Developments in the Built Environment 21 (2025) 100592

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Developments in the Built Environment

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Mortars with enhanced chemical resistance: Effects of sulphuric

acid exposure
Bruna S. Santos a,b, Wesley B.S. Machini a,b, Gina Matias a,b, Nelson F.S.T. Moreira c ,
Paulo M.M. Portugal c, Isabel Torres a,d , António Tadeu a,d, João A.S. Almeida a,b,*
a
Itecons, Coimbra, Portugal
b
University of Coimbra, CERIS, Coimbra, Portugal
c
Lusomapei S.A., Business Parque Tejo XXI, Castanheira do Ribatejo, Portugal
d
University of Coimbra, CERIS, Department of Civil Engineering, Coimbra, Portugal

A R T I C L E I N F O A B S T R A C T

Keywords: In this work, a comparative study on the mechanical, microstructural and chemical properties of mortars with
Acid resistant mortar enhanced chemical resistance was performed to investigate the effects of sulphuric acid attack. For this, speci­
Accelerated ageing test mens of ordinary and improved formulations were immersed in water and sulphuric acid at pH 0.0 for 14 days,
Durability
assessing the relative residual compressive strength and corrosion depth. The sulphuric acid attack resulted in
Sulphuric acid attack
Chemical resistance
pronounced changes in the mechanical properties and severe corrosion for the ordinary mortar. In contrast, the
Acid corrosion improved mortars exhibited moderate to high acid resistance (relative residual strengths up to 94.6% and
minimal corrosion depth of 0.5 mm). A significant quality gain of up to 49% and 180% was also observed when
comparing the improved mortars with a reference mortar resistant to acid in terms of relative residual
compressive strength and corrosion depth, respectively. The effect of sulphuric acid attack on the microstructure
and chemical composition of mortars was further evaluated by mercury intrusion porosimetry (MIP), attenuated
total reflection-Fourier transform infrared spectroscopy (ATR-FTIR), and scanning electron microscopy with
energy dispersive X-ray (SEM-EDX).

1. Introduction deteriorate is variable and can be influenced by various factors beyond

the cementitious material composition (e.g., wastewater properties,
Wastewater facilities are essential for urban areas, ensuring the environmental conditions, nature of microorganisms, and hydraulic
transportation and treatment of wastewater. However, these systems dynamics). Corrosion rates above 10 mm/year have been reported for
face early degradation due to corrosion of the materials caused by the cementitious systems under severe operating conditions (Wu et al.,
transported fluids, which are responsible for creating a chemically 2020; Pramanik et al., 2024).
aggressive environment. Consequently, the lifetime of concrete struc­ The corrosion mechanisms that occur in sewer facilities are very
tures can be significantly reduced, leading to high rehabilitating costs complex. Generically, favourable conditions promote the growth of
(Wu et al., 2020). For example, wastewater system repairs in Germany microorganisms on the concrete surface, which are responsible for
and the United Kingdom cost up to 450 million euros and 85 million producing hydrogen sulphide (H2S) and sulphuric acid (H2SO4). The
pounds per year, respectively (Grengg et al., 2018). Additionally, po­ subsequent reactions of H2SO4 with the concrete components are seen as
tential failures may cause severe environmental damage and pose public the leading cause of deterioration of sewer systems (De Belie et al., 2004;
health risks. Noeiaghaei et al., 2017). Calcium hydroxide (CH) inside concrete reacts
Cementitious materials are extensively used in wastewater treatment with sulphuric acid to form gypsum, which induces volume expansion,
plants because of their low cost, high mechanical strength, and water­ causing cracks and tensile stresses in the concrete (Monteny et al., 2000;
tight properties compared to other materials. However, the corrosive Rendell and Jauberthie, 1999). The calcium aluminate phases inside the
environment inside the hydraulic elements poses a durability challenge cement matrix can also react with gypsum, producing ettringite, which
(Kashaija et al., 2024). The rate at which cementitious materials induces higher expansion and causes more cracking inside the concrete

* Corresponding author. Rua Pedro Hispano, 3030-289, Coimbra, Portugal.

E-mail address: [email protected] (J.A.S. Almeida).

https://doi.org/10.1016/j.dibe.2024.100592
Received 10 April 2024; Received in revised form 9 November 2024; Accepted 6 December 2024
Available online 9 December 2024
2666-1659/© 2024 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
B.S. Santos et al. Developments in the Built Environment 21 (2025) 100592

