Construction and Building Materials 207 (2019) 59–69

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Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Fine aggregate substitution with acidified granular activated carbon

influences fresh-state and mechanical properties of ordinary Portland
cement mortars
Ismael Justo-Reinoso, Alejandro Caicedo-Ramirez, Wil V. Srubar III, Mark T. Hernandez ⇑
Department of Civil, Environmental, and Architectural Engineering, University of Colorado Boulder, ECOT 441 UCB 428, Boulder, CO 80309-0428, USA

h i g h l i g h t s

 Functional groups distribution of GAC-ACID is similar to conventional PCE-Admixtures.

 GAC-ACID improved workability when sand was replaced 1% by mass.
 GAC-ACID increased compressive strength when sand was replaced 1% by mass.

a r t i c l e i n f o a b s t r a c t

Article history: The compressive strength and selected fresh-state responses to incorporating acid-modified granular
Received 25 August 2018 activated carbon (GAC) in cement mortars, were compared to physical cement behaviors associated with
Received in revised form 6 February 2019 the incorporation of otherwise unmodified GAC and a commercial polycarboxylate superplasticizer.
Accepted 10 February 2019
Specific surface area of unmodified and acidified GAC, porosity, pH at charge neutrality (pHPZC), and
Available online 23 February 2019
surface-associated functional groups were compared. Fresh- and hardened-state responses were
observed, including slump, setting time, zeta potential, and compressive strength. Results suggest that
Keywords:
substituting 1% of the fine aggregate mass with GAC particles that had been pre-treated in nitric acid,
Acidified activated carbon
Cement mortar
can improve compressive strength and workability of cement mortar.
FTIR Ó 2019 Published by Elsevier Ltd.
Polycarboxylate-ether
Superplasticizer
Workability
Zeta potential

1. Introduction
1.1. Literature review
Activated carbon is a well-known sorbent that is used in the
water, wastewater, and air treatment sectors. Carbon particles,
however, have been traditionally considered as aggregate contam-
inants when introduced to cementitious materials [1]. In response
to recent methodological studies that have focused on purposeful
additions of carbon particles to concrete [2–10], paradigms for
beneficial use of activated carbon in modern cementitious materi-
als are gaining increased attention. Activated carbon has been
shown to improve some mechanical properties (i.e., compressive
and tensile strengths) and decrease total porosity when GAC parti-
⇑ Corresponding author at: 1111 Engineering Drive, ECOT 441 UCB 428, Boulder,
CO 80309, USA.
E-mail address: mark.hernandez@colorado.edu (M.T. Hernandez).
cles are substituted for between 1% and 2% of the fine aggregate
mass in cement formulations [4,7,10]; this demonstrates potential
for the beneficial use of GAC in next-generation cement formula-
tions. When purposely including activated carbon in cementitious
materials, it is of vital importance to understand the effects these
particle additions may have on fresh- and hardened-state proper-
ties, including the rheological properties of fresh mortars that
evolve during cement hydration [11]. However, understanding
the internal structure and properties of fresh cement paste is not
trivial, as direct measurements and characterization of microstruc-
tural developments are complex due to factors such as non-
uniform dispersity, high solid volume fraction, low-transparency
and the maturing hydration process [12]. Additionally, the inclu-
sion of carbonaceous particles may influence the initial fresh state
microstructure and, in turn, have an effect on the final microstruc-
ture, thereby influencing the mechanical properties of the
hydrated paste or mortar [12].

