Materials Research.

2023; 26: e20230069

DOI: [Link]

Combined Use of Ladle Furnace Slag and Rice Husk Ash

as a Supplementary Cementitious Material

Everton de Freitas Cordova de Souzaa , Tayná Fracão da Silvaa , Mylena Alves de Castrob ,

Gisleiva Cristina dos Santos Ferreiraa,b 

a
Universidade Estadual de Campinas, Faculdade de Engenharia Civil, Arquitetura e Urbanismo,
Rua Saturnino de Brito, 224, Cidade Universitária “Zeferino Vaz”, 13083-889, Campinas, SP, Brasil.
b
Universidade Estadual de Campinas, Faculdade de Tecnologia, Rua Paschoal Marmo, 1888,
Jardim Nova Itália, 13484-332, Limeira, SP, Brasil.

Received: January 15, 2023; Accepted: May 21, 2023

Ladle Furnace Slag (LFS) is a solid waste from steel production that can be used in civil construction
due to its high content of calcium oxides (> 50% CaO), contributing to the sustainability of both
industries. Seeking to study its function as a supplementary cementitious material, the objective of this
work was to determine the properties of coating mortars with the replacement of Portland Cement (PC)
by 30% LFS combined with the pozzolanic effect of Rice Husk Ash (RHA). Prismatic specimens were
produced in a 1:6 mixture proportion (PC:sand) and subjected to mechanical tests and determination
of the dynamic modulus of elasticity. The results indicated that the replacement provided a reduction
in mechanical strength, however the presence of LFS+RHA was beneficial to improve water retention.
These changes were caused by the bigger surface area of RHA grains and the higher CaO content, in
relation to the reference mixture.

Keywords: industrial waste, binder, portland cement, mortar, sustainable construction

1. Introduction
The civil construction industry has dedicated itself Furthermore, the presence of 15 to 20% of amorphous material
to reducing its environmental impacts, and one of the presented in the material favors this use13,14.
solutions found is the use of waste from other productive This incorporation of LFS as SCM does not bring
sectors as raw material, including waste generated by significant differences in essential properties such as
the steel industry1,2. Included in this context are the slags anchoring capacity and dynamic modulus of elasticity in
generated during steel production, with emphasis on Ladle relation to mortars without slag6,15. Even with an increase in
Furnace Slag (LFS), with an estimated world production the water/binder ratio, these properties can be maintained,
of 30 million tons per year3. Searches of the application of with proper choice of batch and dosage of the LFS16.
LFS in civil construction analyzed its use as an aggregate in However, chemical expansion may still be a cause for
cementitious matrices4 and more recently as a Supplementary concern, as some studies have shown elevated values at
Cementitious Material (SCM) as an alternative to Portland 28 days, leading off a search for methods to mitigate the
Cement (PC)5,6. In the search for a binder with a more presence of chemical compounds that trigger volumetric
sustainable composition, this type of insertion makes it instability. A useful way may be its combination with the
possible to develop products that reduce carbon dioxide use of siliceous materials that may favor the formation of
emissions, energy consumption, waste disposal and the C-S-H by the consumption of CaO6,9.
use of natural resources7. In this way, the incorporation of a pozzolana is a favorable
Based on this, LFS utilization has been investigated method to enhance the LFS use as binder, considering that
in order to improve the potential of this material, taking this type of slag has a high content of calcium hydroxide, an
advantage of its chemical composition (high content of essential compound for pozzolanic reactions7,11. Among this
calcium oxides and hydroxides), transforming this residue type of materials, Rice Husk Ash (RHA) stands out as a viable
into a co-product8,9. Its physicochemical properties are alternative due to its satisfactory reactivity from non-crystalline
mostly influenced by the scrap used in steel production silica17,18. RHA is already utilized as a pozzolanic addition,
and by the cooling method adopted in the steel unit, as with positive results in terms of mechanical properties
well10,11, which also affects its chemical composition and and durability, in addition to environmental benefits19,20.
granulometry, which can determine the performance of LFS It has been observed that the pozzolanic reaction converts
as a binder12. So, monitoring free CaO and MgO contents portlandite with amorphous silica into C-S-H phases, which
is essential to control possible chemical reactions expansive11. may lead to a higher content of portlandite in early ages.
On the cementitious microstructure, its effect has brought
*e-mail: e233480@[Link] better results in terms of durability and compressive strength,
2 Souza et al. Materials Research

