Case Studies in Construction Materials 16 (2022) e01119

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Case Studies in Construction Materials

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Case study

Feasibility of sludge generated in water-based paint industries as

cement replacement material
Syed Ishtiaq Ahmad 1, Zanzabil Binte Ahmed, Tanvir Ahmed *, 2
Department of Civil Engineering, Bangladesh University of Engineering and Technology, Dhaka 1000, Bangladesh

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

Keywords: An estimated 2100 tonnes of solid sludge is generated per annum from the water-based paint
Paint sludge industries of Bangladesh. This paint sludge (PS) is usually incinerated, consuming energy and
Cement replacement material generating greenhouse gases and other pollutants. Through chemical analysis and standardized
Durability
tests, it was shown that PS contains a similar array of oxides as Ordinary Portland Cement (OPC)
Pozzolanicity
and has pozzolanic characteristics. Considering these, PS was examined as a cement replacement
material to create an alternative and economically beneficial way of disposing of this waste.
Cement paste and mortar samples were prepared by replacing 5%, 10%, 15%, 20% and 30% of
OPC with PS. To assess mechanical and durability properties of PS-incorporated samples,
different tests were carried out that included consistency, setting time, compressive strength,
soundness, sulfate attack, alkali silicate reactivity and chloride diffusion. Both initial and final
setting times of PS-incorporated cement increased with an increase in PS fraction but remained
within the standard limit. Compressive strength increased for 5% PS replacement but decreased
with further increase in PS replacement compared to 100% OPC mortar. A slightly higher rate of
compressive strength gain was observed at later ages for PS-incorporated cement than 100% OPC,
which confirmed the pozzolanic characteristic of PS. The addition of PS was found to reduce the
expansion of mortar bars in both soundness and ASR tests. It also inhibited ettringite crystal
formation in the mortar matrix for sulfate exposure. Initially, chloride permeability increased in
the early days for PS-incorporated mortar but was found to decrease rapidly at later ages. Alto­
gether, it may be concluded that a 15% replacement of OPC with PS would comply with the
necessary strength and durability standards.

1. Introduction

Concrete is the universal building material, and its use is expected to increase exponentially in the future, particularly in countries
with emerging economies. Concomitantly, the demand for Ordinary Portland cement (OPC), which is the most commonly used cement
and an essential ingredient of concrete, is expected to grow [1]. World cement production capacity is projected to touch 5.8 billion tons
by 2024, according to the Global Cement Volume Forecast Report 2019 [2]. The production of OPC contributes to greenhouse gas
inventory, with almost 1 ton of carbon dioxide (CO2) being emitted for each ton of cement produced [3]. The Cement industry is

* Corresponding author.
E-mail addresses: siahmad@ce.buet.ac.bd (S.I. Ahmad), zanzabilahmed3005@gmail.com (Z.B. Ahmed), tanvirahmed@ce.buet.ac.bd (T. Ahmed).
1
Orcid ID: 0000-0002-4486-3508
2
Orcid ID: 0000-0002-8970-0999

https://doi.org/10.1016/j.cscm.2022.e01119
Received 18 March 2022; Received in revised form 19 April 2022; Accepted 28 April 2022
Available online 2 May 2022
2214-5095/© 2022 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
S.I. Ahmad et al. Case Studies in Construction Materials 16 (2022) e01119