https://doi.org/10.1016/j.conbuildmat.2019.02.063
0950-0618/Ó 2019 Published by Elsevier Ltd.
60 I. Justo-Reinoso et al. / Construction and Building Materials 207 (2019) 59–69
Physical and chemical interactions that occur during the curing
process depend on the amount, shape and gradation of fine aggre-
gates, as well as other potentially reactive co-additives [13],
including but not limited to carbonaceous particles and polymeric
admixtures. Workability is considered to be among the most
important properties of cement-based materials [14,15], and a
key, site-specific factor considered in mortar design. While cement
mortar is considered a relatively low-tech material, the science
underlying its workability remains complex. Difficulties exist in
characterizing the mechanical work which circumscribes ‘‘worka-
bility” in a comprehensive sense, and, given the composite nature
of fresh cement mortar, a fundamental method to measure this
transient property has yet to gain universal acceptance [16]. Nev-
ertheless, observational tests remain widely used on curing cement
to observe macro-scale mechanical property developments. Such
tests include Vicat needle penetration, which is commonly per-
formed to quantify setting time [13,17] as described by ASTM
C191-13 [18]. The most commonly used workability test methods
are based on empirical methodologies [19]. Such is the case with
slump tests, which assess a conglomerate material resistance to
flow [16,20]; its counterpart adapted for cement pastes, the
mini-slump cone test, has been developed by Construction Tech-
nology Laboratories (CTL), Inc. [21]. Along with workability, mortar
strength is the most common physical index of cement paste.
Water content can be adjusted to effectively improve the workabil-
ity of conventional mortars. However, given that increases in water
content correlate with observable reductions in strength [20],
water-reducing superplasticizers are commonly used to increase
the workability of low water-to-cement (w/c) ratio cement pastes,
mortars, and concrete.
Research on the inclusion of activated carbon particles in
cementitious formulations has generally neglected the effects of
incorporating such materials on the fresh-state properties of the
mixtures. Among the few exceptions, a study by ErS ßan and co-
workers, evaluated the setting time of mortar mixtures containing
granular activated carbon (GAC) (5% w/w cement) [4]. Other stud-
ies, incorporating carbon nanotubes (CNTs) in cement mixtures,
have also evaluated fresh-state properties on these cementitious
formulations [22–24]. The goal of these studies focused on the
use of activated carbon particles as metal reservoirs to achieve
antimicrobial properties [8,9]; the use of carbon particles as inter-
nal nutrient reservoirs for microorganisms in bio-mineralizing
mortars [4,25]; or the use of carbon particles to sorb different vola-
tile compounds [2,3,6], among others purposes. However, these
studies did not report specific mechanical and fresh-state behav-
iors associated with incorporating activated carbon particles.
1.2. Scope
This study focuses on the effects that GAC particles, pre-treated
with nitric acid, can have on fresh-state and mechanical properties
of cement mortars—when a small percentage of the fine aggregate
mass is replaced by these carbonaceous particles. The following
formulations were investigated to isolate the effects of the
acidified GAC particles have on select workability and strength
characteristics: Control (0% GAC); Control with superplasticizer
(0% GAC + PCE-Admixture); 1% unmodified GAC substitution; and
1% HNO3-acidified GAC substitution. The substitution percentage
considered in this study (i.e., 1% of the fine aggregate by mass)
corresponds to a range where higher compressive strength is
obtained when using bituminous GAC particles in the particle size
range between 0.3 and 0.8 mm [10].
The pre-treatment of GAC with nitric acid is a common indus-
trial process used to alter the sorption behavior of activated car-
bon. In addition to strength enhancements, GAC particles can be
engineered to present pH-dependent exposure of different biocidal
metals entrained in concrete appurtenances; this approach has
emerged as a promising alternative to inhibit the acidophilic bio-
films responsible for microbially induced concrete corrosion
(MICC) [8,26].
No studies report the effects acidified GAC particles can have on
the different fresh-state properties and compressive strength of
cementitious materials.
Results from this work provide a framework to leverage acid
treated GAC particles into beneficial application for special cemen-
titious material applications. It is not the intention of this study to
validate the use of HNO3-acidified GAC particles as an alternative
to commonly used superplasticizers.
2. Materials and methods
2.1. Materials
2.1.1. Granular activated carbon (GAC)
Granular activated carbon (GAC), supplied by the Calgon Corporation (Pitts-
burgh, USA) and commercially sold as OL 20  50, was used in this study. The
GAC was manufactured from bituminous coal and activated using superheated
steam, resulting in a minimum iodine penetration of 1050 mg/g as reported by
the supplier [27]. The particle size distribution of this GAC was determined by stan-
dard sieve analysis and is summarized in Table 1.
In this study, the GAC was used in two forms: unmodified as received (OL, Cal-
gon) and after subjecting it to a common acidification process with nitric acid.
These two types of activated carbons will be respectively referred to hereafter as
GAC-UNM (unmodified granular activated carbon) and GAC-ACID (acid-modified
granular activated carbon). Acidification was accomplished by adding unmodified
GAC into 1L beaker containing a 5% HNO3 solution, at liquid to solid ratio of 2:1.
The mixture was homogenized and kept at room temperature for 30 min. Next,
the beaker was placed in an oven at 250 °C for 2.5 h. After heat treatment, the
cooled GAC, now referred as GAC-ACID, was thoroughly washed with DI water to
remove any excess of unreacted acid. Then, the GAC-ACID was oven dried at
60 °C overnight and kept at room temperature and low humidity until further
use. Water sorption capacity and saturated surface-dry (SSD) specific bulk gravity
for GAC-UNM and GAC-ACID were determined in accordance with ASTM standard
C128-15 [28], as presented in Table 2.
2.1.2. Graded standard sand (Ottawa sand)
Ottawa test sand was obtained from the U.S. Silica Company (USA), which is a
clean natural sand with high silica content; it contains the following constituents
on a percent basis: between 99.0 and 99.9% crystalline silica (quartz), <1.0 alu-
minum oxide, <0.1 iron oxides, and <0.1 titanium oxides [29]. This sand conforms
to ASTM standard C778-17 [30]. Sorption capacity and saturated surface-dry
(SSD) specific bulk gravity were determined in accordance with ASTM standard
C128-15 [28] and presented in Table 2.
2.1.3. Ordinary Portland cement
The cement used in this study was a commercial ordinary Portland cement (OPC
Type I/II) manufactured by Quikrete (USA) that complies with ASTM C150-18 [31].
The alkali- and metalloid-oxide contents (obtained from X-ray fluorescence spec-
trometry (XRF)), as well as the calculated Bogue composition of the cement, are
summarized below in Table 3.
2.1.4. Superplasticizer
A commercial superplasticizer, Melflux 4930 F (provided by BASF (USA)), was
included in this study to compare its potential interactions with the rheological
behavior observed when GAC particles substitute fine aggregate particles. This
admixture is a polycarboxylate-ether (PCE) with a density between 300 and
600 kg/m3, as described by the manufacturer’s technical data sheet [32]. In addition
to the typical electrostatic properties of this PCE superplasticizer, non-charged side
Table 1
Mass-based standard sieve analysis of Calgon (OL 20  50) granular activated carbon
(GAC).
Sieve # Sieve size (mm) Passing by mass (%)
10 2.000 100.00
20 0.850 99.56
40 0.425 2.08
60 0.250 0.61
100 0.150 0.51
200 0.075 0.32
 I. Justo-Reinoso et al. / Construction and Building Materials 207 (2019) 59–69 61

Table 2 Table 4
Bulk saturated surface dry (SSD) specific gravity and water sorption capacity of GAC Mortar formulations with the corresponding w/c ratios (additional, total, and
(GAC-UNM and GAC-ACID) and Ottawa sand. effective).

