UNIVERSITATIS OULUENSIS ACTA C TECHNICA OULU 2019 C 727 Elijah D. Adesanya A CEMENTITIOUS BINDER FROM HIGH-ALUMINA SLAG GENERATED IN THE STEELMAKING PROCESS UNIVERSITY OF OULU GRADUATE SCHOOL; UNIVERSITY OF OULU, FACULTY OF TECHNOLOGY C 727 ACTA Elijah D. Adesanya
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UNIVERSITY OF OULU P .O. Box 8000 F I -90014 UNIVERSITY OF OULU FINLAND
A C T A U N I V E R S I T A T I S O U L U E N S I S
University Lecturer Tuomo Glumoff
University Lecturer Santeri Palviainen
Senior research fellow Jari Juuti
Professor Olli Vuolteenaho
University Lecturer Veli-Matti Ulvinen
Planning Director Pertti Tikkanen
Professor Jari Juga
University Lecturer Anu Soikkeli
Professor Olli Vuolteenaho
Publications Editor Kirsti Nurkkala
ISBN 978-952-62-2451-0 (Paperback)ISBN 978-952-62-2452-7 (PDF)ISSN 0355-3213 (Print)ISSN 1796-2226 (Online)
U N I V E R S I TAT I S O U L U E N S I SACTAC
TECHNICA
U N I V E R S I TAT I S O U L U E N S I SACTAC
TECHNICA
OULU 2019
C 727
Elijah D. Adesanya
A CEMENTITIOUS BINDER FROM HIGH-ALUMINASLAG GENERATED IN THE STEELMAKING PROCESS
UNIVERSITY OF OULU GRADUATE SCHOOL;UNIVERSITY OF OULU,FACULTY OF TECHNOLOGY
C 727
AC
TAE
lijah D. A
desanya
C727etukansi.fm Page 1 Friday, November 8, 2019 2:27 PM
ACTA UNIVERS ITAT I S OULUENS I SC Te c h n i c a 7 2 7
ELIJAH D. ADESANYA
A CEMENTITIOUS BINDER FROM HIGH-ALUMINA SLAG GENERATED IN THE STEELMAKING PROCESS
Academic dissertation to be presented with the assent ofthe Doctoral Training Committee of Technology andNatural Sciences of the University of Oulu for publicdefence in the OP auditorium (L10), Linnanmaa, on 13December 2019, at 12 noon
Reviewed byProfessor Juan Manuel Manso VillalaínAssociate Professor Guang Ye
ISBN 978-952-62-2451-0 (Paperback)ISBN 978-952-62-2452-7 (PDF)
ISSN 0355-3213 (Printed)ISSN 1796-2226 (Online)
Cover DesignRaimo Ahonen
JUVENES PRINTTAMPERE 2019
OpponentAssociate Professor Maria Chiara Bignozzi
Adesanya, Elijah D., A cementitious binder from high-alumina slag generated inthe steelmaking process. University of Oulu Graduate School; University of Oulu, Faculty of TechnologyActa Univ. Oul. C 727, 2019University of Oulu, P.O. Box 8000, FI-90014 University of Oulu, Finland
Abstract
About 4 Mt of ladle slag is generated in steelmaking processes in Europe per year, a largeproportion of which (80%) is placed in landfills or stored. This pattern is expected to continuewithout further research for their valorisation due to increasing demand for quality steel productsworldwide. Ladle slag (LS) produced in Finland possesses large amounts of calcium andaluminium and mineralogical phases which can exhibit cementitious capabilities and can beutilized in applications where expensive commercial cements are currently being used. The aim ofthis thesis is to investigate the properties of ladle slag in different activation pathways, includingalkali activation and use as a hydraulic binder with gypsum.
The results showed that ladle slag can be used alone as a precursor in alkali activation or as thesole binder or a co-binder with gypsum in hydraulic binding. Depending on the activationpathway, compressive strength between 35-92 MPa can be achieved after 28 days. The reactionproperties of alkali activated ladle slag are characterized, and it is confirmed through X-raydiffraction (XRD) that the reaction product after alkali activation is mainly an x-ray amorphous(calcium aluminate silicate hydrate-like) phase. Characterization techniques (SEM, XRD, TGAand NMR) used to analyze the LS paste binder with just water showed the hydration products ofladle slag to be dicalcium aluminate octahydrate (C2AH8), tricalcium aluminate hexahydrate(C3AH6), gibbsite (AH3) and stratlingite (C2ASH8) was also identified after a prolonged period ofhydration. Furthermore, it was found that to minimize the conversion, the ideal water-to-binderratio is 0.35. The conversion mechanism is reduced at this ratio and the strength is slightlyaffected. Another pathway that can be used to annul the conversion of calcium aluminate hydratesformed in LS paste is through the addition of gypsum to the LS paste system to produce anettringite-rich binder (C6AS3H32). When ettringite is formed in place of calcium aluminatehydrates the strength increases, frost resistance is improved, and drying shrinkage is enhanced.
