Author’s Accepted Manuscript

Thermal activation of air cooled slag to create one-

part alkali activated cement

H.A. Abdel-Gawwad, S.R. Vásquez García,

Hassan Soltan Hassan

www.elsevier.com/locate/ceri

PII: S0272-8842(18)31233-1
DOI: https://doi.org/10.1016/j.ceramint.2018.05.089
Reference: CERI18264
To appear in: Ceramics International
Received date: 25 March 2018
Revised date: 11 May 2018
Accepted date: 12 May 2018
Cite this article as: H.A. Abdel-Gawwad, S.R. Vásquez García and Hassan
Soltan Hassan, Thermal activation of air cooled slag to create one-part alkali
activated cement, Ceramics International,
https://doi.org/10.1016/j.ceramint.2018.05.089
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 Thermal activation of air cooled slag to create one-part
alkali activated cement
H.A. Abdel-Gawwad1, S.R. Vásquez García2* & Hassan Soltan Hassan3,4

1
Raw Building Materials and Processing Technology Research Institute, Housing and Building
National Research Center, HBRC, Egypt.
2
Posgrado de Ingeniería Química, Universidad Michoacana de San Nicolás de Hidalgo, 58000,
Morelia, Michoacán, México.
3
Posgrado de Ingeniería Química, Universidad Michoacana de San Nicolás de Hidalgo, 58000,
Morelia, Michoacán, México.
4
Geology Department, Faculty of Science (New Valley Branch), Assiut University, Assuit, Egypt.

* Corresponding Author: S.R. Vásquez García. Affiliation: 1 Posgrado de Ingeniería

Química, Universidad Michoacana de San Nicolás de Hidalgo, 58000, Morelia, Michoacán, México.

E-mail: salomon.ramiro2018@gmail.com

Abstract
An environmentally friendly alkali activated cement powder was prepared by the

transformation of air cooled slag (ACS), with low reactivity, into high reactive

cementitious material. The recycling process was carried out by thermal activation of

ACS in the presence of fluxing materials followed by quenching and crushing to

produce cement powder with a fixed particle size, yielding alkali activated cement

powder, which can react with water like Portland cement. Type and content of fluxing

material were investigated in this communication. The results proved that there is no

change in the crystalline structure of ACS when it exposed to 1200°C (with no

fluxing materials). Meanwhile, it can convert to amorphous material with a complete

vitreous structure in the presence of sodium hydroxide and feldspar. The

dissolution/condensation process of the amorphous aluminosilicate initiated after

adding water to the prepared cement powder, yielding hardened cement pastes with

higher mechanical properties as compared to untreated alkali activated ACS.

Keywords: Air cooled slag; Thermal treatment; Recycling; Amorphous materials;

Hydration.

1. Introduction

Blast-furnace slag can be defined as a molten material that is formed during the

refining of iron ore at temperature of 1400-1600oC [1, 2]. The slowly cooling of the

molten material produces crystalline stone namely air-cooled slag (ACS) with lower

reactivity compared to the glassy granulated blast-furnace slag (GBFS) that produced

by quenching of the smelted material with water. GBFS has lower hydration

properties in water; it can be accelerated by the addition of alkaline solution, yielding

what is known as alkali activated slag cement or non-Portland cement with an

acceptable compressive strength [2-4]. Although the similarity between ACS and

GBFS in chemical and mineralogical compositions, the former showed lower

hydraulic property in alkaline condition, due to its lower crystalline structure [5, 6].

So, ACS was commonly as partially alternative to silica sand, gravel and dolomite

aggregates in concrete making [6-8].

In this paper, the crystalline structure was completely converted to amorphous one by

thermal activation of ACS in the presence of fluxing materials followed by rapid air

quenching and crushing to generate fine cementitious powder which reacts with

water, forming high performance hardened cementitious materials.