(Jeon et al., 2020). Finally, sulphuric acid can also decompose calcium to quickly evaluate and compare the performance of mortars used in the
silicate hydrate through decalcification, thus causing instability of the construction and rehabilitation of sewage infrastructure elements
cementitious matrix (De Belie et al., 2004; Noeiaghaei et al., 2017; (Wang et al., 2020). Although several studies have reported the simu­
O’Connell et al., 2010; Huber et al., 2016). lation of real conditions (Sand and Bock, 1984; Vincke et al., 1999) and
Concerning the minimisation of the effects of exposure to biochem­ long-term in situ tests (Herisson et al., 2017), these approaches have the
ical attacks, the development of new mortars with improved acid disadvantages of being time-consuming and requiring complex appa­
resistance has attracted significant attention. Particular types of cement, ratus. In turn, chemical tests continue to be the most widely used,
such as calcium aluminate (CAC) and blast furnace slag (BFSC), have allowing a simplified simulation of the entire life of mortars in a short
been shown to perform better than ordinary Portland cement (OPC). The period. Samples are typically kept in a concentrated solution of sul­
better performance of concretes made of CAC has been linked to the phuric acid, followed by studies of loss of mass and/or variations in
higher capacity of acid neutralisation, the formation of a gel phase stable compressive strength (Aliques-Granero et al., 2017; Bernal et al., 2012;
above pH 4, and the low porosity of the microstructure. The higher Vafaei et al., 2019; Marangu, 2021). These tests may differ regarding the
aluminium content may also contribute to anti-bacteriostatic properties specimen geometry, frequency of solution renewal, stirring conditions,
(Grengg et al., 2018). The enhanced performance of CAC concrete was drying cycles, and brushing (De Belie et al., 2002, 2004; De Muynck
also confirmed in natural field conditions over 24 months (Khan et al., et al., 2009; Irico et al., 2020). Different strategies have also been used to
2019). BFSC, a Portland cement enriched with blast furnace slag and accelerate the ageing process, such as increasing the acid concentration,
calcium sulphate, has also been shown to perform better than OPC, but the surface area/volume ratio, the period of immersion, and the tem­
not as good as CAC (Aboulela et al., 2021). perature of the solution (Monteny et al., 2000, 2003; Gu et al., 2018;
The nature of aggregates can also affect the performance of chemical Koenig and Dehn, 2016). The parameters used to evaluate the extent of
resistance of mortars. For example, adding silicon carbide as a filler has corrosion also varied. These include, for example, compressive strength,
been shown to affect mortars’ acid sulphuric resistance positively. This leachate behaviour, physical appearance, weight loss, mineralogic and
was attributed to an improvement in the microstructure. It was also microstructural characterisation, corrosion depth, surface pH, and
demonstrated that silicon carbide does not react chemically with cement porosity (Pramanik et al., 2024; Chaudhari et al., 2022). Moreover, some
hydration products (Jeon et al., 2020). Replacing non-reactive silica-­ authors have raised questions about the robustness of these methods in
based aggregates with reactive calcium aluminate-based aggregates has describing the behaviour of materials of different natures. For instance,
been shown to improve neutralisation capacity too (Aboulela et al., visual appearance is too subjective and may vary depending on the
2021). Moreover, concretes containing alternative aggregates made of mechanism of acid attack. The consumption of acid is also not always
polyethylene terephthalate (PET) have also shown less susceptibility to consistent with the disturbance caused by the test in terms of
weight loss and compressive load reduction when subjected to sulphuric compressive strength. Additionally, the depth of pH neutralisation is
acid (Janfeshan Araghi et al., 2015). highly dependent on the initial alkalinity of the specimens (Gu et al.,
More recently, geopolymer concretes have attracted interest in the 2019).
development of materials with improved resistance to biodeterioration To respond to the urgent need for a standard that allows evaluation
due to chemical stability at low pH, low permeability, sulphate resis­ of the chemical resistance of mortars, the German Committee of Stan­
tance, and cation exchange properties (Grengg et al., 2018; Baščarević dards provided the standard DIN 19573:2016–03 (German Institute for
et al., 2014). However, more research is necessary to characterise their Standardization, 2016). This standard establishes four corrosion resis­
long-term effectiveness and limitations comprehensively. Nano­ tance classes by exposure to sulphuric acid, namely XWW4, for corrosion
materials, such as nanoparticles of titanium and silver, have also been by biogenic sulphuric acid, and XWW1-XWW3, which correspond to
investigated to prevent biological attack. In this case, the significant weak to strong corrosion by sulphuric acid. According to this standard,
increase in surface area-to-volume ratio is expected to result in the XWW4 resistance class is assessed by immersing the specimens in a
improved antimicrobial properties compared to their bulk forms. sulphuric acid solution at pH 0.0 for 14 days and pH 1.0 for 70 days,
Similar antimicrobial properties have been investigated using zinc-, while the XWW1-XWW3 resistance classes are assessed by immersion in
copper- or silver-functionalised zeolites (Noeiaghaei et al., 2017). sulphuric acid at pH 4.0 for 4000 h. This standard currently arouses
In addition to cement chemistry, several supplementary cementi­ increased interest in the academic community with different materials,
tious materials, admixtures, fillers and polymers may play an important such as geopolymer mortar, grouting material, sprayed mixture, and
role in controlling microbial-induced concrete corrosion. Fly ash is silicate-based repair mortar, being tested (Bertron et al., 2025; Sturm
probably the most studied supplementary cementitious material due to et al., 2018; Figala et al., 2021; Figala et al., 2022; Wang et al., 2022).
its relevant pozzolanic nature (Aydın et al., 2007; Figala et al., 2023). Although only available in German, the importance of this standard
Some fillers and mineral admixtures, like sand powder and silica fume, in the current industrial context to support the development of new
have also been studied to lower the corrosion effect of acids (Wanna mortars with improved performance is undeniable. So, in this work, the
et al., 2020; Goyal et al., 2009; Monteny et al., 2003; García-Vera et al., authors aimed to investigate the effects of sulphuric acid attack on
2019). The incorporation of specific polymer technologies (e.g. mortars with enhanced chemical resistance when subjected to the im­
styrene-acrylic ester polymer and vinyl copolymer) into cement mate­ mersion test described in DIN 19573:2016–03 (German Institute for
rials may also contribute to enhancing their chemical resistance Standardization, 2016). For this, three mortars with presumable high
(Monteny et al., 2003). chemical resistance and two control samples were tested by assessing
Alternatively, water-repellent coatings (e.g., silane and its de­ the relative residual compressive strength and the effective depth of
rivatives) and polymer-based sealers such as polyurethane, acrylic and corrosion. As described below, in the materials and methods section,
epoxy resins have been used to prevent the access of aggressive agents, high chemical-resistant mortars were produced by Mapei, using
protecting concrete from acid degradation (Wang et al., 2012; Almu­ sulphate-resistant binders alone and combined with Portland cement.
sallam et al., 2003). These may synergistically impact relevant degra­ The effects of the sulphuric acid attack on the mortar specimens were
dation processes in highly acidic environments, such as diffusion of H2S, discussed based on the results of mercury intrusion porosimetry (MIP),
dissolution rates, acid neutralisation capacity, and biofilm adhesion, attenuated total reflection-Fourier transform infrared spectroscopy
contributing to enhanced system durability. However, surface treat­ (ATR-FTIR) and scanning electron microscopy with energy dispersive
ments may pose several drawbacks, such as poor adhesion, uneven X-ray (SEM-EDX), as well as on the original oxide composition of
coating, and high application costs (García-Vera et al., 2019). specimens.
In addition to the enormous challenge of developing new mortars
with high chemical resistance, there is a lack of standardised procedures

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B.S. Santos et al. Developments in the Built Environment 21 (2025) 100592

