Construction and Building Materials 184 (2018) 11–19

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Construction and Building Materials

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

Effect of a high content in activated carbon waste on low clinker cement

microstructure and properties
Moises Frías a,⇑, Raquel Vigil de la Villa b, Rosario García b, Sagrario Martínez c, Ernesto Villar d, Iñigo Vegas e
a
Eduardo Torroja Institute for Construction Science (IETcc-CSIC), 28033 Madrid, Spain
b
Department of Geology and Geochemistry, CSIC-UAM Associated Unit (Geomateriales), Autonomous University of Madrid, 28049 Madrid, Spain
c
Institute for the Structure of Matter (IEM-CSIC), 28006 Madrid, Spain
d
Department of Physics, Central University of Las Villas, Santa Clara 54830, Villa Clara, Cuba
e
Tecnalia, Parque Tecnológico de Bizkaia, 28160 Derio, Spain

h i g h l i g h t s

Blended cements with 20%–50% additions are standard-compliant.

The binder containing 50% AC qualifies as a low heat cement.

Drying shrinkage is more intense in high AC content cements.

Adding 20%–50% AC to cement lowers its mechanical strength.
3

Computed tomography shows that the addition raises the intermediate macropore (0.001–0.09 mm ) volume.

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

Article history: In the context of cement industry sustainability and socio-economic development, one of the primary
Received 19 February 2018 objectives of the circular economy is the use of industrial waste as a supplementary cementitious mate-
Received in revised form 14 June 2018 rial in the manufacture of future eco-efficient binders. This paper reports a first-time study of the effect of
Accepted 26 June 2018
large proportions of the activated carbon (AC) waste used in low clinker cements on the properties and
Available online 30 June 2018
structure of the new binders. The behaviour of blended cement matrices prepared with 20%–50% AC as a
pozzolan was analysed in terms of their chemical, mechanical and physical (rheology, heat of hydration,
Keywords:
drying shrinkage, microporosity) properties. Macroporosity was also assessed with computed tomogra-
Activated coal waste
Low clinker cements
phy (CT). The findings showed that these blended cements meet standard chemical and rheological
Properties requirements and that the 50% AC binder qualifies as a low heat cement. Drying shrinkage was observed
Behaviour to intensify with higher percentages of AC. A rise in total porosity was attendant upon pore size
Pore structure refinement, with an increase in the <100 nm fraction. Compressive strength declined with rising replace-
ment ratios. Further to the CT findings, macroporosity (0.001–0.09 mm3) also increased with AC content,
especially in the binders bearing 50% of the addition.
Ó 2018 Elsevier Ltd. All rights reserved.

1. Introduction generated is attributable to limestone decarbonation during the

World population growth to an expected 9.2 billion by 2050
will entail a steady increase in the consumption of construction
materials, cement among them. One of the adverse environmental
implications of the manufacture of this artificial material is the
release of greenhouse gases, with the emission of CO2 accounting
for 5%–7% of the worldwide total. Sixty per cent of the CO2
⇑ Corresponding author.
E-mail address: mfrias@ietcc.csic.es (M. Frías).
industrial process. Cembureau [1] has adopted a low carbon
economy strategy, targeting an 80% potential reduction by 2050.
With a view to reaching that goal, the cement industry is backing
a number of innovative approaches [2], one of which would replace
higher percentages of clinker with eco-efficient pozzolans.
On the whole, the wide variety of alternative pozzolans
presently known are scientifically and technically apt for use as
additions in portland cement manufacture [3–8]. As they have
been introduced fairly recently, they are normally added at low
replacement ratios, a practice that provides little or no information
on the behaviour of low clinker cements.

https://doi.org/10.1016/j.conbuildmat.2018.06.216
0950-0618/Ó 2018 Elsevier Ltd. All rights reserved.
12 M. Frías et al. / Construction and Building Materials 184 (2018) 11–19