attributable to about 5% of global anthropogenic emissions of CO2 [4]. In addition to the generation of CO2, the particulate matter
emitted in ambient air during the cement manufacturing process can have adverse consequences to human health [5]. The cement
clinker production process is also responsible for 9% of global mercury emissions (173 tons annually in 2010) as mercury is introduced
through raw materials and fuel [6]. Environmental concerns associated with Portland cement manufacturing have led researchers to
venture into alternatives or partial replacements of cement.
OPC is made from a combination of calcareous materials, silica and alumina, which undergo reaction with water to form binding
compounds [7]. Any material partially replacing OPC needs to possess sufficient cementitious properties. Reusing industrial sludge and
construction solid waste as a CRM has been shown to have good economic potential and poses a win-win situation regarding envi­
ronmental sustainability [8,9]. Many harmful substances (e.g., heavy metals), if present in the industrial solid waste, can be effectively
stabilized in mortar or concrete, as evidenced in various studies [10,11]. However, any waste product used as CRM should be tested for
its pozzolanic characteristics and heavy metal leaching potential.
The effect of cement replacement materials (CRM) on cement, cement-mortar or concrete properties has been widely studied [12].
However, not all CRMs resulted in favorable changes in cement, mortar or concrete properties, and therefore, limits have been imposed
in most studies regarding their addition to the matrix. The compressive and bending strength of specimens increased due to the in­
clusion of natural pozzolan at 5–15% replacement [13]. Similar observations were made with fly ash, though strength properties
decreased after 40% replacement [14]. Concrete prepared with OPC and granulated blast furnace slag showed an inverse relationship
of strength properties with slag replacement, and it was suggested that a 20% replacement of cement would be optimum [15].
Decreased compressive strength in concrete was also observed for CRMs such as stone slurry, waste paper sludge ash, and palm fuel oil
ash [16–18].
On the other hand, sawdust ash and finely ground waste glass as CRM showed higher compressive strength in concrete [19,20]. In
mortar bars, rice husk, sugarcane bagasse and corn cob ashes as partial cement replacement were explored with widely different
results. The mortars produced with rice husk ash (15% replacement) had higher strength than the control sample; mortar with corn cob
ash showed good early strength development but insignificant gain later on, while experiments with sugarcane bagasse ash showed an
intermediate performance [21].
Several authors have highlighted that CRMs that exhibited pozzolanic behavior were responsible for the superior mechanical
properties in the mortar and concrete [20,22,23]. Pozzolanicity has been found to have a strong correlation with relative strength and
cementitious material content (efficiency factor) in experiments with silica fume and metakaolin [22]. Most earlier studies did not
report the pozzolanic characteristics of the CRM, which could have elucidated its compatibility with the cement and explained the
strength gain or loss behavior in the mortar and concrete specimens [13–20].
Like other industrial solid wastes, paint sludge (PS), a semi-solid, organic by-product of the paint industry, can be a candidate for a
CRM. It is estimated that approximately 25–30 million gallons of water-based paint are consumed every year in Bangladesh, which
generates about 2100 tons of sludge. The typical practice of disposal methods of PS is a physical and chemical treatment followed by
incineration [24]. Since incineration is energy-intensive and responsible for GHG and pollutant emissions, environment-friendly
disposal methods through resource recovery and reuse have been suggested by many [25–28]. However, the use of PS as a con­
struction material or its partial replacement has rarely been explored. In one instance, PS was incorporated in asphalt concrete
mixtures to examine its potential in pavement construction [29]. Recently Avci et al. investigated PS from oil-based paint industries as
an aggregate replacement material [30]. To our knowledge, PS has not comprehensively been explored as a CRM in the available
literature.
This paper proposes using sludge generated in water-based paint industries as a CRM in the construction industry. Cement was
replaced with different proportions of PS, and the physical and mechanical behavior of cement-sand mortar specimens were examined.
Pozzolanic behavior, elemental composition and microscopic observation of PS and PS-incorporated cement-sand mortar were

Fig. 1. Gradation Curves of Sand Samples used for different tests.

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investigated to explain the mechanical behavior. The long-term durability properties of PS-incorporated mortar were also evaluated.
The objective of the study is to assess the long-term viability of using PS as a CRM and its ability to enhance the properties of mortar and
concrete in civil engineering construction.

2. Methods and materials

2.1. Cement and fine aggregate

Ordinary Portland Cement (OPC) of Type 1 of ASTM C150 [31] and local sand (Sylhet sand) have been used for this study. The
Sylhet sand is coarse sand extracted from riverbeds of north-eastern Bangladesh and has a fineness modulus (FM) value above 2.5. The
sand was first washed with water several times to eliminate the salts and impurities and was oven-dried at 110 ℃ for 24 h. After that, it
was sieved, and the particles passing through No. 16 (1.19 mm) sieve and retained in No. 30 (0.59 mm), No. 40 (0.42 mm), No. 50 (0.3
mm), No. 100(0.15 mm) sieves were collected. Here, two different types of gradation were used for sand: Gradation A and Gradation B
(Fig. 1). Gradation B was used to make specimens for Alkali-Silica Reaction (ASR) test, whereas Gradation A, prepared following ASTM
C778 [32], was used to make specimens for the remaining tests.