2. Materials and methods for Standardization, 2016). The prisms were prepared as described in
Section 2.1. After 28 days of curing time, 5 half-prisms (40 mm × 40
A reference mortar (RM), an ordinary mortar (OM), and three mor­ mm × 80 mm) were stored in water and 5 half-prisms were immersed in
tars with enhanced chemical resistance (NM1, NM2 and NM3) designed 4 L of sulphuric acid solution pH 0.0, for 14 days at (21 ± 2) ◦ C keeping
by Mapei were evaluated. constant the surface:volume ratio at 20 m− 1. The pH value of the acid
The following subsections provide information about the test sam­ solution was kept constant at 0.00 < pH < 0.03 by daily titration. The
ples, including the preparation and chemical characterisation proced­ specimens were immersed at least 5 mm below the surface under grates
ures. A detailed description of the sulphuric acid immersion test is also and the solution was kept under constant stirring to ensure homoge­
given, including the procedure followed to determine the relative re­ neous exposure to the acid, Fig. 1. The test specimens were not moved,
sidual compressive strength and corrosion depth. This section also pre­ and the corrosion layer was not removed during the entire immersion
sents the instrumental methods further used to evaluate the impact of period.
sulphuric acid attack on test samples’ microstructure and chemical At the end of the immersion period, the specimens were removed
composition. from the solution and brushed with a soft brush, under running water, to
remove loose elements. The prisms were then cut to the height of 40 mm
2.1. Sample preparation from the middle of the corroded mortar test specimens and visually
inspected. A corresponding operation was carried out on the mortar
The RM was prepared according to DIN 19573:2016–03 (German specimens stored in water. After 2 days under the conditions previously
Institute for Standardization, 2016), by mixing a sulphate-resistant described, the compressive strength of the mortar specimens was tested
cement (CEM I 42.5 R-SR 0/NA) and a CEN standardized sand, using a according to EN 196–1:2016 (European Committee for Standardization,
cement/sand ratio of 1/3 and a water/cement ratio of 0.45. The OM is a 2016). In this case, the breaking loads were determined in specimens
commercially available two-component, highly sulphate-resistant prepared from the centre of the corroded mortar specimens, across the
cement-based mortar containing selected fine aggregates (<0.5 mm), cut surfaces, which were ground to be plane-parallel.
special additives and synthetic polymers in water dispersion (as The resistance of the mortars to the sulphuric acid attack was eval­
described by the manufacturer). In the formulation process of NM1, uated in terms of the compressive strength, relative residual compressive
NM2 and NM3, sulphate-resistant binders (e.g., cement free of trical­ strength and the effective depth of corrosion. The compressive strength
cium aluminate (C3A) and aluminous cement) were tested either alone of the mortar after immersion in acid was calculated by relating the
or in combination with Portland cement. Different types of aggregates fracture load of each corroded specimen with its initial cross-section
and additives were also used in the formulation process. For industrial (d0). The relative residual compressive strength was obtained by the
reasons, the composition of these mortars is quantitatively described in ratio between the residual compressive strength of the mortar after
terms of elemental analysis (see Section 3.1) as obtained by X-ray immersion in acid and the residual compressive strength of the mortar
fluorescence (XRF). after immersion in water. The compressive strength of the specimens
Six prisms of 40 mm × 40 mm × 160 mm were prepared according to after acid exposure indicates to what extent the structure of the material
EN 196–1:2016 (European Committee for Standardization, 2016), using was affected, which enables the effective depth of corrosion to be
a standard mixing. Water was gradually added to the dry mix previously determined. The effective depth of corrosion was determined by the
blended, mixing until it reached a homogeneous consistency. The initial cross-section of a test sample minus the corrosion layer of thick­
moulds were filled in two layers, each compacted using a standard ness, which gives the dimensions of the core unaffected in terms of
tamper. The top surface was then levelled using a straightedge to remove compressive strength, using as a benchmark the strength of a sample of
excess mortar. Curing was done in a climate chamber at 20 ◦ C and 90% the same age stored in water. Thus, the depth of corrosion (Xf,D) based
RH for 24 h. After that, the specimens were removed from the mould and on the residual compressive strength ratio was calculated according to
immersed in tap water at 20 ◦ C for a further 27 days. At the age of 14 equation (1).
days, the specimens were cut in half (40 mm × 40 mm × 80 mm) for [ (√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅)] [ √̅̅̅̅̅̅̅̅̅̅̅̅̅̅ ]
immersion in water and sulphuric acid. FD,acid FD,acid
Xf,D = 0.5 × d0 − × d0 = 0.5 × d0 1 − (1)
At the end of the immersion period, all the specimens were sawed FD,water FD,water
longitudinally, with 40 mm sections, and compressive tests were carried
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
out according to DIN 19573:2016–03 (German Institute for Standardi­ where: d0 = (a × b), a and b = edge lengths of the test cross-sections of
zation, 2016), as described in subsection 2.4. The remains of the spec­ the water-immersed specimens, FD,acid = Fracture loads of the acid
imens were reserved for chemical composition, and microstructural and
chemical analysis.

2.2. Chemical composition

Representative portions of the mortar specimens were collected,

ground in a ball mill and passed through a 90 μm sieve. The samples of
powdered mortars were mixed with a binder (Licowax®) and com­
pressed at 20 tons for 2 min to obtain pressed pellets. X-ray fluorescence
(XRF) analyses were performed using a Rigaku Supermini 200 sequen­
tial spectrometer with Pd X-ray tube and X-ray generator operating
under 50 kV and 4.00 mA. Elemental mass percentages were calculated
with the ZSX Primus (Rigaku) software package. Loss of ignition (LOI)
was measured by heating 5.0 g of oven-dried samples to 975 ◦ C in
porcelain crucibles for 2 h.
Fig. 1. Schematic representation of the sulphuric acid immersion apparatus:
2.3. Sulphuric acid resistance testing (1) concentrated sulphuric acid solution; (2) automatic titrator; (3) acid
dispenser; (4) pH electrode; (5) temperature probe; (6) magnetic stirrer; (7)
The acid resistance of the mortars was determined according to the magnets; (8) support grid; (9) test specimens; (10) sulphuric acid solution with
German standard DIN 19573:2016–03 (Appendix A) (German Institute controlled pH.

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B.S. Santos et al. Developments in the Built Environment 21 (2025) 100592

immersion prisms (kN), and FD,water = Fracture loads of the water im­ 3. Results
mersion prisms (kN).
According to DIN 19573:2016–03 (German Institute for Standardi­ As previously introduced, three mortars (NM1, NM2 and NM3)
zation, 2016), the mortar should comply with a relative residual designed to resist to early degradation when exposed to high aggressive
compressive strength higher than 55% and an Xf,D lower than 5.2 mm for chemical environments were submitted to a sulphuric acid attack test to
the pH 0.0 test, in order to obtain XWW4 classification (corrosion investigate the effects on the mechanical, microstructural and chemical
resistance to sulphuric acid). properties. A reference mortar (RM), prepared as described in DIN
19573:2016–03 (German Institute for Standardization, 2016), and an
ordinary mortar (OM), which is commercially available, were also
2.4. Compressive strength test
included in this study for comparison purposes.