resulting from the pronounced dense microstructure, which The characterization of the materials was carried out through
in turn greatly reduced the absorption of capillary water tests to obtain the water content24, specific mass25, and laser
in the specimens21. Positive results were also seen in the granulometry, in addition to X-Ray Fluorescence (XRF),
use of a controlled batch of RHA, which potentiated the and Loss on Ignition (LOI) analysis.
pozzolanic reaction and improved durability and resistance For the mortar study, the replacement content of PC
properties, with an improvement in specific and long-term by LFS was set at 30% based on the study by Silva26, who
compressive strength, greater ductility under compressive evaluated the same batch of slag, while the RHA index
load, in addition to shrinkage rates per drying like the control, was 10%, also according previous literature17. The mix
ensuring tightness22. proportions were defined for coating mortar and based
Therefore, the objective of this work was to determine on similar previous research 6,8 and the water/binder
the mechanical properties of cementitious mortars with 30% ratio was defined according to the Flow Table tests27,
replacement of Portland Cement (PC) by LFS and addition considering a normal consistency of 260 mm (± 5 mm).
of 10% of RHA, as a supplementary cementitious material. Table 1 details the mixture proportions and respective
identifications.
2. Materials and Methods To determine mortar properties, still in the fresh state, water
retention and density tests were also carried out, according
The LFS sample was provided by a company in the steel to NBR 1327728 and NBR 1327829, respectively. Regarding
sector, located in the Piracicaba/SP region, defined according to the properties in the hardened state, tests were carried out to
the type of cooling and texture (by air and fine, respectively), determine the bending tensile strength (Tsm), compression
compatible with the objective of this research (replacement strength (Csm)30, dynamic modulus of elasticity (Ed)31,
part for Portland Cement by LFS). Portland cement (CP II-F), density32 and water absorption by capillarity33. In view of the
rice husk ash (RHA), quartz sand (QS) and local water analysis of the results, obtained the classification of mortars
supply were also used as materials in the research. To carry according to NBR 1328134.
out the tests, the sample was dried in an oven at 105 °C
and cooled to room temperature. To increase its fineness, a
pre-processing with sieving and grinding in a ball mill was 3. Results and Discussion
carried out, using the material that passes through the sieve Figure 2 shows the granulometric curves of the LFS
with an opening of 0.6 mm23, as in Figure 1. after pre-processing, the RHA and the PC. The fineness
Next, the methodology of this research was divided into results of the samples show that the sieving benefited the
two stages: physical-chemical materials characterization LFS because, by making the material thinner, it increases
and the determination of the mortar mechanical properties. its specific surface, favoring hydration reactions23.

Figure 1. (a) Pre-processing of the LFS sample using MA500 ball mill with alumina ceramic jar and (b) LFS after pre-processing.

Table 1. Volume proportions of mortar mixtures.

Binder Aggregate
Identification
PC LFS RHA Sand
REF 1.0 0.0 0.0 6.0
REF-RHA 0.9 0.0 0.1 6.0
LFS 0.7 0.3 0.0 6.0
LFS-RHA 0.6 0.3 0.1 6.0
 Combined Use of Ladle Furnace Slag and Rice Husk Ash as a Supplementary Cementitious Material 3

Table 2. Chemical composition of materials samples.

Chemical elements (%)
Sample LOI (%)
CaO SiO2 MgO Fe2O3 MnO SO3 Si K Ca Al Mn
LFS 54.6 9.78 5.79 7.59 7.29 - - - - - - 12.0
RHA - - - - - - 88.94 5.97 1.66 1.33 1.15 -
CPII-F 63.4 12.4 2.83 3.86 - 2.76 - - - - - 10.8

Figure 2. Granulometric curves of PC II – F, LFS and RHA samples.