2.2. Collection, processing and SEM imagery of paint sludge

PS was collected from Berger Paints factory located at Nabinagar, Savar, Dhaka (23º 55’ 03", 90º 14’ 46"). PS was ground manually
and air-dried for 3–4 days (Fig. 2a). Then the sample was oven-dried at 110 ℃ for 24 h, cooled at room temperature and further
crushed in the Los Angeles Abrasion Test machine. After 2000 cycles, the powdery material was sieved with the No. 200 (0.074 mm)
sieve and the portion passing through the sieve was collected for use as Cement Replacement Material (CRM) (Fig. 2b). The PS had a pH
of 10.2, initial moisture content of 40% and specific gravity of 2.1. The loose bulk density of the PS was 640 kg/m3, and the loss on
ignition was 5.53%. In comparison, OPC used in this work had a specific gravity of 3.11 and an ignition loss of 1.57%. The fineness of
both PS and OPC were measured as per ASTM C204 [33] air permeability method. The specific surface area of PS and OPC was
460 m2/kg and 394 m2/kg, respectively.
SEM (Scanning Electron Microscope) was used to obtain information about the morphology and comparative particle shape of OPC
and PS. A minimal amount of oven-dried sample was placed in the Field Emission Scanning Electron Microscope (Model: JSM-7600 F).
When the sample reached the vacuum chamber, the pressure was reduced to 10ˉ8 Pa, and the voltage was kept at 5.0 KV. Images were
captured at various magnifications (1000×, 2000×, 3000×, 10,000×). The comparative SEM image of OPC and PS with 5000 and
10,000 magnification ratios are shown in Fig. 3. It can be seen that the particle size of OPC varied between 1 and 12 µm. For PS, particle
size had a relatively large variation (between 1 and 40 µm). Both OPC and PS have highly irregular shapes. Furthermore, both
appeared to have flaky elements protruding from the main mass of the particle. However, the surface texture of OPC appeared to be
much rougher than PS. This is because of the higher number of protruding flaky elements and their relatively sharper edges for the case
of OPC.

2.3. Elemental composition

The elemental composition of PS and OPC was determined using X-Ray Fluorescence (XRF). 15 mm diameter tablets of sludge were
prepared by placing the sample in HERZOG Pressing Unit by applying 40 KN of compressive force for 60 s. No binder was used to
prepare tablets as the sample already had sufficient binding capacity. Elemental composition was determined in an XRF

Fig. 2. (a) Raw PS being air-dried; (b) PS in final form to be used as CRM.

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Fig. 3. Comparative microstructure of OPC (3a and 3b) and PS (3c and 3d) through SEM imagery, 3(a) SEM image of OPC (5000×), 3(b) SEM image
of OPC (10,000×), 3(c) SEM image of PS (5000×), 3(d) SEM image of PS (10,000×).

spectrophotometer (Shimadzu XRF-1800) in the form of oxides of major elements.

2.4. Pozzolanicity of PS

Pozzolanicity test of CRM was conducted according to British standard specification EN 196–5 [34]. The concentration of calcium
ion (expressed as calcium oxide or CaO) and hydroxide ion present in the aqueous solution in contact with potential pozzolanic
material is determined after 8 and 30 days. A mixture of 20 gm of PS and 100 ml of water was stored at 40 ◦ C, and concentrations of
calcium oxide and hydroxyl ion were determined using the following equations:
1000 × 0.1 × V3 × f2
[OHˉ ] = = 2 × V3 × f2 (1)
50

1000 × 0.03 × V4 × f1
[CaO] = = 0.6 × V4 × f1 (2)
50

where V3 = volume of 0.1 mol/l hydrochloric acid solution used for the titration in milliliters, V4 = volume of EDTA solution used for
the titration in milliliters, f1 = factor of the EDTA solution, f2 = factor of 0.1 mol/l hydrochloric acid solution.
f1 and f2 are obtained from the following equations:
m1 × 50 m1
f1 = = × 16.652 (3)
100.09 × 0.03 × V1 V1

2 × m2 × 1000 m2
f2 = = × 188.70 (4)
105.989 × 0.1 × V2 V2

where m1 = mass of CaCO3 in grams, m2 = mass of Na2CO3 in grams, V1 = volume of EDTA solution used for the titration in milliliters,
V2 = volume of hydrochloric acid used for the titration in milliliters.

