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The effect of X-ray irradiation upon the structure and morphology of samples of clinker, plaster, and electric furnace slag was studied. Slag was obtained in the process of austenite manganese steel casting. The research objective was to determine the stability of these materials under radiation.
The changes that occurred were analyzed by X-ray diffraction and scanning electron microscopy. The diffractograms show changes in the profile, number, relative intensity of diffraction lines, and measured width values at half the maximum height. The micrographs show swelling and cracking of grains. As the radiation time was prolonged, this phenomenon became more evident, which points to the apparent change in the size and shape of the slag, clinker, and plaster grains, i.e. the elementary components of cement

Rastovčan-Mioč, Alenka

Cerjan-Stefanović, Štefica

Novosel-Radović, Vjera

Mioč, Boro

Sofilić, Tahir

ISSN-0011-1643
CCA-2741 Original Scientific Paper
Influence of X-ray Radiation
on the Phase Composition and Morphology of Electric
Furnace Slag, Clinker, and Plaster
Alenka Rastov~an-Mio~,a,* [tefica Cerjan-Stefanovi},b
Vjera Novosel-Radovi},c Boro Mio~,d and Tahir Sofili}c
a Faculty of Metallurgy, University of Zagreb,
Aleja narodnih heroja 3, 44103 Sisak, Croatia
b Faculty of Chemical Engineering and Technology, University of Zagreb,
Maruli}ev trg 19, 10000 Zagreb, Croatia
c Sisak Steelworks, Bo`idara Ad`ije 19, 44010 Sisak, Croatia
d Felis d.o.o., Bo`idara Ad`ije 19, 44010 Sisak, Croatia
Received June 7, 2000; revised January 5, 2001; accepted February 8, 2001
The effect of X-ray irradiation upon the structure and morphology
of samples of clinker, plaster, and electric furnace slag was studied.
Slag was obtained in the process of austenite manganese steel
casting. The research objective was to determine the stability of
these materials under radiation.
The changes that occurred were analyzed by X-ray diffraction and
scanning electron microscopy. The diffractograms show changes in
the profile, number, relative intensity of diffraction lines, and mea-
sured width values at half the maximum height. The micrographs
show swelling and cracking of grains. As the radiation time was
prolonged, this phenomenon became more evident, which points to
the apparent change in the size and shape of the slag, clinker, and
plaster grains, i.e. the elementary components of cement.
Key words: cement, electric furnace slag, clinker, plaster, radiation.
* Author to whom correspondence should be addressed.
CROATICA CHEMICA ACTA CCACAA 74 (2) 419¿430 (2001)
INTRODUCTION
Slags from iron and steel industries are sometimes classified as indus-
trial waste material. Today these by-products are valuable and extremely
versatile construction materials. Potential fields of slag application have been
extended over the past few years, mostly for environmental and economic
reasons. Construction industry has applied predominantly granulated slag,
obtained by quick cooling of molten blast-furnace slag, basic-oxygen furnace
steel slag and magnesium slag. Quick cooling is performed with large vol-
umes of running water or a slag jet is subjected to a water jet, i.e. air-water
jet. Such slag hardens like glass and it can be used as a raw material for the
production of clinker or as an additive to Portland cement. Slag can also be
used as a potential replacement for Portland cement in concrete. In the pro-
duction of clinker, slag can be used as raw material in the cooled lumpy form
although it hardens to a crystalline stone material and is better used in the
road construction.1,2
Today, due to the ever increasing share of electric steel worldwide, i.e.
reduced production of iron in blast-furnaces, steel mill slag is gaining more
and more significance and is replacing blast-furnace slag in numerous fields
of application.3,4 In metallurgy, steel mill slag is used as iron provider and
flux and it can also be used as construction material. It is very successfully
applied in forestry, agriculture, glass industry, wool industry and in the pro-
duction of water purification filter media.
The starting point of this work was the presumption that slag is used as an
additive in the construction industry. Such an application of slag must deal
with the potential problem: aging of construction material is a consequence
of its exposure to weather or to radiation. The effects of these influences
may not be visible at first, but in the course of time they lead to structural
changes, which directly affect the mechanical properties of the material.5–7
Therefore, this research included the influence of X-ray radiation upon
samples of electric furnace slag,* Portland cement clinker,** and technical
plaster*** (cement ingredients). The phase composition and morphology of
the samples were examined before and after exposure to X-ray radiation for
1, 3, and 5 hours. X-ray diffraction analysis and scanning electron micros-