Fine Bulk saturated surface dry (SSD) specific Sorption capacity Formulation (w/c) add (w/c) total (w/c) eff
aggregate gravity (%)
Control 0.00 0.50 0.50
GAC-UNM 1.35 75.1 1% GAC-UNM 0.02 0.52 0.50
GAC-ACID 1.37 74.2 1% GAC-ACID 0.02 0.52 0.50
Ottawa sand 2.65 0.81 PCE-Admixture 0.00 0.50 0.50

2.2.1. GAC characterization

chains of Melflux products also provide steric repulsion, which improves their func- Brunauer-Emmet-Teller (BET) surface area, micropore and mesopore volumes,
tion as a water-reducing agent. This admixture will be referred to hereafter as PCE- and pore size distributions were determined from N2 isotherm data, collected using a
Admixture. Micromeritics Gemini V Surface Area and Pore Size Analyzer (Micromeritics, GA, USA).
Prior to analysis, GAC samples were degassed under vacuum (2.0  10 1 mbar) at
100 °C for 24 h; the degassed samples were then cooled and weighed, and the sur-
face area and pore size distribution determined using widely accepted BET methods
2.1.5. Cement mortar formulations
[36]. The specific surface area of GAC particles was calculated using the standard
GAC can be considered as a lightweight aggregate, as described by ACI 213R,
BET equation, assuming the surface area occupied by physiosorbed nitrogen gas
and, due to its cellular structure, can sorb more water than conventional fine aggre-
molecules was 0.162 nm2. Mesopore volumes (2–50 nm) and the specific surface
gates. When introduced to a cement mix, the water sorbed by GAC is not immedi-
areas associated with this size range were calculated using the Barret-Joyner-
ately available for initial stages of cement curing; thus, moisture carried by GAC is
Halenda (BJH) method with the Halsey-Faas correction. Micropore volumes (pore
not included with the conventional mixing water mass and not considered in the
diameters < 2 nm) and the specific surface areas associated with this size range
w/c ratio of a mix design. If GAC particles are saturated with water before being
were calculated using the t-plot method with the Harkins and Jura thickness equa-
integrated into the cement mortar formulations (as it was done in this investiga-
tion. The average pore width was calculated from the adsorption and desorption
tion), they do not have an impact in the initial w/c ratio [33,34]. Water sorbed into
curves using BET theory. As mentioned by Scrivener K. et al., desorption curves have
GAC, in addition to that provided for initial mixing, is summarized in Table 4 as w/c
more often been used, but adsorption curves are perhaps less influenced by
add. This additional w/c ratio (w/c add) contributes to the w/c total. The effective w/c
tortuosity and pore shape [37]. A cylindrical shape of the pores was considered
ratio ((w/c) eff) takes into account the amount of water sorbed by the GAC particles.
for these calculations.
Prior to mixing, all GAC particles used in this study were oven-dried at 90 °C for
The pH of point of zero charge (pHPZC) for the GAC particles used in this study
24 h, cooled in dry air, then submerged in Ultrapure water (Milli-Q system, USA) for
was determined by the pH drift method [38]. The equilibrium pH was determined
24 ± 1 h. The net amount of water used in the mix design, included the water mass
by adding 1 g of GAC/admixture to 5 ml of DI water. The suspension was sparged
that saturated the GAC, plus the mixing water required to achieve a w/c eff ratio of
with N2 and mixed for 24 h, after which, the pH was recorded.
0.50. Four formulations with the same (w/c) eff ratio (0.50) were used in this study:
Oxygen-associated surface functionalities were determined through Boehm
Control (0% GAC substitution), 1% of GAC-UNM substitution, 1% of GAC-ACID substi-
titration with the modifications reported by Goertzen et al. [39,40]. Briefly, 0.75 g
tution, and a formulation with no GAC, but with addition of the PCE-Admixture.
of GAC were placed in 25 ml of 0.05 M of NaHCO3, Na2CO3, or NaOH. The mixtures
Where cement was designed to contain GAC, one percent (1%) of the fine aggregate
were sparged with N2, sealed, and mixed for 24 h at room temperature. Then, 10 ml
(sand) mass, was replaced by either unmodified GAC particles of the same size
aliquots were centrifuged at 5000 rpm for 10 min and filtered through a 0.2 mm
(GAC-UNM), or their otherwise identical acid modified counterparts (GAC-ACID).
nylon membrane. HCl 0.05 M was added to completely neutralize the base in each
For the formulations designed to contain PCE-admixture, 0.12% of the dry cement
batch. The volume of acid added was 20 ml for NaHCO3 and NaOH, while the vol-
weight was used, corresponding to the lower end of the dose range recommended
ume added for Na2CO3 batches was 30 ml. Next, the solutions were sparged with
by the manufacturer (0.05% < PCE < 1.00%) [32]. The design aggregate proportion
N2 for 2 h and back-titrated with 0.05 M of NaOH to obtain the contribution of
was one-part cement to 2.7 parts graded standard sand by weight. All mortar for-
the different functional groups on each GAC, as well as the PCE-Admixture.
mulations were manually mixed. In the first mixing step, cement was added to
Fourier Transformed Infrared Spectroscopy (FTIR) spectra were obtained for
the total amount of water (including saturated GAC) and mixed for 30 s. In the next
each type of activated carbon and the PCE-admixture using a Fourier Transform
mixing step, the total amount of fine aggregate (Ottawa sand) was added and mixed
IR spectrophotometer (Nicolet iS10, Thermo Scientific, USA) in the range of 400–
for an additional 30 s. The mortar formulation was then mixed for an additional
4000 cm 1. The samples were examined as KBr disks and the background spectrum
minute, for a total mixing time of 2 min. For the zeta potential assays, the GAC
of air was subtracted from their spectra. All samples were run in triplicate. Initial
replacement (GAC-UNM and GAC-ACID) was increased to 10% in order to observe
sample preparation used a mortar and pestle to crush the material into a fine pow-
the dose–response GAC particles can have on the fresh-state properties of this
der (<100 mesh). Next, a dry preparation of the powdered analyte was mixed with
cementitious formulations. Table 4 presents the different formulations described
KBr powder to include a final mass concentration of 1%. The mixture was then dried
above.
in a vacuum oven at 120 °C overnight and then pressed to obtain the KBr disks.
A high-resolution scanning electron microscope (SEM) (SEM SU3500 from Hita-
chi (Japan)) was used to study the morphology and pore structure of GAC surfaces.
2.2. Experimental methods Magnifications between 35 and 200, an anodic voltage of 10 kV, and a current fil-
ament intensity of 0.13 nA was used for this study.
The two types of GAC used in this study were characterized by their acid-base
behavior (equilibrium pH in buffered solution), their pH of point at zero charge
(pHPZC), surface functionalities, surface area and porosity, and morphology using 2.2.2. Zeta potential
SEM techniques. For evaluating the fresh-state of the mortar formulations, Vicat Mortar formulations were prepared by substituting 10% of the fine aggregate
needle and mini-slump tests were used to describe the initial and final setting with GAC and/or by adding the PCE-Admixture, as described above. Then, 0.25–
times, according to ASTM C191-18 [18] and cement paste consistency, respectively. 0.30 g of the mortar paste were taken and placed in a vessel with 100 ml DI water.
Zeta potential was used as a proxy to judge dispersive behavior. In the hardened- The solutions were continuously stirred as aliquots were taken at different inter-
state, compressive tests (ASTM C109/C109M-16a [35]) at two different ages (7 vals. Next, these extracts were centrifuged for 2 min at 10,000 rpm (MiniSpin Plus
and 28 days) were performed. Eppendorf, Ontario, Canada). The supernatants were analyzed with a Zeta Potential