Lastly, a potential application of ladle slag as a refractory material was also investigated.
Adesanya, Elijah D., Sementtimäinen sideaine terästeollisuuden alumiinirikkaastakuonasta. Oulun yliopiston tutkijakoulu; Oulun yliopisto, Teknillinen tiedekuntaActa Univ. Oul. C 727, 2019Oulun yliopisto, PL 8000, 90014 Oulun yliopisto
Tiivistelmä
Euroopassa syntyy vuosittain noin 4 Mt terästeollisuden sivutuotetta, JV-kuonaa, josta 80% läji-tetään tai kaatopaikoitetaan. Maailmanlaajuisesti syntyvän kuonan määrä tulee todennäköisestikasvamaan laadukkaiden terästuotteiden ennustetun kysynnän kanssa. Tämän vuoksi kuonalletulisi löytää hyötökäyttökohde, jota vältyttäisiin läjitykseltä. JV-kuona sisältääkin suuria määriäkalsiumia ja alumiinia sekä mineralogisia faaseja, joilla on sementtimäisiä ominaisuuksia. Näinkuonaa voitaisiin käyttää sovelluksissa, joissa tällä hetkellä käytetään kalliita kaupallisia sement-tejä. Tämän väitöskirjan tarkoituksena oli tutkia JV-kuonan ominaisuuksia sementtimäisenäsideaineena alkali-aktivoinnissa sekä hydraulisena sideaineena yksinään että kipsin kanssasekoitettuna.
Väitöskirjan tulokset osoittivat, että JV-kuonaa voidaan käyttää prekursorina alkali-aktivoin-nissa tai hydraulisena sideaineena pelkästään veden kanssa tai yhdessä kipsin ja veden kanssa.Saavutetut puristuslujuuset vaihtelivat 35 ja 92 MPa:n välillä, jotka vastaavat normaalin ja eri-tyislujan betonin lujuuksia. JV-kuonan reaktiotuotteet alkali-aktivonnin jälkeen analysoitiinXRD- ja FTIR-analyyseillä. Tuloksista nähtiin, että alkali-aktivoinnin jälkeen reaktiotuote onsementin kaltainen kalsium-aluminatti-silikaati-hydraati (C-A-S-H) –tyyppinen faasi. XRD,SEM, TGA ja NMR –analyysit osoittivat JV-kuonan hydrataatiotuotteiden olevan erilaisia kalsi-um-aluminaattihydraatteja (C2AH8, C3AH6, AH3 ja C2ASH8). Tämän vuoksi työssä tutkittiin erivesi-kuona –suhteita, ja havaittiin, että kun käytetään alhaista kuona-vesi –suhdetta (0,35), reak-tiotuoteiden muutos vähenee ja lujuus paranee. Toinen tapa, jolla voidaan estää reaktiotuottei-den muuttuminen, on kipsin lisäys: lisäämällä kipsiä tuotetaan runsaasti ettringiittiä (C6AS3H32).Kun ettringiittiä muodostuu kalsium-aluminaattihydraattien sijaan, lujuus kasvaa, pakkaskestä-vyys paranee ja kuivumiskutistuma paranee.
Väitöskirjan viimeisessä osiossa tutkittiin JV-kuonan mahdollista käyttöä tulenkestävänämateriaalina ja huomattiin, että sen tulenkestävyysominaisuudet vaihtelevat käytetyn aktivointi-tyypin mukaan.
Because he lives, I can face tomorrow… Dedicated to the loving memory of my Dad, and to my
Wife and Bezalel
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Acknowledgements
The research work reported in this thesis was carried out in the Fibre and Particle
Engineering Research Unit at the University of Oulu in the course of 2015-2019.
The research formed part of the MINSI project, with funding and support from
various companies (SSAB, Stora Enso, Oulun Energia, Pohjolan Voima and
Ekokem) and of the FLOW project, funded by Business Finland in the ERA-MIN
2 Innovation Programme, which is part of the EU Horizon 2020 programme. The
author would like to thank the Auramo Foundation and the Oulu University
Scholarship Foundation for their financial support.
