Pozzolanic Effect in the Use of Nitric Acid to Dissolve Electric Arc

Furnace Slag As a Concrete Mixture

Bahrul Anif
Jurusan Teknik Sipil FTSP Universitas Bung Hatta Padang, Sumatera Barat
Email: bahrulanif@bunghatta.ac.id

ABSTRACT: Steel slag is the residue of the steel production process and composed of silicate
and oxides of unwanted elements in steel chemical composition. There is two electrics arc furnace
slag (EAFS) usage in the study, EAFS that is processed with HNO3 (EAFS-A) and EAFS that is
not processed with HNO3 (EAFS-B). The concrete with EAFS that is processed with HNO3
produces a higher compressive strength than the one without HNO3, although the percentage of
replacement follows the previous experiment. In conclusion, the study shows that EAFS that is
not processed with HNO3 shows no indication of having pozzolanic reaction between EAFS and
Ca(OH)2 in the concrete. On the other hand, EAFS that is processed with HNO3 shows the
occurrence of pozzolanic reaction between EAFS and Ca(OH)2 in the concrete.

Keyword: Steel slag, concrete, nitrite acid (HNO3), Pozzolanic activity, compressive strength

1. Introduction
In the steel production process, there are by-products other than steel, known as
steel slag. Steel slag is a residue from the steel process from iron or smelting bad iron to
produce steel in an Electric Arc Furnace (EAFS) which is formed from unwanted silicates
and oxides in the chemical content of steel (Shi, 2002; Altun, 2002).
There are large differences in the chemical and mineral content of steel slag.
Minerals commonly found in steel slag include olivine, merwinite, C3S, -C2S, C4AF,
RO phase (solid solution of CaO-FeO-MnO-MgO), and free CaO. The presence of C3S,
-C2S, C4AF, and C2F indicate the steel slag has cementitious properties (Shi, 2002).
EAFS has good quality for reuse as an aggregate (Frias and Sanchez de Rojas,
2004) and (Shi, 2002) and also used for coarse aggregate (Yusof et al., 2000) and fine
aggregate (Salmiati, 2003). However, this material has links with several aspects such as
unstable volume caused by the presence of several expanding compounds such as free
CaO, free MgO, sulfur, sulfate, high iron oxide content, chloride, and others. When
viewed from the concentration, EAFS can cause a separation process and a lack of
performance and durability of the slag that has been stirred. The content of free CaO and
free MgO is the most important component when EAFS is used as a cement substitute for
volume stability (Monshi and Asgarani, 1999; Frias and Sanchez de Rojas, 2004). In
addition, EAFS has very high crystal properties such as iron oxides including w/plustite

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(W), magnesioferrite (M), and hematite (H): silicates, including larnite (L),
bredigite/merwinite (B), and gehlinite (G); and oxides, among them birnessite/groutellite
(manganese oxide, Mn). Due to the high crystallinity, there is no pozzolanic activity
(Frias and Sanchez de Rojas, 2004).

2. Purpose of Research
To determine the effect of EAFS dissolved with nitric acid (HNO3) on the
compressive strength of concrete containing EAFS as a cement substitute.

3. Research Method

The study was conducted in the laboratory by dissolving EAFS with HNO3, then
heated at 110oC and the duration of heating was recorded. After that, the EAFS was
washed with distilled water until the EAFS reached a normal pH (pH = 7), then placed in
the oven to dry. If there are lumps, then it grinds using a grinding machine. The dry
material was subjected to a chemical analysis of the composition of the content contained
in EAFS.

4. Experiments
4.1 Dissolving

Dissolution is the process by which a solid crystalline structure dissociates into

ions, atoms, or molecules in the liquid phase (Dingle et al., 1971). The dissolution process
is carried out by pouring nitric acid (HNO3) into a container in which EAFS already
exists (Bahrul, 2006). The EAFS contained in the container is EAFS that has been
pulverized like cement. In this research, there are two EAFS used, namely EAFS that has
not been processed with HNO3 (EAFS-A) and EAFS that has been processed with HNO3
(EAFS-B).
The purpose of the dissolution process is to reduce the oxide content contained in
the EAFS compound (Bahrul, 2009). In the dissolution process, it is expected that a
hydrolysis process will occur which can reduce the chemical content, especially the MgO
and Fe2O3 compounds so that it can affect the compressive strength of the concrete. By
reducing the oxide content of some compounds, it is expected to increase the CaO content
so that the reaction of pozzolanic activity occurs. Then the dissolution process was carried
out using HNO3 (Svehla, 1979), namely by adding HNO3 to the mashed EAFS.

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4.2 Dissolving Process

The EAFS dissolution process was carried out using a 3000 mL beaker filled with
400 mL of EAFS, added distilled water in an amount that could cover the EAFS surface,
then dissolved with 65% (260 mL) HNO3 with a heating temperature of 110 o C in a
beaker. Heating was carried out for 12 hours in 2 heating times (the first day for 6 hours,
and the second day for 6 hours). During heating, the EAFS was continuously stirred and
distilled water was added in the submerged EAFS state. After that, the EAFS was washed
with distilled water until the EAFS was in a normal pH state (pH = 7) and in the oven to
dry. If there are lumps, grind them again using a grinding machine.