The LFS sample also demonstrates similarity with the PC,

presenting very close values for D10 in relation to Portland
cement (PC II-F), a characteristic strongly influenced by the
slow cooling method adopted10. The greatest difference occurs
in the mean diameter of the LFS (44.6 µm) in relation to
that obtained for the PC (25.15 µm), which can be adjusted
during slag processing (grinding and sieving).
Regarding the materials density, the sand sample presented
a value of 2.65 g/cm3, while PC and LFS demonstrated
results of 3.00 g/cm3 and 2.70 g/cm3, respectively. Being
slightly lower than the PC result, the LFS density is another
property influenced by the reactions in the sample cooling
process6,8, where the binding properties of the residue were
also determined10,11,26.
The RHA, on the other hand, presented a significantly
lower density (2.05 g/cm3). For the chemical characterization, Figure 3. Main peaks of compounds presented in the XRD analysis
the XRF and LOI tests were carried out, which results are of the materials.
shown in Table 2. It can be seen that the LFS and PC samples
have a high CaO content (55% and 63%, respectively), as
well as other chemical elements, also important to obtain to verify the combined formation of olivine, portlandite,
hydraulic chemical reactions (FeO2; SiO2), however, in calcite, quartz, periclase, which are also present in the PC
different levels. The amount of free lime in the LFS is sample and in other studied LFS samples11,35. These results
adequate when observing better hydration and controlled of endorse the sample’s potential for use as a SCM, as they
the chemical reactions expansion when used in cementitious demonstrate a composition that leads to the formation
matrices6,13. FeO2 and SiO2 contents varied in relation to of C-S-H in cementitious matrices during the hydration
PC and are relevant since they are correlated with the process6. Meanwhile, the RHA diffractogram exhibited a
hydraulic reactivity potential of LFS, especially between cristobalite (SiO2) peak.
silica and possible volumetric instabilities8. The images obtained by Scanning Electron Microscopy
The XRF analysis (Table 2) showed that the main oxides and Energy Dispersive Spectroscopy (SEM+EDS)
present in the LFS sample are CaO, SiO2, Fe2O3, MgO, allowed obtaining the morphology of the slag particles
MnO. Through XRD analysis (Figure 3), it was possible and identifying the main chemical compounds (Figure 4).
4 Souza et al. Materials Research

In addition, the images demonstrated that the particle shapes As a result, there were larger spreading taxes of mortars with
of this LFS sample are different, due to the pre-processing LFS and with RHA, improving their workability. In time,
performed. The EDS analysis identified the elements: O, Ca, Herrero et al.36 also studied the properties of mortars with
Mn, Fe, Mg and Si, like the sample studied by Henríquez et al.35, LFS (35% replacement of PC), reporting similar behavior.
when the presence of the same compounds was observed, Still on the properties in the fresh state, only mortar with
with the addition of aluminum oxide. The occurrence of LFS+RHA consumed the minimum value of 79% in relation
this element in the LFS is associated with the addition of to water retention, as required by NBR 1328134, inferring that
aluminum during the deoxidation process of the secondary the presence of LFS significantly improved with the mortars
refining of steel in the ladle furnace6. studied, in relation to the fresh state of the reference mortar.
According the characterization results of mortars in the Table 4 presents the results of the mortars in the hardened
fresh state displayed in Table 3, an increase in the water/binder state, also showing the statistical analysis of the results by the
ratio of mortars with LFS (1.62) and LFS+RHA (1.95) is ANOVA method and comparison of means by the Fisher Test.
observed in relation to the reference (1.13), making up Regarding Tsm and Ed, it appears that REF+RHA and REF are
43% and 72% respectively. This raise is justified by the statistically equal, as well as EFP+RHA and LFS. These two
bigger surface area of the RHA grains and the higher CaO properties are crucial in the study of coating mortars as they
and Ca(OH)2 content in the LFS (chemical elements that reflect, respectively, their anchoring capacity and ability to
have a greater capacity for absorbing and retaining water). absorb deformations when acting in a constructive system6,8.

Figure 4. SEM images of LFS sample in (a) 200x and (b) 1000x magnitudes, and (c) EDS spectrum showing relative intensities of
LFS chemical elements.

Table 3. Properties analysis of mortars in the fresh state.

Property REF REF+RHA LFS LFS+RHA
Consistency index (mm) 257 258 260 262
Water binder ratio w/b 1.13 1.26 1.62 1.95
Water Retention (%) 74 77 63 79
Density (kg/m3) 2,158 2,153 2,138 2,174
 Combined Use of Ladle Furnace Slag and Rice Husk Ash as a Supplementary Cementitious Material 5

Table 4. Properties analysis of the mechanical properties of mortars.