My sincere gratitude goes to my principal supervisor, Professor Mirja
Illikainen, for giving me the opportunity to undertake my master’s and PhD
research under her guidance, with great support from Päiviö Kinnunen, PhD,
and Katja Ohenoja, DSc (Tech), both of whom guided, co-supervised and
contributed to all the research undertaken in this thesis. These brilliant people
introduced me to this field of study and nurtured me in it from an intern in 2014 to
a scholar in 2019. Also greatly appreciate the support and collaboration received
from Juho Yliniemi, DSc (Tech), during these years, and I would similarly
like to express my appreciation to Prof. Yiannis Pontikes for the opportunity
to visit his research unit at Katholieke Universiteit Leuven and to both him and
Dr. Lubica Kriskova for their supervision and support during that visit in 2017.
I would also like to express gratitude to all my past and present colleagues in
the Fibre and Particle Engineering Research Unit who have helped to create a
conducive working environment during my research. Special thanks go to Jarno
Karvonen, Jani Österlund, Elisa Wirkkala, Maria Tomperi and Johannes Kaarre for
their help in the laboratory, and to Simo Isokääntä of SSAB for providing the slag
used in this work. Malcolm Hicks is thanked for revising and proofreading the
language of this thesis. Professor Juan Manuel Manso and Associate Professor
Guang Ye are sincerely acknowledged for their thorough reviewing and
constructive feedback of this manuscript. Would also like to appreciate the
guidance from my follow-up group, chaired by Prof. Timo Fabritius and supported
by Dr. Petteri Piltonen and Pekka Tanskanen.
Finally, I wish to express my deepest gratitude to my parents, Baba Ijebu and
Iya Ijebu who went extra miles to ensure that my siblings and I would get the best
education and living conditions. I would also like to appreciate the efforts of my
siblings, most especially my mentor Gbenga Adesanya, Deborah Oguntosin,
Kayode Adesanya, Comfort Adesanya, and my Pastor Adeolu Osho, for always
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believing in me and for their support through and through. Infinite appreciation and
thanks are due to my beloved wife Adefunke Adesanya and our son Bezalel
Adesanya, for their encouragement, support, love and patience during my studies
and during the writing of this thesis.
Oulu, May 2019 Elijah Damilola Adesanya
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Abbreviations
AALS Alkali-activated ladle slag
AH3 Gibbsite
ASTM American society for testing and materials
BFS Blast furnace slag
BOF Basic oxygen furnace
C(N)ASH Calcium aluminate silicate hydrate with sodium composition
C2AH8 Dicalcium aluminate hydrate
C3AH6 Tricalcium aluminate hydrate
CAC Calcium aluminate cement
CAH10 Calcium aluminate decahydrate
CASH Calcium aluminate silicate hydrate
CSH Calcium silicate hydrate
d10 Particle size for cumulative 10% finer (µm)
d50 Median particle size (µm)
d90 Particle size for cumulative 90% finer (µm)
EAF Electric arc furnace
LOI Loss-on-ignition
LS Ladle slag
NASH Sodium aluminate silicate hydrate
OPC Ordinary Portland cement
W/B Water-to-binder ratio
XRD X-Ray diffraction
XRF X-Ray fluorescence
Greek symbols
β-C2S Larnite
γ-C2S Calcio-olivine
Standard cement chemistry notations were used; hence C denotes CaO, A is Al2O3,
S is SO4 and H is H2O.
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Original publications
This thesis is based on the following publications, which are referred to throughout
the text by their Roman numerals:
I Adesanya, E., Ohenoja, K., Kinnunen, P., & Illikainen, M. (2017). Alkali activation of ladle slag from steel-making process. Journal of Sustainable Metallurgy 3(2), 300-310
II Adesanya, E., Ohenoja, K., Kinnunen, P., & Illikainen, M. (2017). Properties and durability of alkali-activated ladle slag. Journal of Materials and Structures, 50:255.
III Adesanya, E., Sreenivasan, H., Kantola, A.M, Telkki, V.-V., Ohenoja, K., Kinnunen, P., & Illikainen, M. (2018). Ladle slag cement – Characterization of hydration and conversion. Construction and Building Materials, 193, 128-134.
IV Nguyen, H., Adesanya, E., Ohenoja, K., Kriskova, L., Pontikes, Y., Kinnunen, P., & Illikainen, M. (2019). Byproduct-based ettringite binder – A synergy between ladle slag and gypsum. Construction and Building Materials, 197, 143-151.
V Adesanya, E., Karhu, M., Ismailov, A., Ohenoja, K., Kinnunen, P., & Illikainen, M. Thermal behaviour of ladle slag mortars containing ferrochrome slag aggregates. Advances in Cement Research, In press.