After storage at (21 ± 2) ◦ C and (60 ± 10) % RH for 2 days, the

compressive strength of the mortar specimens was tested according to 3.1. Chemical composition
EN 196–1:2016 (European Committee for Standardization, 2016).
However, the load was applied to the sawed faces of the specimens, The chemical oxide composition of the different mortars before the
parallel to the longitudinal axis of the original prisms, as specified in the sulphuric acid attack determined by XRF is detailed in Table 1. These
DIN 19573:2016–03 standard (German Institute for Standardization, compositions correspond to a global chemical profile, including binders,
2016). This procedure allows the test specimens to have parallel faces aggregates and other components.
and the same length in the direction of the longitudinal axis of the The XRF results for the RM show a high content of silica and lime,
original prisms, whether they have been immersed in water (reference and a moderate content of Fe2O3 and Al2O3. Conversely, the XRF results
condition) or acid (aging condition). for the OM sample, a non-specific mortar for acidic environments, show
a high content of lime followed by silica, and a moderate content of
2.5. Microstructural and chemical analysis Al2O3 followed by Fe2O3. Significant differences in chemical composi­
tion were introduced for the improved mortars. The XRF results for the
2.5.1. Mercury intrusion porosimetry NM1 show a high content of lime and moisture, carbon, organic matter,
The mortars’ porosimetry was analysed according to the procedure and volatile compounds represented by the loss of ignition (LOI), and a
described in the standard ISO 15901–1:2016 (International Organiza­ moderate content of silica and MgO. The XRF results for the NM2 also
tion for Standardization, 2016). For this, a mercury Porosimeter Auto­ show a high content of lime and a high level of LOI, but with a high
pore IV 9500, from Micrometrics, able to reach 60000 psi, was used. The content of Al2O3 and Fe2O3. Finally, for the NM3 mortar, the XRF results
behaviour of the samples submitted to intrusion and extrusion of mer­ show a high content of silica, Al2O3 and Fe2O3, and the lowest content of
cury, with varying pressure, provides curves of pores diameter (μm) vs. lime and level of LOI.
differential intrusion (mL/g). From these data, the following informa­ The chemical composition profile of the mortars studied is shown in
tion on the porous structure can be extracted: total pore volume, VP Fig. 2 to highlight their differences.
(cm3/g), bulk density, B (g/mL), apparent skeletal density, DS (g/mL), As can also be seen, the RM and NM3 mortars present the highest
average pore diameter, dP (μm), presented as a relation between the amount of (SiO2+Al2O3) and the lowest amount of CaO. In contrast, OM,
total specific intrusion volume (V) and total specific pore area (A), 4V/A, NM1 and NM2 mortars are significantly richer in CaO. Finally, among all
and the porosity, P (%). Note that bulk density corresponds to the the mortars, the NM2 has the most balanced amount of (SiO2+Al2O3)
apparent density of the specimen, including the volume of all pores and CaO. While CaO is essential for initial strength development, an
(open and closed), while the estimated apparent skeletal density corre­ excess of it can lead to the formation of calcium hydroxide (Ca(OH)2).
sponds to the density of the specimen including closed pores, but This form of calcium is highly soluble and reactive in an acidic envi­
excluding open pores. ronment, which may result in the early deterioration of mortars. Addi­
tionally, when exposed to acids, available CaO can result in the
2.5.2. Attenuated total reflection-fourier transform infrared spectroscopy formation of expansive by-products, like gypsum and ettringite, thereby
Attenuated total reflection-Fourier transform infrared spectroscopy increasing the propensity for the occurrence of microcracks and
(ATR-FTIR) analyses were performed using a PerkinElmer Frontier reducing the durability of mortars. In contrast, a balance between
spectrometer equipped with a UATR Diamond/ZnSe with 3 Reflection SiO2+Al2O3 and CaO may contribute to the formation of calcium silicate
Top-Plate. For each spectrum, eight scans from 4000 cm− 1 to 600 cm− 1
were recorded using Spectrum software version 10.4.2. Spectra were Table 1
recorded in duplicate, of which one was used for calibration and the Chemical oxide composition of the studied mortars (in weight %) before the
sulphuric acid attack determined by XRF: RM – Reference mortar according to
other for test set validation. The powder samples analysed by ATR-FTIR
DIN 19573:2016–03 (German Institute for Standardization, 2016); OM – Ordi­
were obtained from representative portions of the mortar specimens,
nary mortar commercially available; NM1, NM2 and NM3 – Improved mortars 1,
which were ground in a ball mill and passed through a 90 μm sieve.
2 and 3, respectively.
Parameter RM OM NM1 NM2 NM3
2.5.3. Scanning electron microscopy and energy dispersive X-ray
spectroscopy Na2O – 0.14 – – 0.57
Scanning electron microscopy was performed using a Phenom Pro MgO 0.51 1.00 2.54 1.49 2.29
Al2O3 2.38 6.57 1.89 9.78 23.80
scanning electron microscope. The mortar surface samples mounted on SiO2 49.60 24.60 6.29 0.62 31.80
stubs were imaged without a coating in low vacuum mode using an P2O5 0.10 0.11 0.05 0.04 0.09
accelerating voltage of 5 kV and a working distance of 2.5 mm. The SO3 1.41 1.53 0.45 0.04 0.07
elemental analyses were also performed using a Thermionic CeB6 source Cl 0.02 0.01 0.01 – 0.02
K2O 0.39 0.44 0.18 0.08 1.04
and a high sensitivity multi-mode backscatter electron (BSE) detector at
CaO 33.60 44.40 48.50 43.20 25.60
15 kV EHT (primary-beam energy) coupled to the Phenom Pro scanning TiO2 0.19 0.95 0.21 0.49 1.17
electron microscope. At least 2 different points were analysed for MnO 0.07 0.09 0.05 0.04 0.11
elemental composition for each mortar studied. The samples analysed by Fe2O3 3.62 2.66 0.29 4.33 10.70
SEM-EDX were taken from small fragments carefully removed from the SrO 0.10 0.08 0.04 0.02 0.06
LOI 8.00 17.30 39.50 39.80 2.40
mortar specimens’ surfaces.

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B.S. Santos et al. Developments in the Built Environment 21 (2025) 100592