Property REF REF+RHA LFS LFS+RHA
Tsm (MPa) 1.82 1.84 1.48 1.14
SD (MPa) 0.09 0.04 0.07 0.16
CV (MPa) 0.05 0.02 0.05 0.011
P-value 0.00121
Homogeneous Groups A A B B
Class R2 R2 R2 R2
Csm (MPa) 6.81 6.19 4.66 4.13
SD (MPa) 0.45 0.23 0.17 0.19
CV (MPa) 0.07 0.04 0.04 0.05
P-value 7.33e-13
Homogeneous Groups A B C D
Class P5 P4 P4 P4
Ed (GPa) 13 12 9 8
SD (GPa) 0.58 0.57 0.29 0.49
CV (GPa)
P-value 4.24e-6
Homogeneous Groups A A B B
SD: Standard deviation; CV: coefficient of variation.

It was possible to state that the presence of RHA did not By this, they were classified as C4 for mixtures without LFS
change the mortars behavior, that is, the expected effect of and C5 for mixtures with LFS34. These changes in compressive
mechanical resistance increase did not occur. This process strength and capillarity coefficient are explained by the increase
took place due to the short curing period (28 days) which in the w/b ratio in mortars with LFS, triggering a decrease in
is not enough for complete pozzolanic chemical reactions. mechanical strength. Nevertheless, this does not necessarily
By comparing the results of the mortars with LFS and RHA represent a loss in the performance of the matrix, since mortars
with the REF mix, it is verified significantly reduced the for coating walls are more requested regarding support and
values of Tsm, Csm, and Ed, same behavior was observed absorb deformations, which require less rigidity, that is, less
with 45 days interval36. In this sense, is worthy to mention mechanical strength38,39. In this sense, Ed is also an important
that the reduction of the mechanical properties of mortars parameter to assess the range of absorption of deformations
with LFS is caused by the average diameter of its particles, between the substrate and the mortar, which occur during the
as well as by the lower percentage of amorphous chemical drying and hydration cycles, in addition to the established
compounds. As for Ed, the decrease can be considered importance in the demands of the structure in service6,38,40.
beneficial for the coating mortars, as the LFS reduced the
stiffness of the mortars studied. Altering this property favors 4. Conclusions
the absorption of tensions resulting from deformation and In view of the proposed objective, it was demonstrated
accommodation (shrinkage, movement of masonry, thermal that the use of LFS as a complementary binder in the partial
variations in the environment). replacement of PC (30%) and addition 10% RHA does not
The mortar classification according to NBR 1328134 affect the behavior of mortars the fresh state. However,
indicates that the mixtures with LFS showed the same changes in the hardened state resulted in changes in relation
behavior as the REF mix, when considering Tsm results, to classification, according to NBR 1328134. But, the lower
all classified as R2. However, the same did not happen values in the compressive strength and capillarity coefficient,
for compressive strength, when REF was classified as can be evaluated as beneficial as it reduced the stiffness of
P5, while the other mixes were in P4 class. This property the mortars, contributing to the reduction of shrinkage and
was more affected at 28 days by the incompleteness deformation cracks. As reasons for changes in the mechanical
of hydration reactions; however, it may have a slight properties of mortars with LFS and LFS+RHA, are cited:
recovery at higher ages due to the slow release of water the average diameter of the slag greater than that of PC,
in the matrix, making it available to react with unreacted chemical composition, and insufficient curing period for
components of LFS37. the expected pozzolanic chemical reactions.
The capillarity coefficient test presented the For the next studies, it is indicated to study the behavior
following results: 4.38, 5.79, 8.95, and 9.35 for the REF, of mortars aged over 28 days, for a better evaluation of
REF+RHA, LFS, and LFS+RHA mix groups, respectively. pozzolanic reactions.
6 Souza et al. Materials Research

