TREATMENT AND CHARACTERIZATION OF ELECTRIC ARC

FURNACE SLAG FOR ITS EFFECTIVE UTILIZATION IN

CEMENTITIOUS PRODUCTS

D. VENKATESWARAN*, D.SHARMA* L.MUHMOOD** S. VITTA**

* Indorama Cement Ltd, New Bombay- 400 705 India

** Indian Institute of Technology, Bombay- 400 076.

Abstract:

Electric Arc Furnace (EAF) slag from one of the steel plants in Western India has been
characterized in detail. Its effectiveness as hydraulic material is examined before and after
heat treatment in an induction furnace. The study shows that while there is a marginal
reduction in the early age strength of the Portland Slag Cement mortar, the later age
strength does not suffer by replacing up to 20% of GGBFS by EAF slag.

The melt-quench treatment of EAF slag containing ~30% Fe2O3, in a graphite lined
induction furnace, shows no improvement in its glass content. However, the resultant slag
is porous and easy to grind with better pozzolanic properties. This is attributable to the
partial removal of iron which separates out as a globular mass at the furnace walls.
However, such separation has not been reported when the slag is subjected to the same
treatment in a platinum crucible or oxide ceramic in a laboratory furnace.

In a separate exercise, the utility of the EAF slag has been examined as sand replacement
material in masonry formulation. For this study, the EAF slag is subjected to size reduction
in a Vertical Shaft Impactor (VSI) in order to obtain suitable size gradation. The results
show that EAF mortar is superior to conventional sand in terms of water demand and
strength. The mortar is volume stable and does not give rise to any abnormal autoclave or
Le-Chatelier expansion tested as per standard procedures.

*
Corresponding Author: dvenkat@indorama.co.in
1. INTRODUCTION:

The solid wastes generated during the metallurgical processes of

extraction and refining are called ‘Slag’. They consist predominantly of oxides and silicates
of magnesium, calcium, aluminum, iron etc. The slags produced during the process of iron
and steel making, are broadly classified in to three categories, viz., the blast furnace slag
from the crude or pig iron production in blast furnace, steel slag from Basic Oxygen
Furnace (BOF) or Electric arc Furnace (EAF) and ladle refining slag from the steel refining
processes in the ladles. The blast furnace slag after granulation and grinding finds extensive
use in cement and concrete. The steel slag, however, is yet to find a value added application
except for its occasional usage as cementitious binders. More often than not it is used as a
landfill material. Most of the recent researches therefore have been focused towards finding
and exploiting the potential advantages of steel slag as a resourceful material1.

The production of finished steel in India increased from 15.2 million

ton in 1993-94 to 36.9 million ton in 2003-2004 recording a growth rate of 9%. The figure
for crude steel output during the 8 month period up to August 06, was 28 million ton. India
is now 7th largest steel producer in the world, just ahead of Ukraine and catching up with
South Korea.2. About 41% of finished steel production comes from integrated steel plants
and 59% of production is through secondary steel route. BOF & EAF account for 55% and
39% respectively, of crude steel production the balance coming from obsolete Open Hearth
Furnace (OHF) process3.

The focus of this paper is on utilization of steel slag for applications

other than filler material. An attempt has been made to characterize the physico-chemical
and mineralogical properties of the slag before and after heat treatment with the view to
assess its potential as a cementitious binder and as sand replacement material in mortars.

2. MATERIALS & METHODS:

2.1 Material:
The steel slag was obtained from the Electric Arc Furnace (EAF) of M/S.
Ispat Industries Ltd located in the vicinity of Mumbai (Bombay) in Western India. The
three million ton integrated steel plant produces both blast furnace slag & steel slag. The
BF slag after granulation, is consumed by the neighboring Indorama Cement Ltd, in the
manufacture of Portland Slag cement and Ground Granulated Blast furnace Slag
conforming to BS-6699. The steel slag after crushing is partly re-cycled through Sintering
Plant. Though the Plant is working towards achieving zero-waste management concept, the
remaining quantity of steel slag is yet to find any useful application.