The author’s contributions to the above Papers I-V were as follows:
The author designed the study with guidance from the supervisors and co-authors,
performed the experiment, analysed the data and wrote the paper, on which the co-
authors provided valuable comments, corrections and proofreading (Papers I & II).
The author designed the study with guidance from the co-authors, performed the
experiment, analysed the data and wrote the paper, on which the co-authors
provided valuable comments, corrections and proofreading. HS, AK and VT helped
with the nuclear magnetic resonance experiment (Paper III).
The author made a partial contribution to the experimental design together with the
co-authors and did most of the experimental work, co-analysis of the results and
writing of the paper as a co-author (Paper IV).
The author designed the study with guidance from the supervisors and the co-
authors, performed the experiment, analysed the data and wrote the paper, on which
the co-authors provided valuable comments, corrections and proofreading. AI
(Tampere University) conducted the dilatometry experiments and MK (Technical
Research Centre of Finland, VTT) helped with the preliminary high temperature
Romania 49.6 14.7 25.5 7.8 1.1 - β-C2S, Anorthite, CaS and
α-Al2O3
[42] Taiwan 48.6 23.7 4.2 8.1 1.21 - -
2.2 Slag-based and high-alumina cementitious binders
Methods for utilizing slags as binders in cementitious systems have been studied
and have gained wide acceptance in civil engineering applications and scientific
research over the past decades. This section will provide a general overview of the
alkali activation of slags, the hydration of crystalline slags and CAC hydration. It
should be mentioned that quite a number of high-quality reviews, books and papers
on the state of the art with regard to alkali-activated slags and slag hydration have
been published, providing a further understanding of this research (e.g. [13], [43]–
[45]), and the hydration and mechanism action of CAC will be introduced in this
current review, too, as high-alumina LS has proved to have similar properties.
25
2.2.1 Alkali-activated slags
The principle of the alkaline activation of slags was identified in the 1940s, but
systematic research into the synthesis of the binder was not undertaken until the
early 1960s [46]. Until the early 2000s, most of the studies on the alkali activation
of slags had been focused on blast furnace slags, and it is only in the past two
decades that attention has turned significantly towards the use of slags from other
metallurgical processes for alkali activation. The number of publications with the
keywords “alkali-activated” and “slags” published in Scopus (Figure 2) shows that
research in this field has grown immensely in recent years.
Fig. 2. Numbers of publications per year with the keywords “alkali-activated” and “slags”
in the last three decades (total: 1024). The data were collected and analysed from the
Scopus database
The basic principle behind this type of cement involves mixing finely ground slag
with a suitable alkali activator, which subsequently hardens to form a concrete-like
structure. Alkali hydroxides or alkali silicates, or both together, are popular
activators that have been used successfully in recent studies. The strength of the
resulting matrix is dependent on the type and dosage of the activator, the fineness
of the slag, the water-to-slag ratio and in some cases the curing temperature [47].
26
The reaction mechanism and products for alkali-activated slags are not
comprehensively understood, but they are dependent on the mineralogy and
fineness of the slag, the pH and type of the alkaline activator, the additives added
and in some cases the curing conditions. Nevertheless, authors of studies dealing
with the alkali activation of slag have described the process as beginning with the
dissolution of Me-O (Me=Ca,Mg) and Si-O-Si bonds to form C-S-H-type reaction
products having a low Ca/Si ratio [48], [49]. Depending on the Al content and
reactivity of the initial slag material, various levels of participation of Al in the
reaction to form a C-A-S-H-type reaction product have been reported previously
[50], [51]. In Figure 3, a schematic representation of the process of alkaline
activation of a high-calcium precursor is given and the reaction products described,
modified from two literature sources [52], [53].
Fig. 3. Mechanism for the dissolving of calcio-aluminosilicate glass (Modified from [52]
and [53]).
The activation pattern in an alkali-activated system has generally been categorised
into one of three types:
Alkaline activation of high-calcium systems: (Na, K)2O-CaO-Al2O3-SiO2-H2O,
Model 1. This model explains the synthesis in high-calcium and silicon-rich
materials, as in the alkali-activation of slags. The main reaction product in this
system is a calcium aluminate silicate hydrate (C-A-S-H) gel. This gel differs from
the C-S-H gel in hydrated OPC, as it has a low Ca/Si ratio and a distinct structure
[54]. The C-A-S-H gel chains in alkaline cements are longer, with up to 13
tetrahedral units as compared with 3 to 5 for the C-S-H gel chains in OPC systems,
in addition to which the gel structure in the former includes aluminium, which
replaces silicon in the cross-linking positions [55]. The main reaction product can
also be written as C-(N)-A-S-H with significant quantities of sodium acting as
charge balancing units or absorbed onto the gel [36]–[38].