5. Acknowledgments 18. Lo F-C, Lee M-G, Lo S-L. Effect of coal ash and rice husk ash
partial replacement in ordinary Portland cement on pervious
This work was funded by the Brazilian Research concrete. Constr Build Mater. 2021;286:122947.
Agency CAPES. Financial Code 001. The authors also thank 19. Siddika A, Mamun MAA, Alyousef R, Mohammadhosseini
ArcelorMittal for supplying the LFS batch. H. State-of-the-art-review on rice husk ash: a supplementary
cementitious material in concrete. J King Saud Univ - Eng Sci.
2021;33(5):294-307.
6. References 20. Nasiru S, Jiang L, Yu L, Chu H, Huang Y, Pei C, et al. Properties
1. WSA: World Steel Association. Annual production steel data of cement mortar containing recycled glass and rice husk ash.
[Internet]. [Link]; 2022 [cited 2023 Jan 10]. Available from: Constr Build Mater. 2021;299:123900.
[Link] 21. Thiedeitz M, Ostermaier B, Kränkel T. Rice husk ash as an
steel-data/?ind=P1_crude_steel_total_pub/CHN/IND additive in mortar – Contribution to microstructural, strength
2. Jin F. Sustainable utilization of slags. In: Tsang DCW, Wang L, and durability performance. Resour Conserv Recycling.
editors. Low carbon stabilization and solidification of hazardous 2022;184:106389.
wastes. USA: Elsevier; 2022. Chap. 20, p. 321-41. 22. Muthukrishnan S, Gupta S, Kua HW. Application of rice husk
3. Li L, Ling TC, Pan S-Y. Environmental benefit assessment biochar and thermally treated low silica rice husk ash to improve
of steel slag utilization and carbonation: a systematic review. physical properties of cement mortar. Theor Appl Fract Mech.
Sci Total Environ. 2022;806:150280. 2019;104:102376.
4. Sideris KK, Tassos C, Chatzopoulos A. Production of durable 23. Papayianni I, Anastasiou E. Effect of granulometry on
self-compacting concrete using Ladle Furnace Slag (LFS) as cementitious properties of ladle furnace slag. Cement Concr
filler material. Procedia Eng. 2015;108:592-7. Compos. 2012;34(3):400-7.
5. Sáez-de-Guinoa Vilaplana A, Ferreira VJ, López-Sabirón 24. ABNT: Associação Brasileira de Normas Técnicas. NM 24:2002:
AM, Aranda-Usón A, Lausín-González C, Berganza-Conde materiais pozolânicos – determinação do teor de umidade.
C, et al. Utilization of Ladle Furnace slag from a steelwork for Rio de Janeiro: ABNT; 2002.
laboratory scale production of Portland cement. Constr Build 25. ABNT: Associação Brasileira de Normas Técnicas. NBR 16605:
Mater. 2015;94:837-43. cimento Portland e outros materiais em pó — determinação da
6. Najm O, El-Hassan H, El-Dieb A. Ladle slag characteristics massa específica. Rio de Janeiro: ABNT; 2017.
and use in mortar and concrete: A comprehensive review. 26. Silva TF, Moura MAN, Souza EFC, Ferreira GCS, Pereira
J Clean Prod. 2021;288:125584. VFR. Influence of the cooling process on the physicochemical
7. de Azevedo Basto P, Estolano de Lima V, de Melo AA No. Effect properties of ladle furnace slag, used in the replacement of
of curing temperature in the relative decrease peak intensity Portland cement. Materia (Rio J). 2022;27(3):e20220089.
of calcium hydroxide pastes for assessing pozzolanicity of 27. ABNT: Associação Brasileira de Normas Técnicas. NBR 13276:
supplementary cementitious materials. Constr Build Mater. argamassa para assentamento e revestimento de paredes e
2022;325:126767. tetos - determinação do índice de consistência. Rio de Janeiro:
8. Borges Marinho AL, Mol Santos CM, Carvalho JMF, Mendes ABNT; 2016.
JC, Brigolini GJ, André Fiorotti Peixoto R. Ladle furnace slag as 28. ABNT: Associação Brasileira de Normas Técnicas. NBR
binder for cement-based composites. J Mater Civ Eng. 2017;29(11) 13277: argamassa para assentamento e revestimento de paredes
9. Martins ACP, Franco de Carvalho JM, Costa LCB, Andrade e tetos - determinação da retenção de água. Rio de Janeiro:
HD, de Melo TV, Ribeiro JCL, et al. Steel slags in cement-based ABNT; 2005.
composites: an ultimate review on characterization, applications 29. ABNT: Associação Brasileira de Normas Técnicas. NBR