2.2 Methods:
The following analytical tools were employed to characterize the
slag.
- XRF & XRD for elemental & phase composition.
- SEM/EDXA/Optical Microscopy for morphological & microstructural analysis.
Test on grindability was carried out in Bond Mill. A small portion of the sample that tends
to get enriched in the coarser fraction was collected and examined for its phase
composition.

One of the reasons cited for the poor hydraulicity or pozzolanicity of the EAF slag is its
lack of glass content. In order to enhance the glass content, the EAF slags was crushed to -
10 mm size and subjected to melting at a temperature of 1500°C in a graphite lined
induction furnace. The melt after homogenizing was quenched in water. The samples of
EAF before and after the treatment were milled in a laboratory ball mill to a fineness of
390M2/Kg- 400 M2/Kg and evaluated for their hydraulic behavior in a Portland Slag
Cement based formulation, as partial substitute for GGBS.

Specific gravity of the samples was determined by both specific gravity bottle using
kerosene medium and by Helium Pycnometer.

To evaluate the suitability of the EAF slag as a sand replacement material in masonry
formulation, the slag was crushed in a Vertical Shaft Impactor (VSI) machine to obtain
desired sand sized fractions. The crushed material was cast in the form of prism of size
25mmX25mmX 282 mm, consisting of 1 part of cement and 3 parts of the crushed EAF
sand. After curing, the prisms were tested for autoclave & Le Chatelier expansion in
accordance with Bureau of Indian Standard (BIS)4. Compressive strength of the mortar was
tested on 50 mm cube as per standard practices5. As a control, normal sand was used in
place of EAF slag for all the tests.

3.0 RESULTS & DISCUSSIONS:

3.1 Chemical Analysis:
The Chemical analysis of EAF slag is given in Table-1. The
following observations can be made on the analysis.
The slag shows gain in weight more than that can be accounted for the presence of
sulphur, indicating the presence of native iron. The iron is present in both bi & tri valence
sate. As compared to some of the European steel slag reported in the earlier works6-8, the
EAF slag examined in this work shows more alumina and almost negligible quantity of free
lime.
TABLE-1; Chemical composition of EAF Slag

OXIDES WEIGHT %
SiO2 18.2
Al2O3 9.8
Fe2O3 29.7
CaO 30.8
MgO 8.5
TiO2 0.84
MnO 0.6
P2O5 0.67
S 0.05
Gain on Ignition 2.10
The Basicity Index of the slag calculated based on CaO/SiO2 and CaO/(SiO2+P2O5) works
out to be 1.85 and 1.78 respectively. The relationship between basicity, phase composition
and hydraulic activity of steel slag as reported in the literature is given in Table-2.

TABLE-2: Classification of Steel Slag based on Basicity & Mineralogy (Ref.9)

Basicity
Hydraulicity Group
CaO CaO
SiO2 (SiO2+P2O5)
Low Olivine 0.9-1.5 0.9-1.4
Merwinite 1.5-2.7 1.4-1.6

Medium Dicalcium Silicate 1.6-2.4

High Tricalcium Silicate >2.7 >2.4

Accordingly, the EAF slag examined in this study falls under Merwinite group of low
reactivity or in the border line of merwinite to di-calcium silicate group of low to medium
activity.

3.2 Mineralogical analysis:

The mineralogical composition of composite EAF slag as well as the harder to grind
fraction obtained in Bond mill were examined by XRD. The slag (Fig-1) shows the
presence of wuestite (FeO), followed by magnesio ferrite (MgFe2O4), gehlenite
(Ca2Al(Al,Si)2O7, monticellite ( CaMgSiO4) and larnite ( Ca2SiO4). The harder to grind
fraction of the EAF is richer in wuestite but depleted in larnite and gehlenite.