27
Activation of low-calcium systems under alkaline conditions: (Na, K)2O-Al2O3-
SiO2-H2O, Model 2. This model describes the synthesis of materials with major
occurrences of aluminium and silicon in their composition, such as metakaolin, fly
ash and other aluminosilicate materials with a low CaO content. The main reaction
product in this model is described as a three-dimensional inorganic alkaline
polymer of sodium aluminosilicate hydrate (N-A-S-H) gel [58]. This model of
synthesis is known as geopolymerization, and the reaction gel is termed a
geopolymer or inorganic polymer [57].
Hybrid or blended alkaline cement systems: Model 3. This third model is a
combination of the previous two. The materials in the synthesis are blends of
aluminosilicates and calcium aluminosilicates (i.e. OPC + BFS + fly ash or LS +
metakaolin), and the reaction products are a complex mix of cementitious gels
which may include a C-A-S-H gel which has sodium in its gel composition and a
high calcium N-A-S-H gel that can be denoted as (N,C)-A-S-H [59].
These reaction products are accompanied by other secondary reaction products,
depending on the type of activating solution used, i.e. monosulphoaluminate
(AFm)-type phases in NaOH-activated binders [60], [61] and AFm phase
strätlingite in alkaline silicate-activated binders [56], [62]. Other factors include the
MgO content of the starting material. Hydrotalcite has been reported in high-MgO
slags [48], [56], [63] and crystalline zeolites in low-MgO precursors (less than 5%)
[53], [64] and some carbonated phases. It is proposed here that the alkali activation
of LS follows Model 1, with some new reaction products that will be discussed
later.
2.2.2 Hydration of crystalline slag
The reactivity of steel slags varies significantly from one slag to another. This is
due to the differences in mineralogy and chemical composition between the raw
materials, furnace processes and cooling methods used. When cooled rapidly with
water, dicalcium silicate (β-C2S) in the slag is stabilized and not transformed to γ-C2S, which is predominant in steel slags. With the exception of LS, some EAF and
BOF when rapidly cooled tend to crystallize further [65], [66]. Hence, most steel
slags are termed crystalline slags because of predominant crystalline mineral
phases and lower glassy content.
Steel slags are generally termed cementitious, though with low activity due to
their mineralogical phases (i.e. γ-C2S), which have lower hydraulic activity than
those in OPC [67], and they therefore require activation in a high-pH environment
28
in order for some of the mineral phases to hydrate. Another factor limiting the use
of steel slags alone in concrete is the potential volumetric instability associated with
the f-CaO and/or f-MgO reaction in the slag [2], [23].
Nevertheless, when ground to fine particle sizes, these slags have shown to be
reactive and have also been used as a co-binder with OPC, fly ash or some other
hydraulic binder [68]–[70]. Other methods that have been used to increase the
reactivity and hydration of steel slags include thermal treatment followed by rapid
cooling [66], [71], [72]. In one previous study pulverized LS was reheated at 900 °C
and rapidly cooled with high-pressure air. It was reported that after this pre-
treatment the slag had a glass content of 92% compared with 6.5% in slowly-cooled
slag. Also, the f-CaO content was negligible after this treatment [71].
In another similar study [66] the authors used water jet cooling after re-melting
EAF and LS and reported an increase in the glass content of the slags. The LS used
in the present work was deficient in f-CaO, however, and pre-treatment methods
are beyond the scope of this study.
2.2.3 Hydration of calcium aluminate cement
LS containing high alumina and calcium bares certain similarities to CAC, mainly
since the elemental composition of CAC consists of calcium, alumina and iron,
with minor proportions of silicon and titanium [73]. Also, these cements are four
or five times more expensive than OPC and thus not an economic replacement for
it. They are nevertheless used in some special applications, either as the main binder
or as a co-binder with other materials (e.g. OPC, gypsum) in a hybrid mix [73].
Other CAC applications include:
– fast-setting concrete
– refractory applications
– resistance to chemical (acid) attacks resistance to impacts and abrasion.