copy were applied.
420 A. RASTOV^AN-MIO^ ET AL.
* Hereinafter referred to as : slag.
** Hereinafter referred to as : clinker.
*** Hereinafter referred to as : plaster.
EXPERIMENTAL
Samples
Samples of slag, clinker, and plaster were examined.
The slag sample was obtained in the production of austenite manganese steel in
the basic electric arc furnace (at 1883 K) at the »Felis« Foundry in Sisak. The sample
was taken with a spoon onto a plate and slowly cooled with a small quantity of wa-
ter. (Although this procedure resulted in a crystalline structure, it is equivalent to
the structure of most slag materials at waste deposits). The cold sample (294 K) was
ground and homogenized for 150 minutes in a Herzog vibration mill. Successive
quartering and crushing of the cold sample provided 100 g of sample.
Samples of clinker (Portland cement clinker made of high carbonate and low car-
bonate raw materials) and plaster (technical stone) were supplied by the »Na{ice-ce-
ment« Cement Factory.
All samples were dried for 2 hours at 378 K and stored in a desiccator above sil-
ica gel.
Part of the samples were placed as thin films on Mylar foil in the sample holder
Philips PW 1427/40. They were irradiated for 1, 3 or 5 hours in the X-ray spectrometer,
Philips PW 1410/10 (Au – anode, 25 mA, 50 kV). The resulting structural and morpho-
logical changes were examined by X-ray diffraction and scanning electron microscopy.
Procedures
Chemical Analysis: Chemical composition of the samples was examined with
standard chemical procedures.8,9
X-ray Diffraction Analysis: In order to determine the phase composition of unir-
radiated and irradiated slag, clinker, and plaster samples, the method of X-ray dif-
fraction was applied. All samples were prepared in a standard procedure.10
X-ray diffraction powder patterns were taken at room temperature using a counter
diffractometer with monochromatized Cr-K radiation (Philips diffractometer, pro-
portional counter and graphite monochromator). Diffraction intensities of the 004 re-
flection (Mn,Mg)2SiO4 (slag), 312 reflection 3CaO  SiO2 (clinker) and 123 reflection
CaSO4  2H2O (plaster) were measured and the full-width at half-maximum (FWHM)
was determined.
In the present work, phases were identified according to the data in the ICDD
Powder Diffraction File (cards: 4–0326, 12–432, 14–376, 1–1127, 14–77, 11–273,
12–145, 12–284, 10–139, 13–209, 13–534, 6–0046, 2–1124, 6–0046, 5–0586, 8–133,
11–179, 5–0490 i 15–776).11 Other phases were identified according to Narita.12
Scanning Electron Microscopy: The morphology of irradiated samples of slag,
clinker, and plaster was determined by means of a scanning electron microscope.
The scanning electron microscopy samples were attached to a support with colloidal
silver and coated with an evaporated layer of copper in a JEOL type evaporator.
Electron micrographs were taken on a JEOL JXA 50A scanning electron microscope.
INFLUENCE OF RADIATION ON SLAG 421
RESULTS AND DISCUSSION
The chemical composition of slag, clinker, and plaster samples was ana-
lyzed. The phase compostion and morphology of these samples were exam-
ined before and after their exposure to X-rays for one, three, and five hours.
Results of the quantitative chemical analysis are shown in Table I.
Results of the X-ray diffraction phase analysis are given in Figures 1 to
3. (Characteristic sections of diffractograms are shown in the figures). The
obtained diffractograms show changes in the profiles of the recorded dif-
fractional lines, their relative intensity, and number. Thus, slag diffractograms
(Figure 1) indicate a change in the profile of diffraction lines, which corre-
spond to the (Mn,Mg)2SiO4 phase. As for the clinker sample (Figure 2), the
most distinct changes were observed in the profiles of diffraction lines corre-
sponding to the 3CaO  SiO2 phase, and in the plaster sample (Figure 3) to
the CaSO4  2H2O phase. The changes were less detectable in the profiles of
diffraction lines corresponding to other identified phases.
The recorded changes resulting from exposure to radiation are implied
by the change in FWHM value of the characteristic diffraction line profile of
the reflection 004 of (Mn,Mg2)SiO4 (slag), 312 of 3CaO  SiO2 (clinker) and
422 A. RASTOV^AN-MIO^ ET AL.
TABLE I
Mass fraction / % of slag, clinker, and plaster
Slag Clinker Plaster
SiO2
Fe2O3
CaO
MgO
K2O
Na2O
Mn2O3
P2O5
31.25
2.00
13.21
16.24
0.85
0.26
35.97
0.048
SiO2
Fe2O3
CaO
MgO
K2O
Na2O
Al2O3
loss on ignition
insoluble/HCl
free CaO
20.76
2.81
65.32
1.81
0.72
0.23
5.89
0.82
0.33
0.65
CaSO42H2O+CaSO41/2H2O
Fe2O3
CaCO3
MgCO3
Al2O3
SiO2 + insoluble
91.24
0.50
3.83
2.34
0.38
1.45
INFLUENCE OF RADIATION ON SLAG 423
F
ig
u
re
1.
X
-r
ay
di
ff
ra
ct
io
n
pa
tt
er
n
s
of
th
e
sl
ag
sa
m
pl
e
be
fo
re
ir
ra
di
at
io
n
(a
)
an
d
af
te
r
ir
ra
di
at
io
n
w
it
h
th
e
pr
im
ar
y
X
-r
ay
be
am
fo
r
1
h
ou
r
(b
),
3
h
ou
rs
(c
),
an
d
5
h
ou
rs
(d
).
Id
en
ti
fi
ed
ph
as
es
:
1:
M
n
O
;
2:
M
n
O