Table 3
Alkali- and metalloid-oxide content and Bogue composition analysis (% by mass) of the cement.

Oxide Composition
CaO SiO2 Al2O3 Fe2O3 K2O MgO Na2O SO3 Loss on Ignition (LoI)
62.8 20.3 4.31 3.85 0.35 1.98 2.08 2.42 3.29
Bogue Composition
C3S C2S C3A C4AF
59.2 13.4 4.9 11.7
62 I. Justo-Reinoso et al. / Construction and Building Materials 207 (2019) 59–69
Analyzer ZETA PLUS (Brookhaven Instruments Corporation, New York, USA). Zeta-
Pals software was used to compile the data. This Phase Analysis Light Scattering
method (PALS) was the method of choice, since it is more sensitive than conven-
tional Laser Doppler Velocimetry (LDV) [41]. The average of twenty measurements
was reported as the zeta potential of the particles observed.
2.2.3. Initial and final setting time
The setting time of cement mortar specimens from each formulation was
reported as judged by Vicat needle penetration in an apparatus conforming to ASTM
standard [18].
2.2.4. Workability
The workability of fresh cement mortar formulations was assessed immediately
after mixing using a miniaturized version of the conventional slump test (modified
mini-slump) [42]. The mini-slump cone test is based on the same principle as that
of the conventional slump test (ASTM C143/C143M-15a [43]) used for concrete. A
plastic cone with the same geometry as Abram’s slump cone, but with proportion-
ally reduced dimensions (bottom diameter of 37.0 mm, top diameter of 19.0 mm
and a height of 57.6 mm), was used in this study. This procedure was applied to
all formulations in triplicate, and the average value is reported herein.
2.2.5. Compressive strength
The compressive strength of cement mortar specimens for each formulation at
pre-determined curing age was executed under uniaxial compression in accordance
with ASTM standard C109-16a [35]. After 7 and 28 days of continuous curing (tem-
perature 23 ± 2 °C; RH > 95%), the compressive strength of triplicate samples was
determined. Pressure was applied to specimens in a calibrated compression press
at a load-controlled rate of 1.32 kN/s using an Instron compression press.
3. Results
3.1. GAC characterization
The surface area and porosity of the GAC-UNM and GAC-ACID
are presented in Tables 5 and 6. HNO3 acidification results in an
approximately 20% reduction of the BET surface area and an aver-
age pore width of 2.4 nm, which corresponds to values in the same
order of magnitude that has been observed in previous studies (i.e.
13–25% and 3.2 nm respectively) [44,45]. The HNO3 acidification
process also reduced pore volumes (total pore volume, micropore,
and mesopore volumes) by 20%, possibly as a result of the destruc-
tion of thin pore walls and constriction of pore entrances by oxy-
gen functional groups, as suggested by previous studies [44,46].
The pH and the oxygen-related functional group content are
presented in Table 7. For each type of carbon, pH and pHPZC corre-
late with the distribution of the measured functional groups. GAC-
UNM showed basic pH and phenolic dominance, while GAC-ACID
showed acid pH and carboxylic dominance [45,47]. Additionally,
the acidification process resulted in an estimated increase of total
(acidic) functional groups by a factor of 10.8. The pH of the PCE-
admixture was close to neutral, while the functional group distri-
bution indicated the dominance of lactonic-related groups
(65.6%), followed by carboxylic (34.4%), but indicated no presence
of phenolic groups.
The 4000–400 cm 1 infrared spectra (FTIR) of the GACs and the
PCE-admixture are presented in Fig. 1. Assignment of observed
bands on the different GACs was based on literature review and
data published by other authors and presented in Table 8.
GAC-UNM showed a faint OAH stretch of alcohol, phenols, and
carboxylic acids, detected as a broad band signal between 3200
and 3700 cm 1 [52–54]. Band associated with stretch of C@O in
cyclic amides at 1546 cm 1 and hydroxyls absorbing at
Table 5
BET surface area and pore size of GAC-UNM and GAC-ACID.
Sample BET Surface t-Plot Micropore t-Plot External BJH Adsorption cumulative