The basic difference between OPC and CAC lies in the main mineralogical phase
that contributes to setting and hardening. The main mineral phases in OPC are
dicalcium and tricalcium silicates (C2S and C3S), which in contact with water forms
calcium silicate hydroxide (C-S-H) and calcium hydroxide (CH). Although, unlike
OPC, there is a wide fluctuation in the chemical composition and mineralogy of
CAC, its major mineralogical phases are calcium aluminate phases such as
monocalcium aluminate (CA), dodecacalcium hepta-aluminate (C12A7), also
known as mayenite, and tricalcium aluminate (C3A). When these phases are
29
hydrated, calcium aluminate hydrates are produced [74]. These calcium aluminate
hydrate formations are chemically quite different from OPC, as their hydrates
include CAH10, C2AH8, C3AH6 and poorly-crystallized AH3. Both CAH10 and
C2AH8 are metastable, in that they form temporarily and convert to a stable product
(C3AH6 and AH3, respectively) over a period of time, as shown in the following
Dilatometry (Paper V) was carried out using a NETZSCH DIL 402 Expedis dilatometer, with samples approximately 8×8×10 mm3 in size. The samples were heated to 1000 ºC at 6 ºC/min and there was a one-hour dwelling time at the peak temperature, after which the furnace was set to a cooling rate of 10 °C/min for the final stage. The heating chamber was open-ended, with a constant flow of nitrogen (40 ml/min) as the purge gas to prevent unwanted gaseous/evaporated matter from entering the measurement chamber, which was separate from the heating chamber and sample holder. The in-situ volume expansion and/or shrinkage during heating was then analysed.
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4 Results and Discussion
4.1 Properties of ladle slag
4.1.1 Reactivity/hydraulic potential of ladle slag
Slags are categorized into three groups according to their basicity coefficient (Mb):
acidic (Mb < 1), basic (Mb >1) and neutral (Mb = 1). Using the equation [Mb =
(CaO + MgO)/(SiO2+Al2O3)] it is clear from their chemical compositions that the
basicity coefficient of all the LS samples used in this study (see Table 3) ranges
between 1.3-1.6, and thus the slag can be classified as basic and potentially
hydraulic [57], [92].
4.1.2 Mineralogy
Quantitative X-ray diffraction (QXRD) was used to determine the amorphous and
crystalline content of the various LS samples, as shown in Table 6. Due to the slow
cooling of LS, the amorphous content of the slag is low and below the
recommended glass phase content of 30-90% reported to be essential for slag
reactivity during alkali activation [92]–[94]. Although the vitreous content of some
slags may play a role in their reactivity, it has been shown in new studies of highly
crystalline slags that there is no general correlation between the glassy phase slags
in their reactivity or hydraulicity [48], [65], [95], [96]. This claim will be
additionally verified in the later part of this section. It suffices here to state, however,
that LS consists mineralogically of mayenite (C12A7), calcio-olivine (γ-C2S),
periclase (MgO), and tricalcium aluminate (C3A), as shown in Figure 6.
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Fig. 6. XRD pattern for LS showing the mineralogy phases: a=mayenite/C12A7, b=calcio-
olivine/γ-C2S, c=periclase/MgO, and d=tricalcium aluminate/C3A.
Table 6. Quantitative mineralogy of ladle slag.
Phase C12A7 γ – C2S C3A MgO Amorphous
Wt.% 26-35 18-22 11-19 7-13 15-22
Since the free lime content of the slag determined using the method described in
EN 450-1 [97, pp. 450–1] varied between 0.0 and 0.4% (see Table 3) of the overall
CaO content of the LS, it may be concluded that the potential volume instability
associated with steel slags is not applicable to the LS used here.
4.2 Effect of alkali activation on the reaction kinetics of LS
Alkali activation of LS results in rapid, intense heat generation, as shown in Figure
7. An exothermic peak is recorded immediately after mixing of the alkaline
activator with the slag and can be attributed to the wetting and initial dissolving of
the slag particles. This peak is similar to the well-known pre-induction period that
occurs in cement hydration, although the physicochemical reactions involved are
markedly different. The breadth of this peak may suggest initial formation of
45
reaction products immediately after adding the activator to the slag. The addition
of citric acid had no significant effect on the reactions, as the induction period was
very short, and further reactions of the binder continued after 3.5 hours. The rapid,
intense heat released in this period is mainly due to the fast-setting properties of the
mayenite phase in the slag.
Furthermore, the acceleration peak was followed by a more intense peak with
a maximum heat release of approximately 16 J/h·g after 5 hours of the reaction,
this peak being attributed to a second formation and precipitation of reaction
products such as C-A-S-H [98] and calcium aluminate hydrates in the activated
slag [99]. The cumulative heat released after 50 hours of reaction was about 125
J/g, which is lower than that observed after 50 hours in hydrated OPC, around 225
to 280 kJ/kg, and similar to the cumulative heat released in alkali-activated blast
furnace slag [100]–[102]. This calorimetry is representative of the alkali-activated
LS with no added silica source (i.e. diatomaceous silica) used in this study (Paper
V).