One of the lines of research presently pursued is the reuse of Mortar microporosity and fluctuations in pore size distribution over time were
determined on a Micromeritics Autopore IV 9500 mercury porosimeter, with a 60
kaolinite-based waste as an alternative to metakaolinite, a highly
nm lower limit.
pozzolanic product referenced in international standards on com- X-ray computed tomography (CT) analyses, conducted on a Nikon XT-H-160
mercial cement manufacture. One such waste is activated carbon scanner fitted with a W target 0.375 mm Cu filter, were recorded at 708 ms per
[9–10], notorious for the environmental damage caused when frame, with a total of four frames and 1100 scans at 155 kV and 57 mA.
stockpiled near the respective coal mine [11]. Particle size and its distribution were found on a Mastersizer 3000 laser spec-
trometer using air as the dispersion medium, with particle size ranging from 0.01
To date, studies [12–14] have been conducted on how substitut-
to 3500 mm.
ing these materials for up to 20% of the cement in binders may alter Heating and heat of hydration were quantified applying the Langavant semi-
the kinetics and properties of the pozzolanic reaction. The findings adiabatic procedure, pursuant to European standard recommendations [19]. An
have served to establish the protocol for their use as supplemen- inert (12 month old) reference cement was placed in the inner bottle of a Dewar
vacuum flask and the paste to be tested in the outer. Heating (°C), defined as the
tary cementitious materials (SCMs).
difference in temperature between the two, was used to calculate heat of hydration.
Despite that progress, the effect of high percentages of activated
carbon waste (AC) on the behaviour and properties of binary
cements is a line of research unexplored by the scientific commu- 3. Results and discussion
nity. The priority objective of the present study was to gain insight
into the chemical, physical and mechanical performance and 3.1. Physical-chemical characterisation of starting materials
microstructure of blended cements bearing up to 50% AC.
The chemical composition of the carbon waste before and after
thermal activation at 600 °C given in Table 2 shows that the AC was
2. Experimental alumino-siliceous. The sum of the acid oxides SiO2 + Al2O3 + Fe2O3
accounted for over 86% of the total, a value much higher than the
2.1. Materials
70% minimum required in the U.S. standard for qualification as a
Activated carbon waste (AC) from coal tailings furnished by an open-pit mine class N pozzolan [20]. It had a reactive silica content of 21.80%
owned by Sociedad Anónima Hullera Vasco Leonesa, sited in the northern Spanish and a free lime content of 0.16%. The chemical compositions of
province of León, was activated under energetically, economically and environmen- the blended cements used in this study, also given in the table,
tally optimal conditions: in a laboratory muffle furnace at 600 °C for 2 h [15]. Table 1
showed that at 1.70% their sulfate and at 0.01% their chloride con-
gives the Rietveld values for the mineralogical phases in both the tailings and the
thermally activated waste. tents were much lower than the ceilings allowed in the European
The potential composition of the CEM I 52.5 R [16] Spanish commercial cement standards in place [16] (SO3  3.5% or 4.0% and Cl  0.1%). Bin-
used, determined with the Bogue method, was: 41.74% C3S; 27.95% C2S; 8.33% C3A; ders containing up to 50% AC would consequently meet the chem-
and 8.79% C4AF. ical requirements for classification as CEM type II or IV cements.
Blended cement pastes were prepared with 20%, 30% and 50% AC (hereafter 20%
Fig. 1 reproduces the particle size distribution curves for the
AC, 30% AC, 50% AC). Three prismatic mortar specimens (4  4  16 cm) were pre-
pared with a water/binder (w/b) ratio of 0.5 and a sand/cement ratio of 1/3, accord- four cements analysed. A major peak at around 20 mm in all four
ing to the existing standard. For each hydration time an average value was obtained declined in intensity with rising percentages of AC, while a less
from 5 compressive strength values. intense shoulder at 4 mm grew in intensity with the replacement
The sand used consisted in standard sand with a minimum silica content of 98%
ratio. Despite these changes in peak intensity, the particle size
and maximum particle size of 2 mm. A melanin-based superplasticiser (Sika,
Madrid: Sikament FF) was added to lower water demand.
range was 0.1 mm–100 mm in all the binders. The D10, D50 and D90
For the shrinkage under the drying condition test, four prismatic specimens (25 values (particle sizes below which 10%, 50% and 90%, respectively,
 25  285 mm3) were moulded from OPC, 20% AC and 50% AC mortars. Six mm of the particles lie) are given in Table 3.
diameter stainless steel cylinders were embedded in both ends of the specimens,
separated by a calibrated distance of 254 mm. The specimens were stored in the
moulds in a humidity chamber for the first 48 h, subsequently demoulded and
3.2. Pozzolanic activity and modelling
immersed in water for 24 h, after which the initial measurements were made. Spec-
imen readings were recorded under laboratory conditions (20 °C, 60% RH) with a The behaviour of activated carbon (AC) waste in a cement
dial gauge comparator. The test was run for 63 d to ensure that shrinkage had matrix depends on its reactivity with the lime released in the
peaked in all the mortars [17].
hydration reaction. The lime fixed by the AC over time is compared
to the values for other types of industrial waste such as fired clay-
2.2. Methods and instrumental techniques based products (CW) and paper sludge (PS) in Fig. 2 [21,22]. With a
high absorption rate of 40% in the first 24 h and 90% after 90 d, the
AC waste pozzolanicity was evaluated with an accelerated chemical method in
AC waste exhibited pozzolanicity similar to that of the other two
which samples were immersed in a saturated lime solution at 40 °C [18]. The lime
absorbed at each test age was calculated as the difference between the concentra- types of waste. The kinetic coefficients for the pozzolanic reaction
tion of the reference solution (17.68 mmol/L) and the CaO content in the problem can be calculated by applying the diffusive kinetic model (Eq. (1))
solution. to the pozzolan/Ca(OH)2 system [23].
The cements were analysed for chemical composition with a Philips PW 1404
X-ray fluorescence (XRF) analyser fitted with an Sc-Mo X-ray tube, a gas scintilla-
tion detector and a PR-10 anode. Table 2
The mineralogical phases identified in the coal tailings and activated carbon XRF-determined chemical composition (%) of starting materials and blended cements.
were Rietveld quantified using rutile as the internal standard at a concentration
% Tailings AC OPC 20% AC 30% AC 50% AC
of approximately 5%.
The 90 d cement mortars were studied for morphology under a Hitachi S4800 SiO2 49.79 56.63 20.80 30.67 35.42 43.19
scanning electron microscope coupled to a Bruker Nano XFlash 5030 silicon drift Al2O3 21.77 25.29 5.70 11.13 14.06 18.64
detector for EDX analysis. Fe3O2 4.07 4.64 2.89 3.16 3.19 3.35
CaO 3.84 4.20 58.99 45.34 37.77 25.51
MgO 0.64 0.77 1.89 1.58 1.45 1.21
Na2O 0.13 0.17 0.93 1.58 1.29 0.94
Table 1 K2O 2.74 3.09 1.36 1.34 1.60 2.28
Coal tailings and activated carbon mineralogical composition (Rietveld, %). SO3 0.27 0.27 4.11 1.69 1.62 1.16
TiO2 1.07 1.17 0.15 0.29 0.37 0.54
% Calcite Kaolinite Quartz Mica Amorphous phase P2O5 0.13 0.14 0.26 0.19 0.19 0.17
Tailings 15 14 29 25 17 Cl <0.01 <0.01 0.02 <0.02 <0.02 <0.02
AC-600 10 – 35 20 35 LOI 15.18 3.09 2.79 2.92 2.93 2.95
 M. Frías et al. / Construction and Building Materials 184 (2018) 11–19 13