2. Experimental

Air cooled slag (ACS), Feldspar (FS) and sodium hydroxide (NaOH) as starting

materials are used in this investigation. ACS as a waste of steel industry was provided

by Helwan Steel Company, Helwan, Egypt, FS was brought from El-Wahat Road,

Giza, Egypt and NaOH with purity of 99.99% was purchased from Fisher Scientific

Company, UK. The chemical compositions of ACS and FS are listed in Table 1. The

X-ray diffractograms (XRD) proved that the ACS is mainly composed of crystalline

peaks related to gehlinte and akermanite; meanwhile albite, microcline and quartz are

the main minerals in FS (Fig. 1).

For thermal activation, 50g of ACS-powder was admixed with solid NaOH (0, 5

and 10 % with respect to the weight of ACS) and transferred to zirconia crucible and

heated in laboratory muffle furnace at temperature of 1200°C with firing rate of

20°/min for 2h soaking time followed by rapid air quenching and pulverizing to pass

from 75µm sieve. The combined effects of two different fluxing materials on the

verification process was carried out by blending of ACS with 10 mass% NaOH and 2

mass% FS. The details of mix proportions are listed in Table 2.

The fresh paste was made by the addition of water (W) to the prepared cement

powder (P) at W/P ratio of 0.27. Meanwhile, untreated ACS powder containing the

same FS content (as counterpart to thermally treated ACS in the presence of 2 mass%

FS and 10 mass% NaOH) was mixed with 10 mass% NaOH at W/ACS ratio of 0.27.

After complete automatic mixing, the fresh paste was transferred to steel molds of 1

cubic inch then cured in 99±1% relative humidity (RH) at 23±2°C for 24h. The

hardened cement cubes were demolded to be cured under the same condition until the

time of compressive strength testing reaches such as 1, 7 and 28 days.

 The compressive strength was applied on three hardened samples (at each curing

age) according to the American standard specification C109M [9], using five tons

German-Bruf-Pressing Machine with a loading rate of 100 kg/min.

Different instruments were applied to characterize the thermally treated and

untreated ACS as well as its hardened cement pastes. XRD was done using Philips

PW3050/60 diffractometer using a scanning range from 5 to 50 (2θo), with a scanning

speed of 1s/step and resolution of 0.05°/step. The Fourier transform infrared (FTIR)

spectroscopy was recorded from KBr discussing Genesis-II FT-IR spectrometer in the

range of 400-4000 cm-1. TGA were carried out by heating the sample in nitrogen

atmosphere up to 1000 °C with a heating rate of 20 °C/min using a DT-50 Thermal

Analyzer (Schimadzu Co-Kyoto, Japan). Scanning electron microscopy (SEM) was

used to investigate the microstructure of hardened pastes using Inspect S (FEI

Company, Holland) equipped with an energy dispersive X-ray analyzer (EDXA).

3. Results and discussion

3.1. Thermal treatment
Interestingly, the exposure of air cooled slag (ACS) to 1200°C does not affect its

crystalline nature as proved by XRD (Fig. 2). Where, there is no difference in the

diffraction patterns before and after ACS-thermal activation, confirming the high

stability of ACS at 1200ºC. The crystalline phases can be converted to amorphous

structure when ACS fired at 1200°C in the presence of fluxing materials. The partial

conversion of amorphous structure was observed after thermal treatment of ACS in

the presence of 5 mass% NaOH (ACS-F0N5-1200). The higher amorphous structure

with the formation of small crystalline peaks (with lower intensities) was obtained in

case of ACS-F0N10-1200. The addition of 2 mass% feldspar (F) to ACS in the

prescience of 10 mass% NaOH (ACS-F2N10-1200), which led to form amorphous

material with a typical vitreous structure. This is associated with the depolymerization

of crystalline gehlinte and akermanite phases containing ACS, yielding amorphous

structure with the deformation in its bond lengths and angles.

The crystallinity and amorphicity percentage of ACS and treated eco-cement

powders were calculated from XRD as given in Table 3. Evidently, ACS showed the

highest crystallinity percentage (76%). After heating ACS in the presence of NaOH

and/or FS the crystallinity significantly decreases. The amorphicity of ACS increases

(low crystallinity) with the increase of the content of NaOH. 100% amorphicity was

detected when ACS thermally activated in the presence of 10 mass% NaOH and 2

mass% FS.