area (m2/g) Area (m2/g) Surface Area(m2/g) surface area of pores between 17
and 3000 Å diameter (m2/g)
GAC-UNM 1341.5 595.2 746.3 209.0
GAC-ACID 1073.6 479.5 594.1 165.5
Table 6
Pore volume of GAC-UNM and GAC-ACID. Micropore volume was obtained from the t-
plot method with the Harkins and Jura thickness equation and mesopore volume was
obtained by using Barret-Joyner-Halenda (BJH) method with the Halsey:Faas
correction.
Sample t-Plot micropore BJH Adsorption cumulative V Micropore/
volume (cm3/g) volume of pores between V total
17 and 3000 Å diameter
(cm3/g)
GAC-UNM 0.2725 0.3079 0.34
GAC-ACID 0.2196 0.2415 0.34
1118 cm 1 were also detected. Bands at 2350 and 670 cm 1 indi-
cated the presence of physiosorbed gaseous carbon dioxide [50].
After acidification, major changes in the FTIR spectra were
observed. Increased intensity of the band located between 3200
and 3700 cm 1 (OAH stretch) was observed, while three new
bands were detected at 1220, 1580, and 1725 cm 1. The first of
the three bands (1220 cm 1) was attributed to a stretch in cyclic
ethers attached to double bonds or asymmetrical stretch in either
bridged group (ACO) [48]. The second band (1580 cm 1) was
attributed to C@O containing groups, namely 1,3 diketone (enol
form) or hydroxy aryl ketone groups [52,53]. The band at
1725 cm 1 was correlated with the presence of ketone, ester, and
carboxylic acid in aromatic rings [52,54].
The spectrum of the PCE-Admixture presented bands character-
istic of PCE molecules. Bands between 1050 and 1150 cm 1 were
attributed to the presence of ether groups (CAOAC) [52,55,56].
The band associated with C@O of ketones, esters, or carboxylic
acids (3200–3700 cm 1) was also observed but with a stronger
absorbance when compared to the GAC-UNM and the GAC-ACID.
The presence of bands at 1580 cm 1 and 1465 cm 1 was assigned
to carboxylate ions [57]. The band at 2885 cm 1 was attributed
to CAH stretching in alkanes [52,54,56].
The surface morphology of GAC-UNM and GAC-ACID was
observed using SEM and is shown in Fig. 2. Surface images were
obtained through the collection and processing of secondary elec-
tron emissions at three different scales for both types of carbon
particles used here. No obvious morphological changes from acid-
ification could be observed at the magnification applied and this
coincides with observations from other authors [47]. SEM images
confirm the GAC particle size, as described in Section 2.2.1.
3.2. Zeta potential
Zeta potential results for the different mortar formulations are
presented in Figs. 3 and 4. All formulations experienced an increase
in zeta potential for the duration of the experiment (120 min). The
control formulation presented the highest and fastest gain, transi-
tioning from 7.05 mV to 10.73 mV in 120 min. A similar behavior
was observed for the formulation containing the PCE-admixture,
showing a continuous increase during the same time lapse and
transitioning from 7.05 mV to 5.68 mV. These initial zeta poten-
tial values are in good agreement with values previously reported
in literature [58].
The formulations containing GAC experienced an initial zeta
potential decrease, followed by a lag (starting at 60 min). Initial zeta
Adsorption average pore Desorption average pore
width (4 V/A by BET) (Å) width (4 V/A by BET) (Å)
24.22 29.71
23.96 26.99
 I. Justo-Reinoso et al. / Construction and Building Materials 207 (2019) 59–69 63

Table 7
pH, pHPZC, and Boehm titration (mmol/g). Number in parenthesis indicate percentage of functional groups for each sample.

Sample pH pHPZC Carboxylic Lactonic Phenolic

GAC-UNM 8.75 9.80 0 (0) 43.1 (42.2) 102.1 (57.8)
GAC-ACID 4.23 4.91 334.8 (46.1) 504.8 (23.4) 726.2 (30.5)
PCE-Admixture 7.21 – 66.8 (34.4) 125.7 (65.6) 0 (0)

GAC UNMODIFIED
Transmittance (%)

GAC ACIDIFIED

PCE-Admixture

Wavenumber (cm-1)

4,200 4,000 3,800 3,600 3,400 3,200 3,000 2,800 2,600 2,400 2,200 2,000 1,800 1,600 1,400 1,200 1,000 800 600 400

Fig. 1. Fourier Transformed Infrared Spectroscopy (FTIR) spectra of GAC-UNM, GAC-ACID and the PCE-Admixture.

Table 8
FTIR vibrations found in GAC-UNM and GAC-ACID.