and performance. Constr Build Mater. 2021;291:123265. 13278: argamassa para assentamento e revestimento de paredes
10. Choi S, Kim J. Hydration reactivity of calcium-aluminate-based e tetos - determinação da densidade de massa e do teor de ar
ladle furnace slag powder according to various cooling conditions. incorporado. Rio de Janeiro: ABNT; 2005.
Cement Concr Compos. 2020;114:103734. 30. ABNT: Associação Brasileira de Normas Técnicas. NBR 13279:
11. Fang K, Zhao J, Wang D, Wang H, Dong Z. Use of ladle determinação da resistência à tração na flexão e à compressão.
furnace slag as supplementary cementitious material before Rio de Janeiro: ABNT; 2005.
and after modification by rapid air cooling: a comparative 31. ABNT: Associação Brasileira de Normas Técnicas. NBR
study of influence on the properties of blended cement paste. 15630 Argamassa para assentamento e revestimento de paredes
Constr Build Mater. 2022;314(Pt A):125434. e tetos - determinação do módulo de elasticidade dinâmico
12. Shi C. Steel slag: its production, processing, characteristics, and através da propagação de onda ultra-sônica. Rio de Janeiro:
cementitious properties. J Mater Civ Eng. 2004;16(3):230-6. ABNT; 2008.
13. Fang K, Wang D, Zhao J, Zhang M. Utilization of ladle furnace 32. ABNT: Associação Brasileira de Normas Técnicas. NBR 13280:
slag as cement partial replacement: influences on the hydration argamassa para assentamento e revestimento de paredes e
and hardening properties of cement. Constr Build Mater. tetos - determinação da densidade de massa aparente no estado
2021;299:124265. endurecido. Rio de Janeiro: ABNT; 2005.
14. Luo Y, Klima KM, Brouwers HJH, Yu Q. Effects of ladle slag 33. ABNT: Associação Brasileira de Normas Técnicas. NBR
on Class F fly ash geopolymer: reaction mechanism and high 15259: argamassa para assentamento e revestimento de paredes
temperature behavior. Cement Concr Compos. 2022;129:104468. e tetos - determinação da absorção de água por capilaridade e
15. Adesanya E, Ezu A, Nguyen H, Rößler C, Sreenivasan H, do coeficiente de capilaridade. Rio de Janeiro: ABNT; 2005.
Ohenoja K, et al. Hydration of blended ladle slag and calcium 34. ABNT: Associação Brasileira de Normas Técnicas. NBR
aluminate cement. J Build Eng. 2023;66:105855. 13281: argamassa para assentamento e revestimento de paredes
16. Sultana I, Islam GMS. Performance of ladle furnace slag in e tetos - requisitos. Rio de Janeiro: ABNT; 2005.
mortar under standard and accelerated curing. Adv Civ Eng. 35. Araos Henríquez P, Aponte D, Ibáñez-Insa J, Barra Bizinotto
2022;2022(Spe):e7824084. M. Ladle furnace slag as a partial replacement of Portland
17. Wang J, Xiao J, Zhang Z, Han K, Hu X, Jiang F. Action cement. Constr Build Mater. 2021;289:123106.
mechanism of rice husk ash and the effect on main performances 36. Herrero T, Vegas IJ, Santamaría A, San-José JT, Skaf M. Effect
of cement-based materials: A review. Constr Build Mater. of high-alumina ladle furnace slag as cement substitution in
2021;288:123068. masonry mortars. Constr Build Mater. 2016;123:404-13.
 Combined Use of Ladle Furnace Slag and Rice Husk Ash as a Supplementary Cementitious Material 7

37. Adesanya E, Sreenivasan H, Kantola AM, Telkki V-V, Ohenoja K, 39. Haddad LDO, Neves RR, Oliveira PV, Santos WJ, Carvalho AN Jr,
Kinnunen P, et al. Ladle slag cement – Characterization of Santos WJ. Influence of particle shape and size distribution on
hydration and conversion. Constr Build Mater. 2018;193:128-34. coating mortar properties. J Mater Res Technol. 2020;9(4):9299-314.
38. Cincotto MA. Argamassas de revestimento: características, 40. Marques AI, Morais J, Morais P, Veiga MR, Santos C,
propriedades e métodos de ensaio. São Paulo: Instituto de Candeias P, et al. Modulus of elasticity of mortars: static and
Pesquisas Tecnológicas; 1995. (Boletim técnico). dynamic analyses. Constr Build Mater. 2020;232:117216.