinElmer Diamond TG/DTA was used for theanalysis.
2.2.5 Consistency, Setting time &Compressive StrengthMeasurements
The Consistency, Initial and Final Setting timemeasurements were done using a Vicat Appara-tus with standard fittings. The experiments weredone in accordance to IS 4031 (Part 4) and IS4031 (Part 5) respectively.EAFS samples were added along withGGBFS and Clinker in the proportion 2:3:5respectively. Control mix of 50% Clinker and50% GGBFS was used. The compressivestrength measurements were done according toIS 4031 (Part 6).
3. RESULTS AND DISCUSSION
The untreated EAFS was seen to have high ironcontent. Figure 3 shows the XRD pattern of theslag sample. From the phase analysis, it was seenthat a majority of the phase was contributed bywuestite (FeO). Here the iron is in the Fe
2+
stateand hence forms crystalline compounds. Tracesof larnite (Ca
2
SiO
4
) were also seen. Table 1shows that the Untreated EAFS was rich in ironcontent.
20 40 60 80 100200300400500600700800900
   I  n   t  e  n  s   i   t  y   (   C  o  u  n   t  s   )
Position (2 Theta)
WMGGW
M
1
W
G G GM
1
W
M
1
L
W - WuestiteM - MerwiniteG - GehleniteM
1
- MagnesioferriteL - Larnite
Fig. 3:
XRD of Untreated EAFS
Treatment of the EAFS was done in order toimprove its reactivity. During the melting theslag foamed and chunks of iron were alsoobtained. The graphite of the crucible reactedwith the iron oxide of the slag to produce carbonmonoxide, which caused the foaming to occur.C + (FeO) → [Fe] + {CO} ------------ (1)Figure 4 shows the XRD pattern of thetreated slag. The pattern showed a better development of the crystalline phases ascompared to the pattern of the untreated EAFS.Here merwinite (Ca
3
Mg(SiO
4
)
2
) was observed to be the dominant phase. Also the larnite phaseshowed substantial growth.
20 40 60 80 10002004006008001000120014001600
   I  n   t  e  n  s   i   t  y   (   C  o  u  n   t  s   )
Position (2 Theta)
MMM WMMM
M - MerwiniteL- LarniteW - Wuestite
L
Fig. 4:
XRD of Treated EAFS
The compositional analysis (Table 1) showed thatthere was a substantial reduction in the weight percentage of iron oxide in the slag. From theanalysis of the XRD patterns it was also obviousthat the wuestite phase of the untreated slagreduced to a considerable extent.
Table 1:
Composition of Clinker and Slagsamples
 
 An Investigation into the use of Electric Arc Furnace Slag as…
180
SampleCaOSiO
2
 Al 
2
O
3
MgOFeOMnOSO
3
 P 
2
O
5
TiO
2
Others*
UntreatedEAFS30.823.36.11224.11.50.40.60.90.4TreatedEAFS30.626.45.933.60.31.40.10.50.70.6
* Cr 
2
O
3
, V
2
O
5
Figure 5 shows the microstructure of theuntreated slag sample. A predominant presence of wuestite and magnesioferrite was seen, both of which contributed to the high reflectivity of themicrostructure. Elongated crystals present wereobserved to be Merwinite. Larnite was seen to present in very small amount and wascharacterized by its bluish striated grainappearance.
Fig. 5:
Microstructure of Untreated EAFS
Fig. 6:
Microstructure of Treated EAFS
The treated slag (Figure 6) shows the presence of merwinite but with grains of smaller size. Thiswas due to the sudden quenching of the heatedslag. The presence of wuestite was also identified but the amount was less compared to that of theuntreated slag. This substantiates the phenomenaof iron oxide reduction during heat treatment.Hydration of the slag samples was done. The pHof the pore water that gives the extent of hydration of the sample was measured. Figure 7shows that the pH of the untreated slag was lesscompared to that of the treated slag.
0 5 10 15 20 25 308.08.59.09.510.010.511.011.512.012.513.013.514.014.515.0
   p   H    o   f   p   o   r   e  w   a   t   e   r
Hydration Time (days)
Clinker EAFS (Treated)EAFS (Untreated)
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 bothslag samples given in Figure 8 depicts that thetreated sample shows greater mass loss indicatinggreater degree of hydration taking place.
0 5 10 15 20 25 303456789
   W  e   i  g   h   t  g  a   i  n   (   %   )
Hydration time (days)
EAFS (Untreated)EAFS (Treated)
Fig. 8:
TGA curves of slag samples
The DTA curves, shown in Figures 10 and11 depicts that the slag samples show two weak endothermic peaks at 200ºC and 670-700ºCrespectively. The treated sample showed
of 00

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