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2.5. Tests of cement and mortar specimens

Cement mortar specimens were prepared, molded the following day and cured in water at 20 ℃ in a foggy room until testing. Six
specimens were prepared- a control mix with 100% OPC, mixes with 5%, 10%, 15%, 20% and 30% of PS as partial replacement of OPC
and marked as P0, P5, P10, P15, P20 and P30 respectively. The compositions evaluated are 1:2.75:0.485 (cement: sand: water) for all
mortars except the mortars used for the Alkali-Silica Reaction (ASR) test, for which the ratio was 1:2.25:0.47. The specimen sizes for
cubes, bars and cylinders were 50 mm × 50 mm× 50 mm, 25 mm × 25 mm × 285 mm and Ø100mm × 200 mm, respectively.
Table 1 summarizes different types of tests conducted on mortar specimens along with their specimen size, number and respective
standard specifications that were followed.
The tests for normal consistency, setting times, compressive strength and soundness were conducted according to ASTM standard
specifications C187 [35], C191 [36], C109 [37] and C1038 [38], respectively. The sulfate resistance of mortars with different ratios of
PS was examined following the procedure described in ASTM C 1012 [41]. The mortar bars were put in a humid chamber for 24 h.
Then the bars were molded and cured until a minimum strength of 20 MPa was obtained. Afterward, they were submerged into a
solution of 5% Na2SO4 which was prepared a day before and stored at 23 ± 2 ◦ C. The bars were then monitored weekly for their
change in length.
Activation of alkali-silica reaction (ASR), i.e., the reaction between alkali from cement and amorphous silica from the aggregates,
can deteriorate the concrete [42]. This work carried out ASR of cement with different PS replacement ratios following ASTM C 1567
[39]. Local reactive river sand having recommended gradation (Gradation B in Fig. 1) in ASTM C1567 [39] was used for prism sample
preparation. After 24 h of casting, the prisms were de-molded and stored in distilled water at 80 ± 2 ◦ C for another 24 h. Then zero
reading of the length of each prism bar was taken with a length comparator. Afterward, prisms were immersed in 1 N NaOH at 80
± 2 ◦ C. Subsequent length measurements were taken up to 14 days of immersion.
The movement of chloride ions under the action of an electrical field was measured by determining the chloride migration coef­
ficient using NT Build 492 [40]. Ø100 × 200 mm cylinders were cast with different PS ratios, and then those were cut into two halves.
After that 50 ± 2 mm thick slices were cut from the central portion. The samples went through 24-hour conditioning. The samples
were sandwiched between sodium chloride solution and sodium hydroxide solution during the exposure period. The test was run at a
voltage determined by the initial current of the sample with an applied 30 V. For all samples in this experimental program, the test
duration was 24 h. After completing the test, the samples were split in half, and a silver nitrate solution was sprayed on the fractured
surface. A white silver nitrate precipitate formed on the face where chloride ions were present. The depth of chloride penetration was
measured. Migration coefficient (Dnssm) was calculated using the equation as per NT Build 492 [40]:
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
0.0239(273 + T)L (273 + T)Lxd
Dnssm = (xd − 0.0238 ) (5)
(U − 2)t U− 2

Where, Dnssm = non-steady state migration coefficient (10–12 m2/s); U = applied voltage (V); T = average of the initial and final
temperatures in the solution (ºC); L = thickness of the element (mm); xd = average penetration depth (mm) and t = duration of test (h).

3. Results

3.1. Characteristics of PS

Table 2 shows the elemental composition of OPC and PS in the form of oxides of major elements. It is observed that the main
constituents of OPC are CaO, SiO2, SO3 and Fe2O3. These are also present in PS but in slightly different quantities. Like OPC, the major
constituent of PS is CaO (41.7%), which can impart cementing properties in water. For the case of SiO2 and SO3, both OPC and PS have
similar quantities. PS has a relatively higher percentage of Fe2O3 than OPC. Overall, O.P.C. and PS have similar constituents with
slightly varying proportions. Therefore, using PS as a partial replacement for OPC is not expected to alter the chemical properties of the
mixture significantly. The combined amount of Silicon dioxide (SiO2), Aluminum Oxide (Al2O3) and Iron Oxide (Fe2O3) in PS was

Table 1
List of tests on cement paste and mortar specimens.
Name of test Type of sample used No of Specification
samples

Normal Consistency of Cement/ Cement-PS mixture – – ASTM C187–11[35]

Setting Times of Cement/ Cement-PS mixture – – ASTM C191–08[36]
Compressive Strength of Mortars Cubes 108 ASTM C109–11b[37]
(50mm×50mm×50mm)
Soundness of Mortars Bars (25mm×25mm×285mm) 12 ASTM C1038–01[38]
Expansion of Mortars Exposed to a Sulfate Solution Bars (25mm×25mm×285mm) 18 ASTM C 1012–04
[38]
Potential Alkali-Silica Reactivity of Combinations of Cementitious Materials and Bars (25mm×25mm×285mm) 18 ASTM C 1567–07
Aggregate [39]
Chloride Migration Coefficient from Non-steady State Migration Experiments Cylinders 6 NT Build 492[40]
(Ø100mm×200 mm)