Table 4
Physical properties of blended cement pastes.

Property OPC 20% AC 30% AC 50% AC Recommended

Without additive
WNC (g) 153 169 180 200 –
With additive
WNC (g) 153 153 153 153 –
Sika FF (g) 0 4 6 7.5 –
IS (±5 min) 2 h 15 2 h 20 2 h 20 1 h 55 45–60 min
min min min min
E (mm) 0.0 1.0 1.5 2.0 10

Fig. 1. Particle size distribution curves.

consistency (WNC), initial setting time (IS) and volume expansion

Table 3 (E) to determine the effect of high AC content on the cement
Particle size (mm) below which 10%, 50% and 90% of cement particles lie.
matrix. The experimental and accepted standard values for those
Sieve size OPC 20% AC 30% AC 50% AC physical properties are listed in Table 4.
D10 1.98 1.57 1.45 1.31 The inclusion of 20%, 30% and 50% AC in the blends raised the
D50 12.8 11.1 10.1 9.12 water demand recorded for the OPC paste by 10.5%, 17.6% and
D90 35.9 35.7 35.6 36.5 30.7%, respectively. That behaviour was comparable to the findings
for other kaolinite-based pozzolans, for the water sorptivity of clay
minerals (metakaolinite, micas, feldspars) is greater than that of
cement particles [26].
In light of this greater water demand in the blended cements
and its possible adverse effect on strength and durability, all the
pastes were prepared with the same w/b ratio, taking the OPC
paste as a reference and adding the amount of superplasticiser
needed to pass the standard slump test (Table 4). The other
physical properties were determined on pastes with the
dosages specified in the table. Initial setting time relative to the
reference paste was not significantly altered by high AC content,
although it was brought forward by 10 min to 15 min in 50% AC.
That may have been related, among others, to the extra alkalis
introduced in the mixing water by the admixture (13.5%,
according to the specifications sheet) and the calcite present in
Fig. 2. Lime fixed versus reaction time. the AC (4%) [27].
Despite the high percentages of AC present in the matrices, the




blended cements did not exhibit significantly greater expansion
C0  Ct 0;23 :Exp 3s t : 1 þ Exp st : 1s 0;23:Exp  st : 1s than the OPC paste.
n¼ ¼1 þ
C0 C o De r s C 0 K r 2s Moreover, all three blended cements were standard-compliant
ð1Þ in terms of both setting and expansion (Table 4).