Fig. 7. Heat evolution in the first 50 hours of the alkali activation of LS. The first 10
hours of the reaction are shown in the inset.
46
4.3 Identification of reaction products in AALS
The dissolving of the vitreous and crystalline phases of LS resulted in formation of
x-ray amorphous reaction product in the AALS (Figure 8) determined after 28 days
of reaction. The broad hump featured between 24° 2θ and 30° 2θ after alkali
activation is consistent with the formation of amorphous phase of aluminosilicates,
typically a C-A-S-H and N-A-S-H or hybrid C-(N)-A-S-H gel, as previously
reported in the literature [103], [104]. A similar amorphous hump can be observed
with an increase in the silica content of the matrix, but it is broader and more intense
and may indicate an increase in the formation of the amorphous phase. No other
new crystalline phases were detected in the AALS diffractograms. The FTIR
spectra in Figure 9 supplement the observations of the formation of a new
amorphous gel gained from the XRD findings.
47
Fig. 8. X-ray diffractograms of raw LS, AALS (Ca/Si=1.6) and AALS (Ca/Si=1.2). a=
mayenite (C12A7) b= dicalcium silicate (ɣ-C2S) and c= periclase (MgO) (Modified from
Paper I).
The IR spectra in Figure 9 represent the bands before and after alkali activation of
the LS. The spectra of the alkali activated LS exhibit a stronger band at 1650 cm-1,
which is assigned to the stretching vibration (-OH) consistent with the presence of
a reaction product [104], [105]. This band is not intense in raw LS. Meanwhile, the
broad band at 1030 cm-1 may be attributed to asymmetric stretching vibration in the
T-O-Si (T=Al or Si) bonds [106]–[108] and shifts to a higher wavenumber after
alkali activation and with increasing silica content, which is consistent with the
formation of polymerized units in an amorphous structure [107], [109]–[111] and
may indicate reduced substitution of Si for Al in the C-A-S-H gel with increasing
silica content [105], [107].
48
Fig. 9. FTIR spectra for raw LS and AALS paste (data from Paper I).
4.4 Effect of aggregates on strength and durability of AALS
4.4.1 Compressive strength
The aggregate content of the AALS mortars had a significant effect on their strength
and durability, as studied in Paper II. As shown in Figure 10, the mortar sample
(SS3) had a greater strength at all ages than the paste samples (SS0). Due to the
low water content, high viscosity and low workability of the mix, the standard sand-
to-binder ratio of 3:1 was unattainable. Hence for SS3, the sand-to-binder ratio used
was 2.3. As observed at 28 days, both samples suffered strength loss due to changes
in the reaction product. This mechanism, known as “metastable hydrate
conversion”, will be discussed further in the next section (see subsection 4.5). In
addition, both samples continued to gain strength after 28 days of conversion, the
effect increasing until the final testing time at 90 days.
49
Fig. 10. Compressive strength of AALS paste and mortar at different curing days
The aim of this work was to study the utilization of LS, a by-product of the
steelmaking process, in high-value applications by determining the potential
hydraulic activity of this slag on the basis of its chemical composition and
mineralogy. Papers I, II and V of this thesis investigated the alkali activation of this
slag and studied its durability after hardening. Since the activated sample set rapidly
by virtue of its major mineral phase, mayenite, citric acid was added as a retarder
between 0.8 and 1 wt.% (of the water content) to prolong its setting.
After alkali activation LS showed considerable mechanical strength, so that it
could be used as a sole precursor in alkali-activated materials. The reaction product
formed in AALS was analysed by XRD and FTIR and shown to be possibly a C-
A-S-H-like gel and, in view of the stoichiometry of the mix with sodium in its
structure, to be acting as a charge balance or to be absorbed onto the gel. Unlike
the situation in fly ash or other aluminosilicates alkali activation, elevated
temperatures are not required for the hardening or curing of AALS as it had no
significant influence on the strength of the matrix.
When the durability of AALS mortars under conditions of severe weathering
was studied, the mortar sample exhibited good frost resistance after 60 freeze-thaw
cycles, losing less than 1% of its strength and less than 2% of its weight. On the
other hand, the shrinkage of the AALS mortar on drying was almost twice that
reported for alkali-activated BFS and 7 times more than for OPC.
In spite of the lower strength, the hydraulic properties of LS (yielding HLS)
offers a cheaper alternative method for utilizing LS. The main hydration products
emerging from this hydraulic system were found to convert from metastable C2AH8
to stable C3AH6 during curing, thereby undergoing a loss of strength. By lowering
the water content of the system to a maximum of w/b: 0.35, the rate of conversion
could be lowered, irrespective of the w/b ratio, while all the samples tested recorded
a continuous gain in strength from 28 days onwards.