Peak (cm 1) In reference Surface group Assignment References

This work
3450 3200–3700 OH Alcohol, phenols and carboxylic acids [48]
2342 Around 2350 CO2 Physiosorbed carbon dioxide [49]
1725 1730 C@O Stretch of C@O [49]
1580 1558 C@O Stretch of C@O [50]
1546 1546 CONH Stretch of C@O in cyclic amides [50]
1220 1253 CO Stretch in cyclic ethers attached to double bonds or asymmetrical stretch in either bridged group [48]
1118 1118 COH OH stretch (Hydroxyl absorption) [51]
672 Around 670 CO2 Physiosorbed carbon dioxide [49]

potential of carbon-containing formulations was higher than those
not containing these particles. Both GAC-UNM and GAC-ACID for-
mulations experienced the smallest potential gains, transitioning
from 1.23 mV and 2.13 mV to 4.59 mV and 0.78 mV, respec-
tively (in 120 min). The zeta potential in DI water for the particles
decreased in the following order: GAC-UNM ( 3.60 mV) > GAC-
ACID ( 8.98 mV) > PCE ( 35.96 mV), all showing negative values.
the control formulation (0% GAC) and the other two formulations
containing GAC (UNM and ACID), while for the formulation includ-
ing PCE-Admixture and no GAC substitution, these times were rel-
atively delayed [59,60].
3.4. Workability

3.3. Initial and final setting time
The initial and final setting times as judged by ASTM Standard
Vicat needle penetration tests are shown in Table 9. A similar
behavior in the initial and final setting times was observed for
A comparison between the initial heights and the final heights
obtained from the mini-slump tests are shown in Fig. 5. The slump
for the studied formulations increased in the following order: 1%
GAC-UNM (2.8 mm) < Control (3.5 mm) < 1% GAC-ACID (6.0 mm)
< PCE-Admixture (10.4 mm).
64 I. Justo-Reinoso et al. / Construction and Building Materials 207 (2019) 59–69
Fig. 2. Scanning electron microscope (SEM) images showing surfaces representative of GAC particles. Left images (A, C and E) show GAC-UNM particles; Right images (B, D
and F) show GAC-ACID particles.
3.5. Compressive strength
Compressive strength results at 7 and 28 days are shown in
Fig. 6. Data are reported as the average of at least three cubic spec-
imens ± one standard deviation.
Analysis of variance (ANOVA) was used to determine the signif-
icance of the inclusion of GAC on the compressive strength at the
age of 7 and 28 days, as well as the significant difference between
the use of GAC-UNM and GAC-ACID at 28-days test age. The results
are shown in Table 10.
4. Discussion
4.1. GAC characterization
The physical–chemical changes that can occur in activated car-
bon from engineered exposure to nitric acid has been previously
described [56,61,62]. The degree to which nitric acid affects the
activated carbon surface depends on the acid concentration, carbon
source (i.e., bitumen), and its preparation. For a 5% HNO3 treat-
ment, the 20% decrease in the specific surface area observed was
consistent with that attributed to blocking narrow pores by surface
oxidized complexes [56]. The acid-induced decrease in specific sur-
face area was ascribed to parallel decreases in both micro- and
mesopore volumes, as no significant changes in the net pore size
distribution were observed. Despite the loss in total specific sur-
face area, no differences in the water sorption capacity between
the GAC-ACID particles and GAC-UNM were observed. A possible
explanation for this behavior has been previously offered by Do
and Do (2000), who suggested that significant amounts of new oxi-
dized functional groups with high affinity for water are introduced
to carbon surfaces during acidification, which may compensate for
what would result in a decrease in water sorption capacity due to
micro/meso-pore reductions with the presence of functional
 I. Justo-Reinoso et al. / Construction and Building Materials 207 (2019) 59–69 65

12 Control
Control+ PCE-Admixture
10
GAC-UNM
GAC-ACID
8

6
Zeta potential (mV)

0
0 20 40 60 80 100 120
-2
Time (Min)
-4

-6

-8

Fig. 3. Zeta potential of the particles in the following cement mortar formulations: Control (0% GAC), 10% GAC-UNM substitution, 10% GAC-ACID substitution, and Control (0%
GAC) + PCE-Admixture (0.122% of cement content).

PCE-Admixture GAC-UNM GAC-ACID

0

-5
-3.60

-10
Zeta potential (mV)

-8.98
-15

-20

-25

-30

-35
-35.96
-40

Fig. 4. Zeta potential of the following GAC-UNM, GAC-ACID and PCE-Admixture particles in DI water.