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Table 2
Elemental composition (expressed as oxides of major cations) and the Loss
on Ignition (LOI) of OPC and PS.
Analyte OPC PS

CaO,% 67.52 41.77

SiO2,% 16.63 18.37
Fe2O3,% 3.9 10.24
Al2O3,% 2.06 6.18
SO3,% 5.02 3.13
MgO,% 1.84 3.00
K2O,% 0.91 0.80
Na2O,% 0.25 0.40
TiO2,% 0.40 9.90
P2O5,% 0.11 0.25
MnO,% 0.11 0.08
ZnO,% 0.02 0.05
Cr2O3,% – 0.05
CuO,% 0.02 0.03
LOI, % 1.57 5.53

found to be 34.8%. As this is below 50%, PS does not fall into any Class (N, F or C) of natural pozzolan specified in ASTM C618 [43].
Nevertheless, such constituents could exhibit pozzolanic properties, which is evident from the results of the pozzolanicity test of PS
(Fig. 4). The combination of calcium and hydroxide ions present in PS after the 8th and 30th days of reaction in the aqueous solution is
shown in Fig. 4. In both instances, the combination of ions falls within the pozzolanic domain of the graph. Although PS does not
strictly fall into any of the categories as a natural pozzolan, it possesses some pozzolanic properties and the benefit of this can be
exploited by using it as a CRM.
The toxicity Characteristic Leaching Procedure (TCLP) test of PS was carried out according to USEPA 1311 method [44]. The TCLP
leaching characteristics are illustrated in Table 3. It can be seen that the leaching of toxic heavy metals is within the permissible limit
by USEPA, and the use of PS in construction is not likely to be associated with any environmental hazard. Altogether, the cementing
and pozzolanic properties of major constituents in PS, and the minimal tendency to leach harmful metals make PS an ideal candidate
for a CRM.

3.2. Normal consistency and setting time of OPC-PS mixture

Fig. 4 and Fig. 5 show the consistency and setting time behavior of cement paste with varying fractions of PS. Normal consistency is
denoted as the percent of water in cement paste at which the steel rod of Vicat apparatus settles at a depth of 10 ± 1 mm in 30 s. It is
evident from Fig. 4 that as the fraction of PS was increased, more water was required to attain the normal consistency of the paste. For
10% PS replacement, water requirement increased by 12.5%, whereas for 30% PS replacement, the increase in water demand was 29%
higher compared to the control specimen. An increase in water demand with increased PS content to attain normal consistency may be
due to two reasons. First, the particle size of PS is much larger than OPC (Fig. 3). A larger particle size might have created higher
resistance for the Vicat rod to settle for the case of PS incorporated mortar resulting in increased water demand to attain normal
consistency. Secondly, the specific gravity of PS (2.1) is lower than OPC (3.11). The lower specific gravity of PS might have increased

Fig. 4. Results of pozzolanicity test according to EN 196–5, showing the combination of calcium and hydroxide ions after the 8th and 30th day
of reaction.

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Table 3
TCLP concentration of hazardous materials present in PS.
Metals TCLP concentration (ppm) Max TCLP concentration (ppm) of hazardous material[42]

Cr <MDL 5.0
Cd <MDL 1.0
Pb 0.60 5.0
As 0.01 5.0
Hg <MDL 0.2

MDL = Minimum Detection Limit.

Fig. 5. Normal consistency of cement with different PS fractions.

paste volume in PS-incorporated mortar, resulting in a slightly higher quantity of water required for normal consistency. In previous
studies with pozzolanic type CRM, it has also been observed that the normal consistency of blended cement is slightly higher than that
of 100% OPC [45–47]. ASTM C618 [43] suggests water requirement be below 115% of control specimen for N-type pozzolan
compared to control specimen. For the case of PS, for up to 10% replacement, the water demand was below this limit.
From Fig. 6, it is evident that both initial and final setting times increased due to an increase in PS fraction in the cement paste. The
initial setting time increased from 70 min to 188 min, whereas the final setting time increased from 240 to 325 min when the PS
fraction in the paste was increased from 0% to 30%. The Effect of PS addition was greater on the initial setting time than the final
setting time of the paste. The increase in initial and final setting times due to the incorporation of PS in the cement paste is due to two
reasons. First, Tricalcium silicate (C3S) is the major component of Portland cement responsible for the early strength gain of cement
paste, and as PS replaced more and more OPC, the amount of C3S in blended cement decreased, resulting in a longer setting time.
Another reason was that hydration of pozzolanic content of PS is much slower than components of OPC [48], resulting in a longer

Fig. 6. Setting time of cement with different PS fractions.