surface due to slight corrosion, and no significant changes are observed

for the cross-section.
Finally, for the NM3, a significant change in the visual appearance
and the formation of a brown layer on the surface of the specimen was
recorded, which remained around the prism during the sulphuric acid
immersion. This change was not observed for the remaining mortars
since the formed corrosion layers detached themselves naturally from
the specimens, and were deposited at the bottom of the boxes. After
removing the thin layer formed on the NM3 surface, the changes to the
specimens due to corrosion caused by the sulphuric acid attack were
clarified. Despite the significant changes in the appearance of the
specimen surface, only slight changes in the appearance of the cross-
section are observed.
In brief, it was found that for all mortars, including those with
greater changes, there was no visible effect on the inner part of the
specimens caused by the sulphuric acid attack. The statements relating
to the corrosion and morphological changes of the specimens will be
confirmed with the compressive strength and microstructural analyses
presented in this paper.
Fig. 2. Chemical oxide composition of the studied mortars (in weight %) before
the sulphuric acid attack determined by XRF: RM – Reference mortar according 3.3. Compressive strength and corrosion depth
to DIN 19573:2016–03 (German Institute for Standardization, 2016); OM –
Ordinary mortar commercially available; NM1, NM2 and NM3 – Improved After 28 days of curing time, 14 days of immersion in water or sul­
mortars 1, 2 and 3, respectively. phuric acid, and 2 days stored at (21 ± 2) ◦ C and (60 ± 10) % RH, the
compressive strength of the specimens was determined, Fig. 4. Accord­
hydrate (C-S-H), calcium aluminate hydrate (C-A-H), and calcium ing to the results for the mortars subjected to immersion in water, the
aluminosilicate hydrate (C-A-S-H) phases. These phases are more stable NM2 showed the highest compressive strength, while the remaining
and, consequently, less prone to dissolve in acidic conditions (Pramanik mortars had compressive strength values within the same order of
et al., 2024). magnitude. For the mortars subjected to sulphuric acid immersion, NM2
recorded the highest compressive strength, followed by NM3, both with
3.2. Visual inspection higher compressive strength than RM. In contrast, low compressive
strengths, even lower than RM, were obtained for OM and NM2 after
After immersion in water and in sulphuric acid, the physical immersion in sulphuric acid. Regarding the difference in compressive
assessment of the specimens was performed by visual inspection. The strength after immersion in water and acid, NM3 showed the smallest
visual inspection involved the assessment of cracking, crazing, colour difference. In comparison, OM showed the largest difference, as ex­
changes and formation of reaction products on the surface of specimens pected, since this mortar is not supposed to be used for this purpose.
stored in water, in sulphuric acid, and after brushing after being in Note that the relatively large error bars are likely due to the geometry of
sulphuric acid. In addition, the cross-sections of the specimens were the test specimens and the specificities of the mechanical test. According
analysed focusing on the external dimension and core changes. Fig. 3 to DIN 19573:2016–03 (German Institute for Standardization, 2016),
shows the visual appearance of the mortar specimens after 14 days of cubic-like specimens of 40 mm × ≤ 40 mm × ≤ 40 mm (degraded by
immersion in water and sulphuric acid. acid attack) are obtained by cutting the original specimens of 160 mm ×
For the RM, it can be seen that the specimens suffered a slight 40 mm × 40 mm after the immersion test. Additionally, the load was
reduction of the initial dimension, and a white layer was formed on the applied to the sawed faces of the specimens parallel to the longitudinal
surface, which was removed after brushing and showed that, despite the axis of the original prisms.
moderate corrosion, the inner part of RM specimen appeared un­ Note that although the compressive behaviour of each mortar was
changed. The cross-section of the specimens immersed in sulphuric acid assessed using half-prisms obtained from the same specimens after im­
clearly shows the difference in dimensions compared with the specimens mersion in water and sulphuric acid, compressive results cannot be
immersed in water, confirming the attack of sulphuric acid on the directly compared due to the irregular geometry of the acid-corrode
mortar. specimens. Additionally, compressive results after acid attack of
A drastic change in the visual appearance of the OM specimens was different mortars cannot be directly compared among them because of
observed after immersion in acid compared to water. In addition to the differences in the initial strength (specimens not subjected to acid
significant reduction in the initial dimension, a thick and non-uniform attack). For these reasons, compressive strengths were calculated
white layer can be seen on the surface of the specimen, which simi­ considering the initial dimensions of the test specimens (the same for all
larly, after removal, revealed severe corrosion of the specimens. Com­ test specimens), and the results were analysed in terms of relative re­
parison of the visual appearance of the cross-section of the test sidual compressive strength, which directly relates to the extent of
specimens clarifies this phenomenon. material structure affected and corrosion depth.
For the improved mortars, NM1 specimens revealed a significant The relative residual strength and the effective depth of corrosion of
change in the visual appearance after immersion in sulphuric acid the mortars were calculated as described above, and shown in Table 2, to
compared with water, which can be seen in the irregular decrease in the assess the requirements to obtain the XWW4 classification according to
initial dimension, as well as the formation of a thick white layer on its DIN 19573:2016–03 (German Institute for Standardization, 2016).
surface. The visual appearance of the cross-section corroborates the In the case of the RM, despite all the corrosion observed in the visual
severe and non-uniform corrosion suffered by the specimens due to the inspection, the results were expected to comply with the necessary re­
acid attack. quirements, which proved to be the case since a relative residual
For the NM2, a small change in the visual appearance of the spec­ strength of 63.5% and effective depth of corrosion of 4.1 mm were
imen, as well as the formation of a thin white layer on its surface was obtained.
detected. After brushing, it is still possible to see the change in the Contrastingly, the results for the OM suggest that this mortar does

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B.S. Santos et al. Developments in the Built Environment 21 (2025) 100592

Fig. 3. Photographic record of the test specimens (RM – Reference mortar according to DIN 19573:2016–03 (German Institute for Standardization, 2016); OM –
Ordinary mortar commercially available; NM1, NM2 and NM3 – Improved mortars 1, 2 and 3, respectively): (a) changes in the external dimension after immersion in
water, after immersion in sulphuric acid, and after immersion in sulphuric acid and brushed (from left to right); (b) cross-sections after immersion in water (top) and
after immersion in sulphuric acid and brushed (bottom).

not comply with the requirements since a relative residual strength of For NM1, in which drastic changes in the appearance and dimensions
33.8% and effective depth of corrosion of 8.4 mm were obtained, of the specimens were observed, a relative residual strength of 45.4%
corroborating the severe corrosion observed in the visual inspection. and effective depth of corrosion of 6.5 mm were obtained, suggesting
Regarding the improved mortars, each one behaved differently, as non-compliance with the requirements.
noted in the visual inspection and confirmed with the relative residual In contrast, both NM2 and NM3 comply with the requirements of
compressive strength and corrosion depth calculations. DIN 19573:2016-03 (German Institute for Standardization, 2016) to

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B.S. Santos et al. Developments in the Built Environment 21 (2025) 100592

Table 3
Relative residual compressive strength in terms of percentual variation of
the mortars under study (NM1, NM2 and NM3) against the reference
mortar (RM) produced according to DIN 19573:2016–03 (German Insti­
tute for Standardization, 2016) and the ordinary mortar commercially
available (OM).
RM OM

NM1 − 29% 34%

NM2 25% 135%
NM3 49% 180%

Table 4
Corrosion depth in terms of percentual variation of the mortars under
study (NM1, NM2 and NM3) against the reference mortar (RM) pro­
duced according to DIN 19573:2016–03 (German Institute for Stan­
dardization, 2016) and the ordinary mortar commercially available
(OM).
RM OM