To modify and stop the conversion of hydration products in this HLS system,
the HLS was blended with gypsum to form an ettringite system. Upon adding the
gypsum, the calcium aluminate phases (mayenite and tricalcium aluminate) reacted
to form ettringite and gibbsite, and later monosulphoaluminate was also detected
as a modified hydration product. No strength loss was recorded in this modified
ettringite binder, and when the efficiency of the modified system was analysed
under severe conditions, the sample exhibited superior durability properties and
strength to those of the HLS mortars. The gypsum used in this case can also be
72
potentially replaced by gypsum produced as a by-product in the phosphoric acid
industry. Gypsum-modified LS binder is a potential low-cost cementitious material.
The last paper in this thesis studied the refractory applications of the mortars
designed here (except for LSG) using a w/b of 0.35. The results obtained by
exposing the mortars to high temperatures (110-1000 °C) showed that HLS
containing ferrochrome aggregate had a better resistance and structural appearance
than commercial refractory cement or AALS mortars. The HLS mortar sample
retained a strength of approximately 18 MPa after exposure to 1000 °C. In a high
alkaline environment (AALS), the introduction of ferrochrome slag as an aggregate
increased the strength of the mortar before its exposure to elevated temperatures.
The increment in strength compared with AALS with sand may be partly attributed
to the alkali-aggregate reaction occurring in the system, and for this reason
ferrochrome slag may not be suitable as an aggregate in high temperature
applications of alkali-activated materials.
The results of this study on the use of LS as a cementitious binder show that
LS could be used to achieve high-strength mortars. Additionally, as a cementitious
material with almost zero environmental footprints, it could be used as a cheaper
alternative to commercial calcium aluminate cement and Portland cement in
refractory and structural applications in civil engineering. The fast setting of this
slag and its rapid gain in strength can be advantageous when using it for structural
repairs. In addition, to avoid strength loss, the optimal water-to-binder ratio of 0.35
should be used, save if the composition of the mix is modified with an addition of
gypsum. And it is imperative that proper strength value is considered before use in
structural design. However, it is also necessary to point out that the free lime
content of the slags used in this thesis was below 1% which pose no deleterious
effect on the mortars. Also, free MgO (<5% recommended) content should be put
into consideration before the use of the slag in structural applications due to long
term volumetric expansion caused by carbonation and hydration of the free MgO.
Here in this thesis, the content of the ladle slag varies between 0 to 7%. The use
should be limited if it’s above the recommended value of below 5%. The presence
can however be specially utilized under suitable conditions for their gainful use in
structural applications.
To conclude, the present results contribute to the scientific understanding of
high-alumina slag hydration, including its relation to CAC cements, modification
of the reaction and potential fields for its utilization in connection with inorganic
binders.
73
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Appendices
Appendix A
Fig. A1. XRD of HLS samples with different w/b ratio (a) 0.35 and (b) 0.50. The letters
I Adesanya, E., Ohenoja, K., Kinnunen, P., & Illikainen, M. (2017). Alkali activation of ladle slag from steel-making process. Journal of Sustainable Metallurgy 3(2), 300-310
II Adesanya, E., Ohenoja, K., Kinnunen, P., & Illikainen, M. (2017). Properties and durability of alkali-activated ladle slag. Journal of Materials and Structures, 50:255.
III Adesanya, E., Sreenivasan, H., Kantola, A.M, Telkki, V.-V., Ohenoja, K., Kinnunen, P., & Illikainen, M. (2018). Ladle slag cement – Characterization of hydration and conversion. Construction and Building Materials, 193, 128-134.
IV Nguyen, H., Adesanya, E., Ohenoja, K., Kriskova, L., Pontikes, Y., Kinnunen, P., & Illikainen, M. (2019). Byproduct-based ettringite binder – A synergy between ladle slag and gypsum. Construction and Building Materials, 197, 143-151.
V Adesanya, E., Karhu, M., Ismailov, A., Ohenoja, K., Kinnunen, P., & Illikainen, M. Thermal behaviour of ladle slag mortars containing ferrochrome slag aggregates. Advances in Cement Research, In press.
Reprinted with permission from Springer Nature (I, II), Elsevier Ltd. (III, IV)
and ICE Publishing (V).
The original publications are not included in the electronic version of this thesis.
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A CEMENTITIOUS BINDER FROM HIGH-ALUMINASLAG GENERATED IN THE STEELMAKING PROCESS
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