where De is the effective diffusion coefficient, K is the reaction rate 3.3.2. Blended cement mortars
constant, Co is the initial concentration of the solution and s is a As in the cement pastes, the inclusion of large percentages
time constant (time interval in which the radius of the pozzolan of AC waste in mortars at a constant w/b ratio of 0.5 induced
nucleus declines to 37% of its starting radius (rs)). The starting a loss of workability, which was accentuated at higher poz-
radius, rs, of the pozzolan particles was taken as 0.090 mm. The zolan contents. As the data in Table 5 show, the inclusion
dimensionless magnitude n = (Co  Ct)/Co represents the relative of thermally activated carbon raised water demand by 10.6%
loss of lime concentration and Ct the absolute loss of lime concen- in the 20% AC mortars, by 13.3% in the 30% AC mortars and
tration over time in the pozzolan/lime system. by 29.7% in the 50% AC mortars relative to the reference.
The reaction rate constant K (h1) for AC was (6.8 ± 0.54)  Similar patterns were reported by researchers working with
103, a value very close to the K for paper sludge [(8.69 ± 0.94)  pozzolans derived from sanitary ware waste [28],
103] and one order of magnitude higher than for fired clay- metakaolinite-based paper industry waste [29] and agroindus-
based waste [(6.19 ± 0.82)  104]. Those findings would be trial ash [30–32].
related to the activation temperature: whilst AC and paper sludge
were activated at 600 °C, the clay was fired at 800 °C to 1000 °C,
inducing greater metakaolin crystallisation to mullite or spinel
[24] and hence a slower reaction rate. Table 5
Cement mortar physical parameters.

3.3. Physical properties OPC 20% AC 30% AC 50% AC

Water demand (g) 225 249 255 292
3.3.1. Blended cement pastes Slump (±1 mm) 165 165 166 165
Adjstd wtr dmnd (g) 225 225 225 225
In keeping with European standard 196-3 [25] recommenda-
Admixture (g) 0.0 4.0 4.4 5.9
tions, the present study focused on the water required for normal
14 M. Frías et al. / Construction and Building Materials 184 (2018) 11–19

3.4. Heat of hydration Table 6

Heating and heat of hydration in 41 h mortars.

One of the key factors affecting cement matrix durability is the OPC 20% AC 30% AC 50% AC
heat of hydration generated in the first 10 h–20 h, for the low Peak time (h) 10 12 13 15
thermal conductivity of these matrices gives rise to steep thermal Temperature (°C) 38.9 34.7 33.1 26.3
gradients in their interior, particularly when large volumes of bulk Heat of hydration (J/g) 351 313 300 255
concrete are used. In such circumstances identifying the cement, Std EN196-9 Low heat cement < 270 J/g at 41 h

dosage and pozzolan type (and quality within a given pozzolan)