Table 9
Initial and final setting time for the formulations tested as judged by Vicat needle
penetration.
Formulation
Control
1% GAC-UNM
1% GAC-ACID
Control + PCE-Admixture
groups that can bind water through chemisorption and hydrogen
bonding [63].
Acidification lowered the pH and pHPZC of the carbon particles,
with a concomitant shift in both relative and absolute abundance
of oxygen-containing functional groups from Phenolic > Lac-
tonic > Carboxylic in unmodified carbon, to a dominance profile
of Carboxylic > Phenolic > Lactonic in acid-modified carbon. Incor-
poration of carboxylic groups has been described as the major con-
sequence of HNO3 treatment [62] and is consistent with the
aggregate treatment we observed here. FTIR analysis and Boehm
titration confirmed the increased oxidation of GAC-ACID surfaces
through detection of previously absent ester-, ketone-, and
carboxylic-related groups, while indicating a decreased content
of phenol- and alcohol-containing groups.
Acidification of the GAC used as a fine aggregate substitute here,
resulted in a shift of associated functional group profiles (on the
GAC surface), which are similar to functional groups associated
Initial set time (min) Final set time (min)
with the PCE class of superplasticizers. These plasticizers are com-
230 330 posed of a charged ‘‘backbone” (i.e., acrylic, methacrylic, maleic
215 330
acids, vinyl, allyl) and uncharged side chains (i.e., polyethylene
215 345
287 375
oxide) esterified (or amidified) with the carboxylic groups from
the backbone [64]. Significant variations in the chemistry of PCE
backbones and side chains are commercially available. FTIR spec-
trum of the admixture used in this study indicates the presence
of ether, carboxylate, and alkane groups, confirming the described
polymeric nature of the PCE type admixture used here. When
added to cement pastes, PCEs sorb to cement particles, inducing
local areas of negative charge density on a nano-scale. Particle
repulsion results from this electrostatic effect, which can be
enhanced through the steric hindrance of the polymeric chains
on the PCE molecule—the net result is retardation of cement hydra-
tion and consequent setting time, while improving fluidity [65,66].
Substitution of acid-treated GAC particles (GAC-ACID), for fine
aggregate in cement tested here, produced an unambiguous
dose–response, which manifested in a plasticizing effect similar
to that of PCE alone (0.12%) [20,67]. Fig. 2 shows the SEM images
of (A, C, E) GAC-UNM (as-received) and (B, D, F) GAC-ACID samples.
66 I. Justo-Reinoso et al. / Construction and Building Materials 207 (2019) 59–69

60
57.6 57.6 57.6 57.6
Mini-slump cone height (mm)

54.8
54.1

51.6

50

47.2

40
Control 1% GAC-UNM 1% GAC-ACID PCE-Admixture

Fig. 5. Difference between initial height (57.6 mm) and final height during the mini-slump test for each of the following formulations: Control (0% GAC), 1% GAC-UNM
substitution, 1% GAC-ACID substitution, and Control (0% GAC) + PCE-Admixture (0.12% of cement content). Bar height represents the average of three independent
observations.

60
Control
1% GAC-UNM
50 1% GAC ACID 44.3
44.7
Compressive Strength (MPa)

PCE-Admixture 41.1 40.4

40
32.8

30 28.2 26.4
25.8

20

10

0
7 Days 28 Days

Fig. 6. Results represent the average compressive strength (7 and 28-days) response of three cubic specimens for the respective different formulations: 0% GAC (Control), 1%
GAC-UNM substitution, 1% GAC-ACID substitution and 0% GAC + PCE-Admixture. Error bars represent ± one standard deviation.

Table 10
ANOVA results for the compressive strength results.

Source of Variation SS df MS F p-value F critical

GAC Addition (CS at 7-days) 9.93 2 4.96 7.9 0.021 5.1
Within Groups 3.78 6 0.63
Total 13.71 8
GAC addition (CS at 28-days) 23.10 2 11.55 24.3 0.001 5.1
Within Groups 2.85 6 0.48
Total 25.95 8
Type of GAC (CS at 28-days) 0.20 1 0.20 1.8 0.250 21.2
Error 0.45 4 0.11
Total (SQT) 0.65 5

SS: sum of squares; df: degree of freedom; MS: mean square; F: F-statistic (source/error); p-value: obtained from Fisher’s distribution table; F critical: F-critical value.