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setting time. For all fractions of PS addition, both the initial and final setting times of the paste increased; however, they remained
within the standard limits as per ASTM C595 [49](initial setting time not less than 45 min, final setting time not higher than 420 min).
These limits are shown in Fig. 6 with dashed lines corresponding to 45 and 420 min.

3.3. Compressive strength of cement-sand mortar

The compressive strength of mortar specimens with different cement-PS fractions was tested at 3, 7, 28, 90 and 180 days after
casting (three specimens for each case). The compressive strength of all cube specimens and the average trend line for a particular PS
ratio is presented in Fig. 7. It can be seen that the compressive strength of the control sample (P0) is higher than all samples at the age of
3 and 7 days. At the age of 28, 90 and 180 days, the compressive strength of P5 was slightly higher than that of the control sample.
Apart from it, mortar with all PS fractions at all ages had lower compressive strength than the P0 specimen. As PS fraction increased,
compressive strength decreased noticeably. Two aspects of PS impart cementing properties to mortar: hydration of CaO and pozzolanic
characteristics of other components. To assess pozzolanicity, ASTM C618 [43] has defined the Strength Activity Index (SAI) as the ratio
of compressive strength of the control specimen (for this case, P0) and that of pozzolan added mortar at a particular age. SAI ratio was
evaluated for PS incorporated mortars at different ages and is shown in Table 4. For the case of P5, at 28, 90 and 180 days, SAI values
slightly over 1 indicate somewhat better performance of P5 compared to P0 mortar at those ages. For P10 mortar, SAI values varied
from 0.93 to 0.97, indicating that more than 93% compressive strength than the control specimen could be achieved with 10% PS
replacement. For P15, SAI values varied between 0.81 and 0.87. For P30, SAI decreased further and was as low as 0.58 on the 28th day.
As per ASTM618 [43], all classes (N, F or C) of pozzolan replacement must achieve an SAI of 0.75 or more on the 7th and 28th days. For
the case of PS, up to 15% replacement was found to meet this criterion. It is apparent from Table 3 that as the PS ratio in mortar
increased, SAI at 90th and 180th days were higher compared to SAI at 7 or 28th days. This shows a higher rate of compressive strength
development at later ages, indicating pozzolanic characteristics of PS. Pozzolanic components of PS have been found to form additional
Calcium Silicate Hydrate (C-S-H) gel by reacting with Ca(OH)2 from cement hydration. Fig. 8 shows the SEM images of P0 and P5
specimens after 180 days of curing. Two distinctive features can be observed from these two images. Firstly, C-S-H gel is more
abundant in the P5 sample due to secondary C-S-H gel formation resulting from pozzolanic action. Secondly, the P5 sample appears to
be denser without any internal voids than the P0 sample. These attributed to the higher strength development for PS incorporated
mortar samples at later ages.

3.4. Soundness test

The soundness of cement refers to its capability to maintain its volume as it hardens. If any alteration in the volume occurs, cement
mortar inflates or contracts, for which cracks may occur. Hence, a soundness test is a good indicator of the durability of cement [7,50,
51]. Fig. 9 shows that with an increasing percentage of PS, the increase in mortar bar length, i.e., volume expansion, decreased. For all
PS ratios, expansion was less than 0.02%, the maximum limit specified in ASTM C1157 [52]. Excess sulfate in the cement causes
excessive expansion of the mortar bar. The XRF analysis of OPC and PS indicates that OPC has greater sulfate content than PS, and
increasing PS fraction has resulted in overall lower sulfate content in the blended mortar. That could be a probable reason why
expansion decreased with the increasing PS fraction. These results imply that the addition of PS makes cement more sound; there is
likely to be a lesser tendency to form cracks due to volume change.

Fig. 7. Compressive strength development of mortar with varying PS fractions.

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Table 4
Strength Activity index (SAI) and of mortar with different PS fractions.
Mortar type Strength activity index (SAI)

3 days 7 days 28 days 90 days 180 days

P5 0.98 0.98 1.01 1.01 1.01

P10 0.95 0.93 0.93 0.95 0.97
P15 0.81 0.83 0.83 0.84 0.87
P20 0.69 0.71 0.73 0.72 0.76
P30 0.60 0.60 0.58 0.60 0.66

Fig. 8. C-S-H gel formation in P0 (Fig. a) and P5 (Fig. b) sample.