S
iO
2;
3:
(M
n
,
M
g)
2S
iO
4;
4:
M
n
3O
4;
5:
3C
aO

2S
iO
2;
6:
M
gS
iO
3;
7:

C
aO
·
S
iO
2;
8:
C
aO

F
e 2
O
3;
9:
2F
eO

S
iO
2;
10
:
M
n
F
e 2
O
4.
424 A. RASTOV^AN-MIO^ ET AL.
F
ig
u
re
2.
X
-r
ay
di
ff
ra
ct
io
n
pa
tt
er
n
s
of
th
e
cl
in
k
er
sa
m
pl
e
be
fo
re
ir
ra
di
at
io
n
(a
)
an
d
af
te
r
ir
ra
d
ia
ti
on
w
it
h
th
e
p
ri
m
ar
y
X
-r
ay
be
am
fo
r
1
h
ou
r
(b
),
3
h
ou
rs
(c
),
an
d
5
h
ou
rs
(d
).
Id
en
ti
fi
ed
ph
as
es
:
1:
3C
aO

S
iO
2;
2:

2C
aO

S
iO
2;
3:

2C
aO

S
iO
2;
4:

F
e 2
O
3;
5:
2C
aS
O
4

H
2O
;
6:
C
a 3
A
l 2
(O
H
) 2
.
INFLUENCE OF RADIATION ON SLAG 425
F
ig
u
re
3.
X
-r
ay
di
ff
ra
ct
io
n
pa
tt
er
n
s
of
th
e
pl
as
te
r
sa
m
pl
e
be
fo
re
ir
ra
di
at
io
n
(a
)
an
d
af
te
r
ir
ra
d
ia
ti
on
w
it
h
th
e
p
ri
m
ar
y
X
-r
ay
be
am
fo
r
1
h
ou
r
(b
),
3
h
ou
rs
(c
),
an
d
5
h
ou
rs
(d
).
Id
en
ti
fi
ed
p
h
a
se
s:
1:
C
aS
O
4