No significant difference in the surface morphologies of the sam- 4.2. Zeta potential
ples (at the maximum magnification possible) could be observed.
This finding implies that the oxidation treatment of the GAC with Rate of changes in the electrokinetic potential of cementitious
5% HNO3 did not produce any apparent modification in the surface suspensions can describe the repulsive electrostatic double-layer
morphology of the carbon particles used here, which is in agree- interactions associated with hydration [69,70]. For this study, zeta
ment with observations by other authors that have altered GAC potential was leveraged to detect changes in cement particle reac-
with various acids [47,68]. tivity in response to the presence of the various forms and doses of
 I. Justo-Reinoso et al. / Construction and Building Materials 207 (2019) 59–69
GAC (GAC-UNM and GAC-ACID) and PCE-admixture. These mea-
sures indicated a negative potential for both forms of GAC as well
as the PCE. However, the zeta potential was lower in the PCE-
admixture, suggesting an effect of particle size, molecule shape,
and solubility of this powdered admixture as compared to the car-
bon particles, especially GAC-ACID, which contained a significantly
higher number of oxygen-related functionalities (parallel to those
functionalities responsible for the electrostatic interactions associ-
ated with PCEs). The evolution of the zeta potential with respect to
the time elapsed for the PCE-Admixture formulation showed the
behavior mentioned by other authors when superplasticizers are
used in cement pastes [71,72]. Conversely, a higher initial poten-
tial, followed by net zero potential gained in the first 60 min,
was observed for the GACs. The final potentials of GAC particles
were lower than that for the PCE superplasticizer, with GAC-ACID
having the lowest value and the lowest overall potential gain
among the formulations tested. These results indicate different
mechanisms of particle–particle interaction between the admix-
ture and the carbons during the first 120 min.
4.3. Initial and final setting time
Initial and final setting times of cement mortars were not signif-
icantly affected by the substitution of sand with the either type of
GAC (GAC-UNM and GAC-ACID). However, the PCE-Admixture
formulation (at a dose of 0.12%) delayed the setting times when
compared any of the other formulations (i.e., Control (0% GAC),
1% GAC-UNM and 1% GAC-ACID). The literature substantiates some
consensus [16,20,66,73] that larger amounts of PCEs superplasti-
cizers may retard setting time, mainly due to adsorption of these
polymers on the surface of the cement particles and preventing
the formation of hydration products, as well as slowing the kinetics
and morphology of early hydrates.
4.4. Workability
The results obtained show that the substitution of 1% sand with
GAC-ACID increased the slump of the cement mortar by 71.4%
when compared with the Control formulation (0% GAC substitu-
tion). On the other hand, when using the same percentage of sub-
stitution of GAC-UNM, the slump response decreased by 20%,
resulting in a stiffer cement mortar. For the PCE-Admixture formu-
lation, the slump increased 197.1% with respect to the Control for-
mulation, resulting in a more workable cement mortar. As judged
by the mini-slump responses, the substitution of fine aggregate
by GAC-ACID particles in the cement mortar formulations pro-
duced a mechanical plasticizing effect similar to the one observed
when the PCE-Admixture was used.
4.5. Compressive strength
Two different behaviors where observed between the compres-
sive strength results of 7-days and 28-days. First, at the age of
7-days, the PCE-Admixture formulation exhibited a higher com-
pressive strength than the other three formulations (i.e., 16.3%
more than the Control formulation). Even though the Control and
the PCE-Admixture formulations have the same components and
same w/c ratio, this early strength is attributed by Mehta P. K.,
et al. (2006) [20] to a greater rate of cement hydration in response
to a PCE-induced enhancement of particle dispersion. Second, the
formulations containing GAC substitutions, either GAC-UNM or
GAC-ACID, exhibited lower compressive strengths (7-day) when
compared to the Control formulation (i.e. 9.3% and 6.8% lower
strength, respectively). This result suggests that at 7 days, the
porous nature of the GAC particles may be more significant than
67
the additional cement hydration provided by the GAC grains in
the overall compressive strength.
After 28 curing days, however, compressive strength increased
in response to a 1% mass substitution of fine aggregate with simi-
larly sized activated carbon grains (GAC-UNM and GAC-ACID).
These GAC substitutions manifest in an increase of the compressive
strength of the cement mortars formulations of 7.7% and 8.8%,
respectively. The parallel PCE-containing formulation, with only a
1.7% compressive strength increase, exhibited a more modest
strength gain with respect to the Control formulation (0% GAC).
Some authors have observed gain in compressive strength of
cementitious materials with activated carbon substitutions
[4,10]. The strength response observed in this study for 1% GAC
substitution may be attributed to local hydration produced by
the water released from the GAC pores; this water may have pro-
moted micro-scale curing around the GAC grains, a process that
less porous sand particles cannot achieve. A 1% sand replacement
by GAC may maximize this internal curing and compensate for a
decrease in the intrinsic compressive strength resulting from
replacing solid silica sand grains with weaker and porous GAC
grains [10]. Results by Justo et al. (2018), suggest that microscale
capillary segmenting may occur in cured cement mortars when
hydrated GAC is substituted for fine aggregate (1% by mass), result-
ing in a more dense cement matrix with a lower porosity (20%
decrease) when compared to identical cement mortars with no
GAC substitutions [10]. The results from compressive strength
were statistically analyzed through the analysis of variance
(ANOVA). Results showed that GAC particles substitution has a sig-
nificant effect on the compressive strength (7 and 28-days) as the
p-value obtained was less than 0.05 (95% confidence level) and F-
statistic was greater than F-critical value. On the other hand,
results showed that the type of GAC used was statistically not sig-
nificant on the results of compressive strength at 28-days, since p-
value was greater than 0.05.
5. Conclusions and significant findings
This investigation isolated the effects of acidified granular acti-
vated carbon (GAC-ACID) on the fresh-state and mechanical prop-
erties of ordinary Portland cement mortars. The study compared
the effect of acidified GAC admixture additions against a polycar-
boxylate (PCE) superplasticizer and otherwise unmodified GAC.
The significant findings of this work are as follows:
- Acidification of GAC with nitric acid (HNO3) resulted in a signif-
icant addition of oxygen-containing functional groups (acidic
groups) to these particles. When acid-treated GAC was substi-
tuted for fine aggregate above a certain threshold, this condition
contributed to a cementitious materials response similar to that
observed when incorporating only conventional PCE
superplasticizers.
- Substituting fine aggregate with 1% GAC-ACID by mass
improved workability without impacting significantly initial
and final setting times, unlike the PCE-containing formulation,
which exhibited a delay in setting time compared to the exper-
imental control.
- Substituting fine aggregate with 1% GAC-ACID by mass
decreased compressive strength at 7 days by 6% compared to
the control, but the GAC-ACID increased compressive strength
at 28-days between 9% and 11% when compared to the control
(0% GAC) and the control containing the PCE-admixture (0.12%),
respectively. ANOVA results indicate that no significant differ-
ences were observed in compressive strength when comparing
1% substitutions of GAC particles with and without
acidification.
68 I. Justo-Reinoso et al. / Construction and Building Materials 207 (2019) 59–69
Conflict of interest
None.
Acknowledgments
The authors gratefully acknowledge to Dr. Jennifer Underwood
and Dr. Tyler Kane (USGS-Boulder), Catherine Lucero, P.E. (USBR-
Denver) and, CIDI-UAG (Centro de Investigación para el Desarrollo
Industrial) belonging to the Universidad Autónoma de Guadalajara
(UAG) (México) for their support during the experiments of this
study. This research was supported by the Mexican National Coun-
cil for Science and Technology (CONACYT) (Fellowship No. 103259)
and by the Department of Civil, Environmental & Architectural
Engineering at the University of Colorado-Boulder through a Doc-
toral Dissertation Completion Fellowship.
This work represents the views of the authors and not necessar-
ily those of the sponsors.
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