As shown in Fig. 3, the fluxing materials content and type strongly affect the

physical properties of thermally treated ACS. The exposure of ACS to 1200°C (ACS-

F0N0-1200) leads to produce dark black aggregates. Meanwhile, the heating of ACS

in the presence of 5 mass% NaOH (ACS-F0N5-1200) generates the combination of

coarse black aggregates and light brown aggregates. With increasing the content of

NaOH up to 10 mass% (ACS-F0N10-1200), light brown aggregates having a glassy

structure was observed. The glassy nature and color brightness were enhanced after

ACS thermally treatment in the presence of NaOH and/or FS (ACS-F2N10-1200).

3.2. Hydration

The highly reactive thermally treated alkali activated cement powder possess high

ability to react with water, forming hardened cement pastes. The compressive strength

values of the hardened cement pastes are shown in Fig. 4. Clearly, the compressive

strength of all hardened pastes increase with curing time, highlighting the continuous

activation of cement powder hydration and the formation of strength-giving-phases.

The ACS-F2N10-1200 mix showed the highest compressive strength values at all

ages. In contrast, the compressive strength values of un-treated ACS-F2N10 (as

counterpart to thermally treated ACS-F2N10-1200) found to be 8-times lower than

that of thermally treated ACS-F2N10-1200. This confirms the efficacy of thermal

treatment, in the presence of NaOH/FS, on the enhancement of ACS reactivity to

produce eco-cement powder with high performance.

The hardening process initiates by the removal of Na-cations (attached in

amorphous structure) which react with water to produce NaOH. Thereafter, Al-O-Si,

Si-O-Si and Al-O-Al were dissolved by alkali hydroxide solution to produce alkali

activated species (SiO4 and AlO4) which condensed with each other to produce

aluminosilicate polymer with high binding capacity.

3.3. Phases identification

FTIR spectroscopy proved that the absorption band related to asymmetric stretching

vibration of Si-O-Si(Al) located at 968 cm-1, in case of untreated ACS, which shits to

higher wavenumber (at 992 cm-1) after thermal treatment in the presence of 10 mass%

NaOH and 2 mass% FS (ACS-F2N10-1200) (Fig. 5). Also, the high full width at half

maximum (FWHM) of this band, which formed in ACS-F2N10-1200, is broader than

those of ACS. The shift to the higher wavelength and the increase in FWHM confirm

the transformation of crystalline phases to amorphous structure with high

deformations in the lengths and angles of Si-O-Al, Si-O-Si and Al-O-Al bonds. At 28

days of ACS-F2N10-1200 hydration, this band shift again to lower wavenumber (974

cm-1) and the band broadness became narrower. Moreover, a new absorption bands

related to H-O-H bending vibration and stretching vibration of OH groups at 1642 and

3462 cm-1, respectively was observed. This should be explained by the activation of

cement powder hydration and formation of binding phases such as calcium silicate
hydrate (CSH), calcium aluminosilicate hydrate (CASH) and magnesium silicate

hydrate (MSH) with high ordering structure. All bands intensities that formed in

untreated ACS-F2N10 found to be lower than those formed in case of thermally

treated ACS-F2N10-1200, confirming the lower hydration property of untreated ACS-

F2N10.

The TG/DTG-thermograms of hardened ACS-F2N10 and ACS-F2N10-1200

at 1 and 28 days was shown in Fig. (6a, b). Obviously, the weight loss (Fig. 6a) of

thermally treated ACS-F2N10-1200 increases with time, indicating that the activation

of cement hydration was ongoing during the test period up to 28 days. The untreated

ACS-F2N10 presented the lowest weight loss, confirming its lower hydration rate.