2H
2O
;
2:
C
aC
O
3;
3:
F
eC
O
3;
4:
3C
aO

A
l 2
O
3

C
aS
O
4

13
H
2O
;
5:
S
iO
2;
6:
3A
l 2
O
3

2S
iO
2.
123 of CaSO4  2H2O (plaster), as well. This is shown in Table II. The FWHM
value within individual samples does not change uniformly. Thus, in the slag
sample, the FWHM value of the 004 reflection of (Mn,Mg)2SiO4 increases
from 1.09°2 (not exposed sample) to 1.22°2 (after three-hour exposure) and
then it decreases to 1.14°2 (after five-hour exposure). In the clinker sam-
ple, the FWHM value of the 312 reflection of 3CaO  SiO2 gradually grows
from 0.308°2 to 0.349°2 as the exposure time increases. The plaster sam-
ple’s FWHM of the 123 reflection of CaSO4  2H2O decreases from 0.342°2
(not exposed sample) to 0.243°2 (after three-hour exposure) and then grows
to 0.254°2 (after five-hour exposure).
According to Warren and Averbach, the observed changes in FWHM values
result from the microstructural changes (crystallite fragmentation and/or
microstresses produced in the crystal lattice) induced exclusively by exposure
to radiation.13 According to Tucker and Sieno, although the recorded diffracto-
grams indicate still good crystallinity, some changes occurred, nevertheless,
as a consequence of exposure to radiation.14 The research results influence
of radiation on samples of cellulose, starch, and graphite point to changes in
grain size and shape.15–17 Analogous phenomena were detected by scanning
electron microscopy on the samples of slag, clinker, and plaster exposed to
radiation (Figures 4 to 6). The obtained micrographs show a morphological
change of small grains, cracks, and adhesive substances. When applying
slag, clinker, and plaster in construction industry, one has to consider the
observed changes in the properties of such materials due to radiation.
CONCLUSION
The influence of radiation time on samples of slag, clinker, and plaster
as cement ingredients was examined. Diffractograms of the exposed sam-
426 A. RASTOV^AN-MIO^ ET AL.
TABLE II
FWHM values for different time of radiation in slag, clinker and plaster
Sample Time of radiation / hours
0 1 3 5
FWHM / °2
slag
clinker
plaster
1.090
0.308
0.342
1.150
0.335
0.330
1.220
0.347
0.243
1.140
0.349
0.254
INFLUENCE OF RADIATION ON SLAG 427
Figure 4. Scanning electron micrographs of the slag sample: (1) after irradiation for
1 hour; (2) after irradiation for 3 hours; (3) after irradiation for 5 hours; Magnifica-
tion: (a) 500 x; (b) 1500 x.
ples, compared to the non-exposed samples, show a change in the number
and intensity of recorded diffraction lines and in their FWHM. Changes
caused by radiation are recorded on the scanning electron micrographs in
the form of grain swelling and cracking, as well as emergence of grains in
various forms and sizes. Based on the available references and obtained re-
sults, it can be concluded that the alterations recorded on the examined
samples resulted from radiation-induced micro-structural changes. Accord-
ing to the latest references, these alterations directly affect the mechanical
properties of material and accelerate the ageing process.
428 A. RASTOV^AN-MIO^ ET AL.
Figure 5. Scanning electron micrographs of the clinker sample: (1) after irradiation