best suited to the intended application is of cardinal importance.
This section analyses the effect of high AC content on heating
and heat of hydration in standardised mortars. The results for the
first 80 h found by applying the Langavant semi-adiabatic method
[19] are shown in Fig. 3.
The data on fluctuations in mortar temperatures showed that
heat peaked at 10 h–15 h after initial hydration, with higher AC
contents retarding peak time: the 50% AC mortar peak appeared
5 h later than the reference peak.
The maximum temperature reached followed a similar pattern,
with values 10.8% lower in the 20% AC, 15% lower in the 30% AC
and 32.4% lower in the 50% AC mortar than in the reference.
Similarly, heat of hydration was lower in all the AC mortars
than in the reference across the entire measuring range (Fig. 3).
Whilst no significant differences were observed between the 30%
AC and 20% AC mortars, higher replacement ratios (50% AC) low-
ered heat of hydration substantially. The 41 h heat of hydration
value for 20% AC mortars was 10.8% lower than the reference, for
30% AC, 14.5% lower and for 50% AC, 27.3% lower (Table 6). The
steeper decline in heat of hydration in the mortars bearing 50%
of the addition would be related to a number of possibly overlap-
ping factors. Such a high percentage might have generated an
excess of the pozzolan and consequently insufficient lime with
which to react. Under those conditions, the AC would act as a filler.
The delay might also be associated with metakaolin’s high water
sorptivity, as reported by Jiang et al. [33]. That effect would be
reinforced by the presence (13%) of micas in the waste which, as
Table 5 shows, have a high water demand.
Lower heat of hydration would have a beneficial effect on dura-
bility in applications involving large volumes of bulk concrete or
concrete cast in place at high ambient temperatures. This feature
of metakaolinite-based waste resembled that found in pozzolans
traditionally used in commercial cement manufacture [34], but dif-
fered widely from 100% metakaolinite; Frías et al. [35], observed
heat of hydration to be 10%–30% higher in MK blended mortars
than in the reference. The presence of other compounds such as
micas and calcite very probably prompted the differences relative
to pure MK observed here. Shananham et al. [36], in turn, found
a linear relationship between the reduction in total heat and the
rise in portland cement replacement by fly ash, silica fume and
metakaolin.
Further to European standard EN 196-9 specifications, the 50%
AC mortars, which exhibited 41 h heat of hydration lower than
270 J/g, would be categorised as low heat cements.
3.5. Entire shrinkage under the drying condition
Shrinkage is another property to be considered when manufac-
turing new eco-efficient cement matrices. The entire shrinkage
under the drying condition covers both the drying shrinkage, due
to the water loss; and autogenous one, as a consequence of the
internal hydration of tne cementitious materials. The autogenous
shrinkage is mainly attributed to the chemical reaction among
the cementitious constituents, while the factors primarily affecting
the drying shrinkage are ambient humidity, element geometry and
curing time [37].
The dosages for the OPC, 20% AC and 50% AC mortars are given
in Table 7, whilst entire shrinkage for the three materials is plotted
against age in Fig. 4. The 20% AC and 50% AC mortars exhibited con-
sistently greater drying shrinkage than the OPC mortar. The great-
est differences were recorded in the first 18 h, where the 20% AC
mortar shrank 18.6% more and the 50% AC mortar 24.6% more than
the unadditioned mortar. A turning point was observed between
the two additioned mortars at 27 h, when the 20% AC material

Table 7
Mortar dosage.

Cement type Standard Binder (g) Water (g) Admixture

silica sand (g)
CEM I 52.5 N AC (g) (%)
OPC 675 225 – 112.5 – –
20% AC 675 180 45 112.5 2.00 0.89
50% AC 675 112.5 112.5 112.5 2.95 1.31

Fig. 3. Heating and heat of hydration in mortars versus time. Fig. 4. Drying shrinkage versus hydration time.
 M. Frías et al. / Construction and Building Materials 184 (2018) 11–19 15

slightly outpaced the 50% AC mortar and continued to exhibit of resistances between the unadditioned and additioned mortars,
greater shrinkage through the end of the test. In the 63 d materials, an indication that the pozzolanic reaction between calcium
entire shrinkage was 18.5% greater in 20% AC and 11.61% higher in hydroxide and the metakaolinite present in AC was underway.
50% AC than in OPC. The inversion observed might be related to the Strength loss fluctuated very little at later ages, with 180 d
higher water demand in the 20% AC mortar, where the hydration strength 10% (20% AC), 21% (20% AC) and 38% (50% AC) lower than
and pozzolanic reactions took place simultaneously, whereas in in the reference mortar. Earlier studies conducted by Vegas et al.
the 50% AC mortar the effects of the high replacement ratio and [38] showed that mortars with activated carbon contents of up
lower effective water content available for the reaction would to 10% exhibited higher 28 d compressive strength than the refer-
prevail. ence mortar. Here, however, strength was observed to decline with
Generally speaking, including active additions in cement raises rising replacement ratios. That finding was corroborated by the
entire shrinkage under drying conditions, an observation that SEM micrographs (Fig. 6), which clearly showed the presence of
would be directly related to the changes induced by pozzolans in spherical pores in the blended cement matrices, particularly in
cementitious systems as a result of the filler effect (hastening the 50% AC mortar.
hydration), the pozzolanic effect (chemical capacity to react with
calcium hydroxide) and pore structure refinement (fewer capillary
pores, hindering water transport) [38,4].
The entire shrinkage induced by AC additions is in line with
observations for traditional additions such as silica fume [39], slag
[40], metakaolin [41] and limestone [42], as well as for agroindus-
trial pozzolans [43]. All the studies cited highlighted the impor-
tance of the pozzolan in entire shrinkage under drying
conditions, which depended on the chemical and mineralogical
properties of the pozzolan, its fineness, the replacement ratio used,
geometric considerations, the thermal gradient and the water/bin-
der ratio.
The incorporation of fibers might lead to a reduction in the
entire shrinkage under drying conditions. Recent studies [44]
report that steel fibers lead to higher reduction in the entire
shrinkage when comparing to polymeric fibers.