NM1 − 59% 23%

Fig. 4. Compressive strength of the mortar specimens after immersion in water
NM2 46% 74%
(blue columns) and in sulphuric acid (red columns): RM – Reference mortar
NM3 88% 94%
according to DIN 19573:2016–03 (German Institute for Standardization, 2016);
OM – Ordinary mortar commercially available; NM1, NM2 and NM3 –
Improved mortars 1, 2 and 3, respectively. the improved mortars (NM1, NM2 and NM3) outperform the OM, with
an even more significant quality gain in terms of relative residual
compressive strength (up to 180%) and corrosion depth (94%).
Table 2
Relative residual compressive strength and corrosion depth results
Summary of relative residual strength and effective depth of corrosion of the
studied mortars: RM – Reference mortar according to DIN 19573:2016–03 can be directly compared to those obtained for test specimens exposed to
(German Institute for Standardization, 2016); OM – Ordinary mortar commer­ actual conditions over months or years (not the purpose of this work).
cially available; NM1, NM2 and NM3 – Improved mortars 1, 2 and 3, Actual corrosion rates above 10 mm/year have been reported for
respectively. cementitious systems under severe operating conditions (Wu et al.,
Mortar Relative DIN 19573 Corrosion DIN 19573
2020), as those expected under the conditions recreated by the test at pH
specimen residual requirement to depth requirement to 0.0 described in DIN 19573:2016–03.
compressive XXW4 class (mm) XXW4 class
strength (%) (>55%) (<5.2 mm)
4. Discussion
RM 63.5 Comply 4.1 Comply
OM 33.8 Not comply 8.4 Not comply The results presented in the previous section are now discussed in
NM1 45.4 Not comply 6.5 Not comply
NM2 79.3 Comply 2.2 Comply
terms of microstructural deterioration and chemical changes induced by
NM3 94.6 Comply 0.5 Comply the sulphuric acid attack based on the following analyses performed:
mercury intrusion porosimetry (MIP), attenuated total reflection-
Fourier transform infrared spectroscopy (ATR-FTIR), and scanning
obtain XWW4 classification. The NM2, which had the smallest visual electron microscopy (SEM) with energy dispersive X-ray (EDX). The
change, presented a relative residual strength of 79.3% and an effective results were also discussed in terms of each mortar’s original oxide
depth of corrosion of 2.2 mm. Finally, the best relative residual composition.
compressive strength and corrosion depth values, 94.6% and 0.5 mm,
respectively, were obtained for the last mortar developed, NM3, which
showed a significant apparent change. In fact, despite the visual 4.1. MIP analysis
changes, the layer formed on the surface of the specimens protected
their cores, ensuring high relative residual compressive strength and low As noted above, changes in the porous structure of the mortars
corrosion depth. submitted to acid attack were evaluated by means of mercury intrusion
Still, regarding the performance of the NM2 and NM3, in comparison porosimetry. The resulting distributions of pore sizes are presented in
with the RM, these mortars recorded greater relative residual Fig. 5.
compressive strength and less corrosion depth, suggesting a high resis­ Although, in general, no drastic changes are observed in the pore size
tance to sulphuric acid attack. distribution profiles after acid attack, more significant modifications can
A more in-depth analysis of the chemical resistance of the mortars be found for the mortars RM and NM3. Thus, for RM there is a clear
under study (NM1, NM2, and NM3) was pursued, assessing the relative reduction in the number of pores with diameters above 6.0 μm and an
residual compressive strength and corrosion depth in terms of percen­ increase in the number of pores with diameter between 0.02 μm and 0.3
tual variation against the reference mortar (RM) produced according to μm. Additionally, NM3 had a reduction in the number pores under 0.2
DIN 19573:2016–03 (German Institute for Standardization, 2016), and μm, which were converted into a peak between 0.3 μm and 0.7 μm after
the ordinary mortar commercially available (OM). The results obtained acid attack.
are presented in Tables 3 and 4. These profiles were further treated to extract information on the
Considering the RM, a significant quality gain is observed for NM2 characteristics of the porous structure. The results obtained for the
and NM3 regarding relative residual compressive strength (up to 49%) volume of pores, average pore diameter and porosity are presented in
and corrosion depth (88%). In contrast, for NM1, a quality loss of 29% Table 5. Estimated densities are also presented in Table 6. For each
and 59% was respectively observed for the same properties. In turn, all sample, the relative variation (%) between the specimens immersed in
water and acid was calculated.

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B.S. Santos et al. Developments in the Built Environment 21 (2025) 100592

Fig. 5. Pore size diameter (in log scale) of the studied mortars after immersion in water (blue lines) and in sulphuric acid (red lines) obtained by MIP: RM –
Reference mortar according to DIN 19573:2016–03 (German Institute for Standardization, 2016); OM – Ordinary mortar commercially available; NM1, NM2 and
NM3 – Improved mortars 1, 2 and 3, respectively.

Although relatively small variations were found between specimens compressive strength was further investigated. However, no clear rela­
immersed in water and acid both for the total volume of pores and tion emerges between these two properties, suggesting that, more than
porosity, more significant changes were recorded for the average pore the internal skeleton structure of the mortars or the initial mechanical
diameter, especially for the NM3 mortar. In this case, an increase was resistance, it is the chemical composition that plays the major role in the
also recorded for the total volume of pores and porosity. acid resistance.
Regarding the bulk and apparent densities, no significant changes
were observed after the acid attack. However, as expected, all samples
immersed in acid had lower values than samples immersed in water, 4.2. ATR-FTIR analysis
which can be attributed to the loss of material caused by the corrosion
process. The deterioration of the mortar specimens after sulphuric acid attack
A possible correlation between porosity and relative residual can be identified by ATR-FTIR through the detection of infrared peaks at
different wavenumbers formed as a result of symmetric and asymmetric

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B.S. Santos et al. Developments in the Built Environment 21 (2025) 100592

Table 5
Total pore volume (VP), average pore diameter (dP), porosity (P), and respective relative variation (Δ%) between the test specimens immersed in water and acid for the
studied mortars calculated based on MIP results: RM – Reference mortar according to DIN 19573:2016–03 (German Institute for Standardization, 2016); OM – Or­
dinary mortar commercially available; NM1, NM2 and NM3 – Improved mortars 1, 2 and 3, respectively.
Mortar Immersion conditions VP (cm3/g) ΔVP (%) dP (μm) ΔdP (%) P (%) ΔP (%)

RM H2O 0.055 − 3.3% 0.046 16.6% 12.3 − 5.1%

H2SO4 0.053 0.054 11.6

OM H2O 0.053 4.0% 0.031 − 23.0% 11.5 3.1%

H2SO4 0.055 0.024 11.8

NM1 H2O 0.081 2.7% 0.013 16.3% 16.7 1.2%

H2SO4 0.083 0.015 16.9

NM2 H2O 0.048 − 1.0% 0.046 − 6.5% 10.8 − 1.0%

H2SO4 0.048 0.043 10.7

NM3 H2O 0.080 13.4% 0.042 92.4% 16.5 10.4%

H2SO4 0.091 0.081 18.2

peaks, which can be attributed to the deterioration of the mortars due to

Table 6
the sulphuric acid attack, characterized by the formation of gypsum, as
Bulk density (B) at 0,0037 MPa, apparent (skeletal) density (DS), and respective
mentioned earlier. In this context, the ATR-FTIR spectra for the OM,
relative variation (Δ%) between the test specimens immersed in water and acid
NM1 and NM2 samples showed a new band at 1125 cm− 1, falling in the
for the studied mortars calculated based on MIP results: RM – Reference mortar
according to DIN 19573:2016–03 (German Institute for Standardization, 2016); range of 1100–1165 cm− 1, which corresponds to SO2− 4 vibration (v3) in
OM – Ordinary mortar commercially available; NM1, NM2 and NM3 – Improved sulphates (Ylmén et al., 2009; Yaseen et al., 2019). For these mortar
mortars 1, 2 and 3, respectively. samples, including the RM, other peaks related to the production of
gypsum were found at 1680 and 1620 cm− 1, which correspond to O–H
Mortar Immersion conditions B (g/mL) ΔB (%) DS (g/mL) ΔDS (%)
bending vibrations (v2) in hydrous form (Rosi et al., 2010; Lee and Lee,
RM H2O 2.219 − 1.8% 2.530 − 2.5%
2016), and at 670 cm− 1, which corresponds to SO2− 4 vibration (v4) in
H2SO4 2.180 2.467
sulphates (Jeon et al., 2020; Ramachandran and Beaudoin, 2001).
OM H2O 2.161 − 0.8% 2.441 − 0.4% Additionally, the appearance of doublet bands at 3530 and 3410 cm− 1
H2SO4 2.143 2.430
are probably associated with the formation of gypsum (Jeon et al., 2020;
NM1 H2O 2.057 − 1.5% 2.470 − 1.2% Ramachandran and Beaudoin, 2001; Ariffin et al., 2013). For the NM3
H2SO4 2.027 2.439
sample, the peaks observed for the non-attacked sample were the same
NM2 H2O 2.237 0.0% 2.508 − 0.1% as those observed for the attacked sample, suggesting the maintenance
H2SO4 2.237 2.506 of the mortar microstructure and chemical composition, which reflected
NM3 H2O 2.057 − 2.7% 2.463 − 0.6% the greater resistance to acid attack.
H2SO4 2.003 2.448