The DTG thermograms were applied to characterize the endothermic peaks related to

weight loss at different temperatures. Three main endothermic peaks related CSH,

MSH and hydrotalcite (Ht) were observed in DTG curves (Fig.6b). The combined

water in CSH and MSH as well as physically adsorbed water have been decomposed

at 50-200°C [10, 11]. The endothermic peaks characteristic for Ht are located at the

temperature range of 200-400°C [3, 11]. Meanwhile, MSH with higher crystallinity

was observed at 400-600°C [10]. The DTG proved that the intensities of CSH, MSH

and Ht peaks in case of ACS-F2N10-1200 increase with time. At 28 days of curing,

the intensities of these peaks in case of untreated ACS-F2N10 found to be lower than

those of ACS-F2N10-1200. The TG/DTG-thermograms are in a good harmony with

FTIR spectra and compressive strength results.

3.4. Microstructure

Fig.7. depicts SEM-micrographs of thermally treated ACS-F2N10-1200 powder and

its hardened paste at 28 days as well as the hardened pastes of 28-days cured ACS-
F2N10 hardened sample. The microstructure of ACS-F2N10-1200 powder seems to

have aggregates with different sizes and morphologies. After addition of water to

cement powder and at 28-days of curing the microstructure of hardened cement pates

(ACS-F2N10-1200/28) found to be high compacted with lower porosity. This reflects

the compressive strength development with time. The hardened paste of untreated

ACS-F2N10 exhibits high porous microstructure with unreacted aggregate prevalent

along cement matrix, highlighting the lower reactivity of untreated-ACS-F2N10 mix.

4. Conclusions

An experimental work was carried out to produce high performance eco-cement by

thermal activation of air cooled slag at 1200°C in the presence of sodium hydroxide

and feldspar as fluxing materials. Sodium hydroxide percentage strongly affected the

verification process. Where, the amorphicity of eco-cement powder increased with

sodium hydroxide content. The highest glassy structure of ACS was obtained when

thermally treated in the presence of 10 mass% sodium hydroxide and 2 mass%

feldspar (as optimum condition). The molten material was subjected to rapid air

quenched, and then pulverized to produce eco-cement powder which reacts with water

to form hardened cement paste with higher compressive strength as compared to the

hardened paste of untreated alkali activated ACS.

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of hydraulic cement mortars, .

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 Fig. 1. XRD-patterns of air cooled slag and feldspar

Fig. 2. XRD-pattern of ACS thermally treated with or without fluxing materials

ACS ACS-F0N5-1200 ACS-F0N10-1200 ACS-F2N10-1200

Fig. 3. Digital photos of untreated and thermally treated ACS with or without fluxing
materials

Fig. 4. Compressive strength of hardened cement pastes

 H-O-H Si-O- Al
OH CO32-
Si-O-Al(Si)

Fig. 5. FTIR-spectra of ACS, thermally treated powder as well as hardened pastes at

28-days of curing
 (a)

6.32%

10.51%
11.74%

(b)

Fig. 6. (a) TG and (b) DTG-thermograms of alkali activated hardened pastes at 28

days of curing
(a) (b)

(c)

Fig. 7. SEM-photographs of (a) ACS-F2N10-1200 cement powder and (b) its

hardened paste at 28-days of curing as well as (c) 28-days cured alkali

activated paste of untreated ACS-F2N10

 Table 1: Chemical oxides composition of starting materials, mass%

Oxide, % SiO2 Al2O3 Fe2O3 CaO MgO Na2O K2O SO3

ACS 38.6 12.43 3.10 35.67 6.09 1.21 0.11 1.32

FS 72.31 14.18 0.90 1.95 0.32 3.08 4.92 0.02

Table 2: Mix proportions of the prepared cements

Mix designation ACS,% NaOH,% FS,% Temperature, oC
ACS-F0N0-1200 100 - - 1200
ACS-F0N5-1200 100 5 - 1200
ACS-F0N10-1200 100 10 - 1200
ACS-F2N10-1200 100 10 2 1200
ACS-F2N10 100 10 2 -

Table 3: Crystallinity and amorphicity, (%) as calculated from XRD patterns

Mix designation Crystallinity, % Amorphicity, %

ACS 76 24
ACS-F0N5-1200 53 47
ACS-F0N10-1200 12 88
ACS-F2N10-1200 0 100