4.3 Concrete Sample Making

EAFS-A and EAFS-B were made into concrete with a concrete quality of K 300
with a water-cement ratio (a/s) of 0.5 and the same composition. Table 2.3 shows the
mixed form that has been used, where the mixture without slag mixture is used as control
concrete (SP concrete). Each type of EAFS-A and EAFS-B is made into a mixture
containing 10%, 20%, and 30% EAFS content. EAFS is added to the mortar to partially
replace the cement by weight. In this study, concrete with cubes measuring 100 mm was
used for compressive strength tests. Samples that have been made, preserved in a humid
state until the time to be tested at the age of 3, 7, 28, and 90 days. To test the compressive
strength of this sample, the TONIPACT 3000 tool was used.
Table 4.1: Composition of concrete mix in 1 m3 volume (Bahrul, 2009)

Material weight for concrete mix

No. Mied Type
Cement Slag (kg) Water Fine Corse
(kg) (kg) Agregate Agregate
(kg) (kg)
1 SPB 396.0 - 198 835 981
2 10J-A 356.4 39.6 198 835 981
3 10J-B 356.4 39.6 198 835 981
4 20J-A 316.8 79.2 198 835 981
5 20J-B 316.8 79.2 198 835 981
6 30J-A 277.2 118.8 198 835 981
7 30J-B 277.2 118.8 198 835 981

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5. Result and Discussion
5.1 Results of Chemical Analysis

In the process of dissolving EAFS with HNO3, magnesium oxide (MgO) and
calcium oxide (CaO) compounds contained in EAFS react with water to form hydroxides.
Then react with HNO3 which causes the oxides to dissolve (Cotton et al., 1999). The
main compounds contained in EAFS such as SiO2, Al2O3, Fe2O3, and MgO decreased
in content due to the dissolution of HNO3 (Svehla, 1979) as shown in Table 5.1.

Table 5.1: Chemical composition in SP and EAFS tested by XRF

(Bahrul, 2009)
Chemical composition (%)
No. Chemical
SP (%) EAFS-A (%) EAFS-B (%)
Compound
1 CaO 62.26 13.97 30.20
2 SiO2 20.56 20.63 17.83
3 Al2O3 4.79 6.71 5.83
4 Fe2O3 2.07 34.65 27.81
5 MgO 2.53 9.47 8.17
6 K 2O 1.01 0.03 0.02
7 Na2O 0.55 0.29 0.18
8 MnO 0.04 1.80 1.36
9 TiO2 0.19 1.03 0.77
10 P2O5 0.07 0.40 0.33
11 L.O.I 5.93 11.02 7.50
Amount 100.00 100.00 100.00

Chemical analysis was carried out using XRF on Portland cement (SP) and both
types of EAFS, namely EAFS-A and EAFS-B. In this test, the chemical content of the
material was checked using an XRF device at the Faculty of Science Technology
laboratory at Universiti Kebangsaan Malaysia (FST-UKM) and the results were obtained
as shown in table 5.1.

Referring to Table 5.1, the results of the study show that in the dissolution process
with HNO3, it appears there is a reduction in the oxide compounds contained in EAFS.
Oxide compounds contained in EAFS can affect the compressive strength in concrete,
namely Fe2O3 and MgO compounds (Bahrul, 2009). The reduction in the content of
Fe2O3 and MgO compounds in EAFS-A compared to EAFS-B was 19.74% and 13.73%,
respectively. On the other hand, in CaO compounds there was an increase in the content
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of 116.18% in EAFS-B compared to EAFS-A due to CaO not soluble in HNO3 solution
and resulted in an increase in the amount of CaO compared to other compounds.