FIG-1: XRD of the EAF Slag Composite

3.3 Physical Characteristics:

The specific gravity of the slag as determined by Helium Pycnometer is 3.72 as against
3.65 determined by specific gravity bottle method using kerosene. The Bond Work Index
of the slag is 27 Kwh/ short ton which is some what lesser than the values 29-30 Kwh/short
ton, reported for the LD steel slags of Indian origin10.

3.4 Properties of Melt-Quenched EAF slag.

The changes in the mineral oxide concentration before and after the treatment are given in
Fig-2. The phase composition by XRD is shown in Fig.3. From the XRD pattern, it is
apparent that the melt quench treatment of the sample in graphite lined furnace has not
resulted in any enhancement of the glassy phase. A similar treatment on fly ash has been
reported to give a glass content of over 95% with much improved pozzolanic properties11.
On the contrary, in case of EAF slag, the crystallinity has improved over the untreated slag.
There is a noticeable reduction in iron oxide content in the treated slag samples with
concomitant increase in CaO and SiO2 contents. This reduction can be attributed to the
observation that during melting some of the iron separates out as nodular mass and tends to
settle down at the bottom &side walls of the graphite lined furnace. These were physically
removed from the rest of the materials before analysis. The phase composition shows
increase in merwinite, larnite and reduction in wuestite phase.
 FIG-3: XRD OF EAF SLAG AFTER MELT-QUENCH TREATMENT

The specific gravity of the slag is 3.5 which is marginally lower than the corresponding
untreated EAF slag. The slag is porous and shows easy grindability characteristics. Under
identical loading conditions in a laboratory ball mill, the treated slag takes just half the time
to that of untreated EAF slag, to attain the fineness of 400 M2/Kg

3.5 Microstructure:

The microstructure of the EAF slag before & after heat treatment is given in Fig-4. The
EAF slag shows predominant presence of Wuestite with high reflectivity and magnesio
ferrite and silicates. The melt quenched sample exhibits typical dentritic structure with
smaller crystals of merwinite and larnite showing preferred orientation. Wuestite is present
to a lesser extent often as an interstitial phase in the matrix.

(A) (B)
FIG:4 : Microstructure of EAF Slag Before (A) & After (B) Melt-Quench treatment in a
graphite furnace. The bright crystals of Wuestite are lesser and the elongated crystals of
Melilite give rise to dentritic type smaller crystals of Merwinite & Larnite. (After Nital
Etch)
A similar study conducted on Indian Steel slags in which the author was involved, no such
reduction of iron content or any change in phase assemblage is reported10. In this study the
melt-quench experiment was conducted on a laboratory scale using Platinum crucible and
oxide ceramic refractory. The microstructure, however, showed distinct difference, similar
to the one reported in this work- Fig.5

A B C

FIG:5: Microstructure of LD Steel Slag before (A) and after melt quench experiment on
lab scale in Pt crucible (B&C).-NITAL etched. The phase composition (Wuestite, Larnite
& Mg-ferrite) remains the same before & after treatment. But the microstructure shows
distinct differences. XRD showed no difference in glass content. ( Ref:10)

3.6 Strength Characteristics

It has been reported that a specialty Portland-Steel slag- Blast furnace slag cement
(PSBC) comprising of 30% steel slag, 30% GGBFS, 35% cement clinker and 5% gypsum
is commercially marketed in China for more than 20 years9. This type of cement though
lower in early age strength and has longer setting time it has the advantage of low energy
cost, lower heat of hydration, higher later age strength development and higher abrasion
resistance. More or less similar composition has been tested in this work using treated and
untreated EAF slag. The results are given in Table-3.