4.3. SEM-EDX analysis

stretching and bending due to the presence of carbonate (CO2− 3 ) and
sulphate (SO2− To analyse the microstructure of the mortar surface and better un­
4 ) groups, as well as the spectral variations of primary
phases relating to the non-attacked mortar specimens (Lo and Lee, derstand the effect of the sulphuric acid attack on the mortar surface
2002). The ATR-FTIR spectra obtained for the mortar samples after morphology, scanning electron microscopy (SEM) analysis was per­
immersion in water (blue lines) and after immersion in sulphuric acid formed. Accordingly, the photomicrographs captured from the SEM
(red lines) are shown in Fig. 6. analysis for samples of the surface of the mortar specimens after im­
The spectra for RM and OM samples, as well as for NM1 and NM2 mersion in water and after immersion in sulphuric acid are illustrated in
samples, after water immersion have a similar profile, resulting in a Fig. 7.
degree of similarity of 79% and 98%, respectively. As noted, the NM3 The deterioration of the mortars is usually found as a result of the
sample is the most different in appearance of all the mortar samples severe external damage, where the sulphuric acid attack creates a layer
studied. Therefore, the major bands for the mortar samples after im­ of gypsum on the mortar’s surface, as a visible white coating. This can be
mersion in water (Fig. 6, blue lines) were identified. The small peak at observed both by visual inspection as well as in SEM micrographs. In the
3645 cm− 1 is assigned to stretching vibrations from O–H bonds in cal­ SEM micrographs of the RM, OM and NM1 attacked specimens, signif­
cium hydroxide as portlandite (García Lodeiro et al., 2009). The struc­ icant changes in the microstructure as well as typical gypsum acicular
ture of molecular water in the system was characterized by the O–H forms were observed. In the SEM micrographs of the NM2 and NM3
stretching vibrations (v1 and v3), from 3400 to 3100 cm− 1, while the attacked specimens, changes in the microstructure were also observed.
H–O–H bending vibration (v2) of the adsorbed water was located at However, the typical gypsum acicular forms were less noticeable for the
1640 cm− 1 (Jeon et al., 2020; Ramachandran and Beaudoin, 2001; NM2 specimen, while for the NM3 specimen none were seen. These
Ylmén et al., 2009). The fundamental bands of calcite attributed to the results corroborate the main conclusions of the ATR-FTIR analysis.
C–O asymmetric stretching (v3), out-of-plane and in-plane bending (v2 Another important aspect revealed by SEM micrographs concerns the
and v4) vibrations were found at 1425, 875 and 713 cm− 1 (Jeon et al., surface morphology of the mortar specimens in terms of microcracks.
2020; Fernández-Carrasco et al., 2012), respectively. Finally, the band The SEM micrograph for the surface of the RM specimen after sulphuric
related to the asymmetric Si–O stretching vibration (v3) in SiO2− acid attack showed the presence of small microcracks compared to the
4 at 970
cm− 1, was observed due to the polymerization in C–S–H (Ylmén et al., non-attacked specimen. For the OM, which is not specialized for this
2009; Yaseen et al., 2019; Horgnies et al., 2013). purpose, and the mortar initially developed, NM1, large microcracks
The ATR-FTIR spectra for the mortar samples after immersion in were observed on the surface of the specimen. For the NM2 specimen,
sulphuric acid (Fig. 6, red lines) showed lower peak intensities than the the SEM micrograph revealed a significant change in the surface
spectra of the non-attacked samples and revealed the presence of new morphology and the presence of small microcracks compared to the non-
attacked specimen. Although there are microcracks, they are

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B.S. Santos et al. Developments in the Built Environment 21 (2025) 100592

Fig. 6. ATR-FTIR spectra of studied mortars after immersion in water (blue lines) and after immersion in sulphuric acid (red lines): RM – Reference mortar according
to DIN 19573:2016–03 (German Institute for Standardization, 2016); OM – Ordinary mortar commercially available; NM1, NM2 and NM3 – Improved mortars 1, 2
and 3, respectively.

significantly smaller than those seen on the surface of the previous Considering that previous studies have shown that mortars exposed
specimens. Finally, the SEM micrograph for the surface of the NM3 to acid attack may contain a higher concentration of sulphur than non-
specimen (Fig. 7) does not show a significant difference in morphology attacked mortars (García-Vera et al., 2018), energy-dispersive X-ray
from that before immersion, mainly with respect to the presence of spectroscopies (EDX) were carried out, Fig. 8.
microcracks. Before immersion in sulphuric acid, none of the mortars show
The development of products creates stresses that result in the in­ sulphur in the surface composition. In turn, after immersion in sulphuric
crease of microcracks on the surface of the specimens. Consequently, the acid, sulphur percentages ranging from 9% to 14% were observed for all
presence of microcracks, porosity, and a soft structure of gypsum result the samples except for NM3, which can be attributed to the formation of
in a profound degradation of the microstructure, which is associated gypsum on the surface of the mortar. A reduction in calcium content is
with a significant reduction in the strength of the specimens, as shown in also observed, with a more pronounced effect on the RM, OM, and NM1,
Fig. 7. These results thus confirm that NM3 is more resistant to sulphuric which is indicative of calcium leaching as a consequence of the deteri­
acid attack than the others. oration of the cement matrix. The increase in the amount of silica

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B.S. Santos et al. Developments in the Built Environment 21 (2025) 100592

observed for the RM, OM and NM3 may also suggest that aggregate or
silicious phases become more exposed on the surface of test specimens
due to the deterioration of the cement matrix.