5.2 Compressive Strength Results

Table 5.2 shows that the compressive strength of SP concrete increases with the age
of the concrete from 3, 7, 28, and 90 days, as well as 10S-A, 10S-B, 20S-A, 20S-B, 30S-
A, and 30S concrete. -B. However, SP concrete has a higher compressive strength than
10S-A, 10S-B, 20S-A, 20S-B, 30S-A, and 30S-B concrete which are preserved up to 90
days.
The results of this test show the difference in the compressive strength of EAFS
concrete for sample B, exceeding the compressive strength of EAFS concrete sample A
for all mixtures as shown in Table 5.2 with a mixture of 10% EAFS can be seen the
increase in compressive strength from the age of 3, 7, 28, to 90 days for both samples A
and B, while the difference in compressive strength between samples B and A from ages
3, 7, 28, to 90 were 1.37%, 2.76%, 8.35%, and 10.97%, respectively. Likewise, for a
mixture of 20% EAFS, it can be seen that the increase in compressive strength from the
age of 3, 7, 28, to 90 days for both samples A and B, while the difference in compressive
strength between samples B and A was 4.65%, 8.48%, 12.35%, and 15.51%. .
Furthermore, for a mixture of 30% EAFS, an increase in compressive strength from ages
3, 7, 28, to 90 days for both samples A and B, while the difference in compressive
strength between samples B and sample A from ages 3, 7, 28, and 90 respectively was
3.28%, 5.62%, 9.51%, and 11.91%.
From these results, it appears that there is a difference in the compressive strength
of concrete between sample B and sample A. The effect of the increase between sample B
and sample A is that the concrete in sample B has undergone a process of dissolving
oxides using HNO3. By using the Luxan method, both EAFS-A and EAFS-B substitutes
have been tested. Referring to the conduction table of the Luxan method, EAFS-A is not a
pozzolanic because the electrical conductivity variation value is less than 0.4 mS/cm
while EAFS-B has good pozzolanic activity because the electrical conductivity variation
value is more than 1.2 mS/ cm.

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Tabel 5.2: The compressive strength of SP concrete, EAFS-A concrete, and EAFS-B
concrete
Compressive Strength (N/mm2)
Days
SP 10S-A 10S-B 20S-A 20S-B 30S-A 30S-B
3 25.06 21.81 22.11 18.79 19.66 15.15 15.65
7 31.19 25.25 25.95 21.49 23.32 17.95 18.96
28 37.43 30.42 32.96 27.63 31.10 23.09 25.28
90 40.20 33.05 36.67 29.96 34.60 25.97 29.06

6. Conclusion

The effect of EAFS dissolved with nitric acid (HNO3) on the compressive
strength of concrete containing EAFS as a substitute for cement is; can reduce the oxide
content contained in the EAFS compound. Due to the reduced oxide content in the EAFS
compound, the overall percentage of magnesium oxide (MgO) is reduced. By the
reduction of MgO can cause an increase in the concrete compressive strength.

References

Altun, I.A. Yilmaz, I. (2002). Study on steel furnace slags with high MgO as additive in
Portland cement. Cement and Concrete Research. (32)8: 1247-1249.

Bahrul Anif (2006). Potensi Penggunaan Jermang Keluli Relau Arka Elektrik Dalam
Konkrit. Proceeding International Conference on Construction Industry. June 21-
24, Padang, Indonesia: Universitas Bung Hatta.

Bahrul Anif (2009). Sifat-Sifat Konkrit Dengan Jermang Relau Arka Elektrik. Universiti
Teknologi Malaysia: Ph.D. Thesis.

Cotton, F. A., Wilkinson, G. and Murillo, C. A. (1999). Advanced In-organic Chemistry.

6th ed. New York: John Willey and Sons.
Dingle, C.F., Simpson, O.J., Southcott, R.A. (1971). Basic Chemistry. London: Arnold

Frias R. M. and Sanchez de Rojas, M.I. (2004). Chemical assessment of the elecric arc
furnace slag as constuction material: Expansive compounds. Cement and
Concrete Research. (34)10. 1881-1888.

Luxan, M.P., Sanchez de Rojas, M.I., and Frias, M. (1989). Investigations on the fly ash-
calcium hydroxide reactions. Cement and Concrete Research. (19)1: 69-80.

138
Luxan, M. P., Madruga, F. and Saavedra, J. (1989). Rapid Evaluation of Pozzolanic
Activity of Natural Products by Conductivity Measurement. Cement and Concrete
Research. 19(1): 63-68.

Monshi, A. and Asgarani M. K. (1999). Producing Portland Cement from Iron and Steel
slags and Limestone. Cement and Concrete Research. (29)9: 1373-1377.

Rajeh, Z. Al-Zaid, Faisal, H. Al-Sugair and Abdulaziz I. Al-Negheimish (1997).

Investigation of Potential Uses of Electric-Arc Furnace Dust (EAFD) in Concrete.
Cement and Concrete Research. 27(2): 267-278

Salmiati (2002). Analisis Kimia dan Penggunaan Jermang Keluli Relau Arka Elektrik
(EAF) sebagai aggregat dalam mortar. Universiti Teknologi Malaysia: Master
Thesis.

Shi, C. and Qian, J. (2000). High Performance Cementing Materials from Industrial Slags
– a Review. Resources Conservation and Recycling. (29): 195-207.
Shi, C. (2002). Characteristics and cementitious properties of ladle slag fines from steel
production. Cement and Concrete Research. (32)3: 459-462.

Svehla, G. (Ed.) (1979). Vogel’s textbook of macro and semi micro qualitative in organic
analysis. New York, USA: Longman.

Yusof, A., Makhtar, A.M dan Salmiati, M.Y (2000). Kajian Penggunaan Jermang Keluli
dari Kilang Penghasilan Keluli Tempatan Untuk Batu Baur Kasar. Prosiding
Seminar Persekitaran 2000. Perak: Universiti Sains Malaysia, 187-194.

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