One of the striking features of the steel slag incorporation is the noticeable
reduction in water demand for the standard consistency. No significant change in setting
time was observed with respect to control sample containing only GGBS and no EAF.
Though there is a marginal reduction in the early age strength up to 7 days, the strengths
become equal at 28-days. The sample containing treated EAF slag supersedes the control at
28 days. It is expected that the strength of the samples containing EAF slags would surpass
the control samples at ages beyond 28 days.
 Table-3: Strength characteristics of slag cement mortar with EAF slag

COMPOSITION CONTROL EAF EAF HEAT

UN-TREATED TREATED
OPC % (Including Gypsum) 50 50 50

GGBS % 50 30 30

EAF % 20 20

STD. CONSISTENCY
WATER % 29.5 26.5 26.5
SETTING TIME (MIN)

INITIAL 120 130 120

FINAL 210 220 220

COMPRESSIVE
STRENGTH (MPa) @27°C
1-DAY 14.1 13.8 14.1
3-DAY 32.2 28.0 31.0
7-DAY 47.0 45.0 44.8
28-DAY 58.6 58.0 61.0

3.7 Expansion & Masonry Strength Characteristics:

One of the major constraints reported for steel slag’s utilization as an aggregate has
been its volume instability7. The volume change is caused mainly due to the presence of
free lime and free magnesia in the form of periclase. Though the EAF slag examined in this
study has a free lime content of less than 1%, no accurate quantification could be carried
out for free magnesia in the sample. In the absence of any reliable chemical method for free
magnesia estimation, XRD technique is generally employed for its detection. In this study
the presence of periclase could not be established unambiguously in XRD due to peak
overlaps. In order to assess the expansion characteristics and volume stability certain
accelerated tests were carried out4.

TABLE-4: Soundness Test of Mortar with crushed EAF sand (IS-4031, PART-3 1988 )

MORTAR MIX % AUTOCLAVE EXPAN LE CHATELIER EXP (MM)

1 Part OPC Cement

3 Part Std. Sand (0.1to 2
mm size) 0.022 0.75
1 Part OPC Cement
3 Part Crushed (EAF) 0.035 0.5
Sand (0.1to 2 mm size)
The results confirm that the sand made of EAF slag is sound and volume stable and on par
with standard sand.

TABLE-5: Strength of Masonry mortar based on EAF Sand ( IS- 4031 PART-7, 1988)

FEATURES CONTROL STD SAND CRUSHED EAF SAND

Masonry Cement 420 gm 420 gm

Sand 0.1 mm to 3 mm 1440 gm 1440 gm
%Flow 105% 110%
Bulk density of Mortar
(gm/cc) 1.7 2.0
Strength (MPa)
3-DAYS 5.4 10
7-DAYS 7.0 12.6

The standard 50 mm cube cast as above with masonry cement at a fixed water-cement ratio
of 0.5, shows much superior strength characteristics compared to standard quartz sand of
similar size gradation.

4.0 SUMMARY:

- Electric Arc Furnace slag from an integrated steel plant has been characterized
for its physico-chemical and mineralogical properties. It is classified as low to
medium reactivity slag, based on its chemical composition (basicity) and phase
assemblage.

- The melt-quench treatment in a graphite lined furnace failed to yield improved

glass content. There is a tendency for iron to separate out as granular mass,
settling down at the bottom & side of the graphite lined furnace.

- At 20% substitution level for GGBFS in a Portland Slag Cement formulation,

the EAF slag gives comparable strength at 28 days as that of the control sample
and results in better workability. The heat treated EAF slag supersedes the
control sample in strength at 28 days. However, there is some marginal
reduction in early age strength.

- The mortars made of crushed EAF shows good volume stability as assessed
from standard autoclave and Le Chatelier expansion tests. The crushed and
graded EAF sand gives higher strength as compared to standard sand in the
masonry cement mortar.

- The study confirms the potential of EAF slag as a valuable cementitious binder.
The crushed and graded EAF sand is an ideal substitute for the sand in masonry
mortar especially where availability of good quality sand is limited.
ACKNOWLEDGMENT:

The authors thank Mr. Sanjeev Parasrampuria, Executive Director,

Indorama Cement Ltd for his encouragement and sponsoring this study at Indian
Institute of Technology, Bombay, where part of the work has been carried out. The
authors also thank M/S. Ispat Industries Ltd, for useful interaction during the course
of this work.

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