Fig. 9. Expansion of mortars with various fractions of PS as CRM.

3.5. Sulfate resistance

Sulfate reacts with the hydration product Calcium Hydroxide [Ca(OH)2] to create gypsum [Ca(SO)4.2 H2O]. Subsequently, gypsum
reacts with Tricalcium Aluminate [3CaO.Al2O3], commonly abbreviated as C3A, a primary constituent of OPC, to form ettringite
[3CaO_Al2O3_3CaSO4_32H2O] [7,53]. The volume of gypsum and ettringite is much higher than their original compounds and creates

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expansive stresses in the cement matrix, leading to damage and disintegration. Ettringite formation may increase or decrease due to the
addition of pozzolanic materials depending on the chemical composition of pozzolan. If pozzolan contains high alumina (i.e., Meta­
kaolin, activated clay), then it may intensify ettringite formation, whereas high silica content in pozzolan (i.e., silica fume, nano-silica)
lessens ettringite formation and resists sulfate attack [54]. For the case of PS, alumina content is low, whereas the silica content is high.
Hence it is expected that sulfate resistance due to the addition of PS would not be reduced. The sulfate resistance is reflected in Fig. 10,
which shows the volumetric expansion of the mortar bar having different PS fractions immersed in sodium sulfate solution for 14
weeks as per ASTM C1012 [41]. It can be seen that the control sample (P0) had the highest expansion during the entire period under
observation (0.016% at the 14th week). The trend and expansion rate of the control sample conformed to those reported in available
literature for OPC [55,56]. As the PS fraction increased from 0% to 30%, the expansion due to NaSO4 exposure decreased, and bars
with 30% PS had the lowest expansion of 0.007% after 14 weeks. The reduction in the volume change of PS-blended cement due to
immersion in sulfate solution was due to two reasons. First of all, as the PS fraction was increased, the quantity of OPC decreased.
Hence, there was less C3A available to react and form ettringite. Secondly, the pozzolanic action of PS reduced the amount of Ca(OH)2
available to react with sulfate. Hence, the formation of gypsum was also much less in PS blended cement. Fig. 11 shows the SEM images
of P0 and P10 mortar after being exposed to Sodium Sulfate solution for 14 weeks. It is evident from these figures that needle-like
ettringite crystals are much more plentiful in P0 mortar than in P10 mortar, confirming that the addition of PS inhibits ettringite
formation. Previously, the addition of lime powder and pozzolan was also found to reduce sulfate attacks on cement paste [56]. Thus, it
may be concluded that adding PS with OPC would enhance mortar performance concerning sulfate attacks.

3.6. Alkali-silica reaction test

The average expansion of all mortar mixtures as per the ASTM C1567 [39] test procedure over 14 days is presented in Fig. 12.
Except for replacing cement with PS, other factors were the same for all samples. As can be seen, the control specimen with 100% OPC
expands up to more than 0.6% on the 14th day, confirming the reactive nature of river sand used in the mortar preparation. This is
much higher than the 0.1% acceptable expansion limit in ASTM C1567 [39]. From Fig. 11, it is apparent that the addition of PS reduced
the ultimate expansion of mortar significantly. For 5% and 10% PS replacement, ultimate expansion reduced to 0.30% and 0.14%,
respectively. But the ultimate expansion in these cases was beyond the acceptable limit of 0.1%. 15% was the minimum cement
replacement level to achieve expansions below the acceptable limit. The expansion increase was significantly lower for mortars having
a PS fraction of 10% and above.
Alkali availability in the system, amount and nature of reactive silica in the aggregate, moisture availability, temperature and the
degree of internal and external restraint to movement control the expansion of concrete affected by ASR [57]. Since all other factors
were kept constant, the alkalinity of pore water mortar affected the ASR behavior of PS blended cement. Pozzolanic characteristics of
PS reduced alkali concentration from cement pore solutions. The addition of pozzolanic CRM has previously been observed to reduce
ASR significantly by reducing alkali concentration in the pore solution of cement paste [58,59]. The reduction observed in the ASR
expansion for mortar with different replacement fractions of PS may be due to these reasons. Nevertheless, from the experimental
results, it may be stated that replacing OPC with PS would have a beneficial effect compared to ASR characteristics of 100% OPC.