4.4. Chemical composition and overall performance

As previously mentioned, the chemical composition of the system is

the basis of the strategy to optimise the durability of mortars exposed to
acidic environments. Mortars should incorporate the most stable and
less reactive matrix components possible to withstand aggressive acid
attacks. A correlation analysis between the relative residual compressive
strength and the original chemical composition of mortars further sug­
gests that certain components were more relevant for the global per­
formance than others (e.g., Fe2O3, Al2O3, CaO). Iron-rich systems are, in
fact, gaining attention because of their higher sulphate resistance. Iron
has the ability to modify the initial hydration product layer and accel­
erate the hydration process, resulting in more calcium silicate hydrate
(C-S-H) gel formation and a denser microstructure (Baral et al., 2024;
Zhang et al., 2023). The acid resistance of high content of alumina and
silica binders has also been attributed to the higher neutralisation ca­
pacity provided by aluminium hydroxide and the stability of calcium
silicate hydrate (C-S-H), calcium aluminate hydrate (C-A-H) and calcium
aluminosilicate hydrate (C-A-S-H) phases. After an acid attack, a cohe­
sive alumina gel is formed, offering a protective action (Damion and
Chaunsali, 2022). In contrast, an excess of CaO can lead to the formation
of calcium hydroxide, which is responsible for reacting with sulphuric
acid to form gypsum, which induces volume expansion (Monteny et al.,
2000, 2001).

5. Conclusions

This paper investigated the effect of sulphuric acid attack on the

mechanical, microstructural and chemical properties of chemically
resistant mortars for use in sewers and wastewater plants. Mortar
specimens were immersed in sulphuric acid (pH 0.0) for 14 days,
assessing their relative residual compressive strength and corrosion
depth against the identical specimens immersed in water for the same
period following DIN 19573:2016–03. The effects were analysed using
MIP, ATR-FTIR, and SEM-EDX.
The results showed that the new mortars, specifically designed to
tolerate highly acidic environments, outperformed the commercially
available ordinary mortar under the conditions of the immersion test
followed.

1. NM2 and NM3 exhibited high relative residual strengths of 79.3%

94.6%, respectively, meeting the best corrosion resistance class
(XWW4) of DIN 19573:2016–03;
2. The corrosion depth for NM2 and NM3 were 2.2 mm and 0.5 mm,
respectively, i.e., 1.9 and 8.2 times smaller than that of the reference
mortar (4.1 mm);
3. A significant improvement of up to 49% and 180% was observed in
terms of relative residual compressive strength and corrosion depth,
respectively, for NM2 and NM3, compared to the reference mortar
produced according to DIN 19573:2016–03;
4. SEM micrographs and FTIR spectra revealed the occurrence of
microcracks and gypsum formation for all the acid exposed mortars,
except NM3;
Fig. 7. SEM micrographs recorded from the surface of the studied mortars after
5. The results suggest that the chemical composition of the mortars,
immersion in water and in sulphuric acid (14 days, pH 0.0) with identification
of microcracks (yellow arrows) and typical gypsum acicular forms (red arrows): rather than the porous structure or the initial mechanical resistance,
RM – Reference mortar according to DIN 19573:2016–03 (German Institute for is the key factor in determining the acid resistance. No clear rela­
Standardization, 2016); OM – Ordinary mortar commercially available; NM1, tionship was found between porosity and relative residual
NM2 and NM3 – Improved mortars 1, 2 and 3, respectively. compressive strength;
6. The results suggest that sulphate-resistant binders could be a sig­
nificant solution to mitigate the effects of sulphuric acid attack;
7. The overall findings underscore the importance of optimising the
systems’ chemical composition, which should result in more stable

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B.S. Santos et al. Developments in the Built Environment 21 (2025) 100592

Fig. 8. EDX spectra acquired from the surface of the studied mortars after immersion in water (blue lines) and after immersion in sulphuric acid (red lines): RM –
Reference mortar according to DIN 19573:2016–03 (German Institute for Standardization, 2016); OM – Ordinary mortar commercially available; NM1, NM2 and
NM3 – Improved mortars 1, 2 and 3, respectively.

phases when in contact with sulphuric acid, thereby reducing the risk review & editing, Supervision, Project administration, Methodology,
of early deterioration. Conceptualization.

CRediT authorship contribution statement Declaration of competing interest

Bruna S. Santos: Writing – original draft, Investigation. Wesley B.S. The authors declare that they have no known competing financial
Machini: Writing – original draft, Investigation. Gina Matias: Writing – interests or personal relationships that could have appeared to influence
original draft, Investigation. Nelson F.S.T. Moreira: Investigation. the work reported in this paper.
Paulo M.M. Portugal: Investigation. Isabel Torres: Writing – review &
editing, Validation. António Tadeu: Writing – review & editing, Vali­
dation, Methodology, Conceptualization. João A.S. Almeida: Writing –

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B.S. Santos et al. Developments in the Built Environment 21 (2025) 100592

Acknowledgements Figala, P., Drochytka, R., Mészárosová, L., 2023. Research of a new chemically resistant
repair mortar modified with secondary raw materials. Solid State Phenom. 351,
9–14. https://doi.org/10.4028/p-n4hdBp.
This study was funded by the Portugal 2020, with the support of García Lodeiro, I., Macphee, D.E., Palomo, A., Fernández-Jiménez, A., 2009. Effect of
FEDER, under the project Mortar4Sewage (POCI-01-0247-FEDER- alkalis on fresh C-S-H gels. FTIR analysis. Cement Concr. Res. 39, 147–153. https://
039829). The authors are grateful for the Foundation for Science and doi.org/10.1016/j.cemconres.2009.01.003.
García-Vera, V.E., Tenza-Abril, A.J., Lanzón, M., Saval, J.M., 2018. Exposing sustainable
Technology’s support through funding UIDB/04625/2020 from the mortars with nanosilica, zinc stearate, and ethyl silicate coating to sulfuric acid
research unit CERIS (DOI: 10.54499/UIDB/04625/2020). The authors attack. Sustain. Times 10, 3769. https://doi.org/10.3390/su10103769.
are also grateful for the Portuguese Pluriannual Base Funding for García-Vera, V.E., Tenza-Abril, A.J., Saval, J.M., Lanzón, M., 2019. Influence of
crystalline admixtures on the short-term behaviour of mortars exposed to sulphuric
Technology and Innovation Centres (Call No 03/C05-i02/2022) as part acid. Materials 12, 82. https://doi.org/10.3390/ma12010082.
of the Mission Interface supported by the Recovery and Resilience Plan German Institute for Standardization (DIN). Mortar for Construction and Rehabilitation
(RRP) and Next Generation EU mechanisms. The authors thank Mapei of Drains and Sewers outside Buildings. Berlin: DIN 19573:2016-03.
Goyal, S., Kumar, M., Sidhu, D.S., Bhattacharjee, B., 2009. Resistance of mineral
Spa (Building Lab, Via Cafiero, 22, 20158 Milan, Italy) for the technical admixture concrete to acid attack. J. Adv. Concr. Technol. 7, 273–283. https://doi.
and scientific support provided in this investigation. org/10.3151/jact.7.273.
Grengg, C., Mittermayr, F., Ukrainczyk, N., Koraimann, G., Kienesberger, S., Dietzel, M.,
2018. Advances in concrete materials for sewer systems affected by microbial
Data availability induced concrete corrosion: a review. Water Res. 134, 341–352. https://doi.org/
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