for 1 hour; (2) after irradiation for 5 hours; Magnification: (a) 500 x; (b) 1500 x.
INFLUENCE OF RADIATION ON SLAG 429
Figure 6. Scanning electron micrographs of the plaster sample: (1) after irradiation
for 1 hour; (2) after irradiation for 3 hours; (3) after irradiation for 5 hours; Magnifi-
cation: (a) 500 x; (b) 1500 x.
REFERENCES
1. D. W. Lewis, History of Slag Cements, Slag Cement Seminar, University of Ala-
bama, Alabama, 1981, pp. 181–186.
2. F. M. Lea, The Chemistry of Cement and Concrete, Edward Arnold Publishers,
London, 1976.
3. J. Geiseler and S. R. Schlosser, Investigation Concerning Structure and Properties
of Steel Slags, 3rd International Conference on Molten Slags and Fluxes, Glas-
gow, 1988, pp. 66–69.
4. [. Cerjan-Stefanovi}, A. Rastov~an-Mio~, and Vj. Novosel-Radovi}, Metalurgija
36 (1997) 93–99.
5. B. A. Gurovich, E. A. Kuleshova, and Y. A. Nikolaev, J. Nucl. Mater. 246 (1997)
91–120.
6. A. R. Kuznetsov, Fiz. Met. Metaloved. 85 (1998) 418–420.
7. Y. Dai, F. Carsughi, H. Ulhmarer, S. Maloy, and W. Sommer, J. Nucl. Mater. 265
(1999) 203–227.
8. EN 196 TEIL 2 (UDC: 666.94:691.54:620.1).
9. DIN 1164 TEIL 3 (UDC: 666.96:691.55:620.1).
10. H. P. Klug and L. E. Alexander, X-ray Diffraction Procedures for Polycrystalline
and Amorphous Materials, John Wiley and Sons, New York, 1974, pp. 365–376.
11. International Centre for Diffraction Data, Newtown Square, PA 19073–3273,
USA, Powder Diffraction File.
12. K. Narita, Kristali~eskaja Struktura Nemetali~eskih Vklu~enij v Stali,
Metalurgija, Moskva, 1966, p. 59, 61, 63.
13. B. E. Warren and B. L. Averbach, J. App. Phys. 23 (1952) 496–501.
14. C. W. Tucker and P. Sieno, Acta Cryst. 7 (1954) 456.
15. Vj. Novosel-Radovi}, Da. Maljkovi}, and N. Nenadi}, Spectrochim. Acta 40B
(1985) 701–704.
16. Vj. Novosel-Radovi}, Da. Maljkovi}, and N. Nenadi}, Fresenius Z. Anal. Chem.
320 (1985) 159–162.
17. Vj. Novosel-Radovi} and Da. Maljkovi}, Chemia 7–8 (1998) L15.
SA@ETAK
Utjecaj rentgenskog zra~enja na fazni sastav i morfologiju
elektrope}ne troske, klinkera i gipsa
Alenka Rastov~an-Mio~, [tefica Cerjan-Stefanovi}, Vjera Novosel-Radovi},
Boro Mio~ i Tahir Sofili}
Provedena su istra`ivanja utjecaja rentgenskog zra~enja na strukturu i morfo-
logiju uzoraka klinkera, gipsa i elektrope}ne troske dobivene u procesu proizvodnje
austenitnog manganskog ~eli~nog lijeva, kako bi se odredila stabilnost tih materijala
prema zra~enju.
Nastale promjene analizirane su uporabom rentgenske difrakcije i elektronske
mikroskopije. Na difrakcijskim slikama zapa`ene su promjene profila, broja i relativ-
nog intenziteta difrakcijskih linija te izmjerene {irine na polovici visine maksimuma.
Na dobivenim mikrografijama uo~ava se pojava bubrenja i pucanja zrna. S porastom
vremena ozra~ivanja ta pojava biva sve vi{e izra`ena i dovodi do izrazite promjene
veli~ine i oblika zrna osnovnih komponenata cementa, tj. troske, klinkera i gipsa.
430 A. RASTOV^AN-MIO^ ET AL.


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Influence of X-ray Radiation on the Phase Composition and Morphology of Electric Furnace Slag, Clinker, and Plaster

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