3.7. Rapid chloride migration test

Fig. 13 shows chloride migration coefficient (CMC) calculated using Eq. (5) for mortars with different PS ratios at the 28th, 90th
and 150th days after casting. On the 28th day, CMC increases rapidly with the increase of PS fraction in the mortar. CMC coefficient
increased by approximately 7%, 32%, 121% and 185% as PS fraction in the mortar was 5%, 10%, 15%, 20% and 30% respectively. On
the 90th day, however, mortar containing 5%, 10%, and 15% PS fractions performed better than 100% OPC mortar. For later age, i.e.,
150th day, CMC for mortar with PS further decreased. Even for this age, mortar with 5%, 10% and 15% PS fractions showed better
performance than 100% OPC mortar. Mortars with a high percentage of PS (i.e., 20% and 30%) showed a large reduction in CMC as the
age progressed. For 30% PS mortar, CMC decreased from 49 to 24.2 (x10− 12 m2/s), i.e., more than 50% reduction. This reduction of
CMC with age for mortar with PS is for pozzolanic reaction in the mortar matrix. Due to this reaction, the internal structure became
dense with subsequent porosity reduction, resulting in lower chloride migration at later ages. This is evident in Fig. 8, where two SEM
images of P0 and P5 samples after 180 days of curing are presented. The P5 sample appears to be denser without any internal voids as
opposed to the P0 sample. Also, C-S-H gel is more visible in the P5 sample due to secondary C-S-H gel formation from the pozzolanic
reaction. As a lower migration rate corresponds to a more durable cement mix, it is apparent from these experimental results that
incorporating PS up to 10% would be beneficial in terms of durability compared to a 100% OPC mix.

4. Conclusions

This work examined the effects of replacing cement with PS in the cement-mortar matrix. The basic properties of PS-incorporated
cement and cement-mortar samples were analyzed through setting time, soundness, sulfate resistance, ASR, chloride migration and
compressive strength experiments. The chemical composition of PS was examined using XRF, the microstructure and hydration
products of PS and PS-incorporated cement-mortar were observed by SEM. Based on these observations, the following conclusions can
be drawn:

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Fig. 10. Expansion vs. Immersion time of mortars exposed to 5% Na2SO4 solution.

Fig. 11. Needle-like ettringite crystal for P0 (Fig a)and P10 (Fig. b)samples after 14 days of immersion in sodium sulfate solution.

1. Incorporation of PS increases the setting time of cement, which may be beneficial for cases where additional operational time for
molding and mixing is required, such as concrete transported to the construction site far away from the mixing plant.
2. Although PS cannot be classified as a pozzolan as per ASTM C618, the strength gain characteristics exhibited by PS-incorporated
mortars (SAI of 0.75 or more at the 7th and 28th days) are manifestations of pozzolanic characteristics of PS. The higher strength
development at later ages can be attributed to secondary C-S-H gel formation (resulting from pozzolanic action) and dense internal
structure in PS-incorporated mortars.
3. Addition of PS reduced the expansion of mortar significantly, possibly due to the lower sulfate content in PS compared to OPC. The
expansion from the alkali-silica reaction (in the ASR test) is also reduced, and a 15% replacement can bring the ultimate expansion
to acceptable limits.
4. Addition of PS inhibits ettringite crystal formation in the cement-mortar matrix, contributing to less expansion and enhanced
mortar performance under sulfate attacks.
5. Mortar with high PS substitutions showed a large reduction in chloride migration over a long period.

This study provides evidence that the strength and durability characteristics of PS-blended cement can be beneficial for

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Fig. 12. ASR Expansion of Mortars during the ASTM C1567 Test.

Fig. 13. Chloride ion permeability coefficient for mortar with different PS fractions.

construction. A 15% substitution with OPC is recommended to comply with the necessary strength and durability standards. Appli­
cation of PS can potentially reduce cement consumption and concomitantly utilize a waste product in construction, eliminating the
need for looking into other costly solid waste management options. The suitability of application of PS may be further vindicated
through observing different mechanical and durability properties of concrete incorporating PS.

Funding

This research did not receive any specific grant from funding agencies in the public, commercial, or not-for-profit sectors.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to
influence the work reported in this paper.

Acknowledgment

The authors would like to show gratitude to the Concrete Laboratory staff of the Department of Civil Engineering for their assis­
tance in conducting experiments. Graduate student funding from CASR, BUET is also acknowledged.

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