3.6. Mechanical properties/SEM

Mortar compressive strength was determined on standard

mixes prepared with sufficient superplasticiser for each dosage
to ensure that all the blended cement mortars had the same 165
mm slump as the OPC reference (Table 5).
Compressive strength is plotted against time, up to 180 d, in
Fig. 5. The patterns observed were similar for all the materials,
with strength rising substantially in the first 28 d. Thereafter in
OPC, 20% AC and 30% AC the values fluctuated only slightly, by
around 5.6%–7.0% through the end of the test, whereas a 12.2%
strength gain was observed between 28 d and 180 d in the 50%
AC mortar. Compressive strength clearly declined relative to the
reference in the 1 d blended mortars, more steeply at higher
replacement ratios, turning downward by 26% in 20% AC, 43% in
30% AC and 70% in 50% AC (Fig. 5-1). Those findings might be the
result of delayed cement particle hydration due to the presence
of the pozzolan, an effect that would intensify with rising AC con-
tent. At 7 days, there is a significant reduction in the relative losses Fig. 6. SEM micrographs of 90 d OPC and 50% AC mortars.

Fig. 5. Compressive strength versus time.

16 M. Frías et al. / Construction and Building Materials 184 (2018) 11–19

Fig. 7. Correlation between compressive strength and heat of hydration.

3.7. Relationship between strength and heat of hydration

One of the key issues explored in this study was the analysis of
the possible relationship between compressive strength and the
heat generated in mortars with high percentages of activated car-
bon. If such a relationship could be established, either of the two
parameters could be estimated on the grounds of the values of Fig. 8. Total porosity and mean pore diameter versus reaction time.
the other. Earlier results in this regard identified different correla-
tions, found to be directly dependent upon cement type, cement
The addition of AC induced a significant decline in mean pore
plant and nature and quality of the pozzolan. Research recently
diameter (4V/D) relative to the reference mortar at all ages,
conducted by Endogan et al. [45] yielded a good correlation
although the 90 d differences among the three additioned mortars
between 12 h and 48 h heat of hydration and 1 d–7 d strength
were minor. Mean pore size was 33%–40% smaller in the 180 d
for all the blast furnace slag blended cements studied taken as a
blended cement mortars than in the 180 d reference OPC. That pat-
whole, but less promising results when taken one by one. In the
tern was clearly visible in the 7 d and 180 d pore size distribution
latter case, the highest correlation was obtained for heat of hydra-
curves (Fig. 9), indicative of pore size refinement, particularly in
tion in the 24 h to 48 h range. Baran and Pichniarczyk [46],
the 180 d additioned mortars in which the nanopore fraction
working along those same lines, obtained a good correlation for
28 d type I and type III (blast furnace slag) cements manufactured
at just one cement plant. For all the rest, the relationship between
compressive strength and heat of hydration was moderate to weak.
In light of that prior research, the correlation between the two
parameters was studied in the four cements analysed (0%, 20%,
30% and 50% replacement), plotting the 12 h, 24 h and 41 h heat
of hydration (J/g) values against 1 d, 7 d and 28 d compressive
strength. In this study, the 41 h heat of hydration age specified in
connection with the Langavant semi-adiabatic method by the stan-
dards in place [32] was used instead of 48 h, although the values
for the two times were practically identical.
As the regression lines reproduced in Fig. 7 show, a very high
correlation was obtained for all three series, with linear correlation
coefficients (R2) of 0.95–0.97 in all cases. Those findings attested to
the high pozzolanicity of the thermally activated carbon in the
cement matrix, inferring that strength could be reliably calculated
from the heat of hydration values, thereby obviating the need for
experimental tests.

3.8. Microporosity

The total porosity and mean pore diameter values found with
mercury porosimetry, a technique widely used to characterise
microporosity, are plotted against time up to 90 d in Fig. 8. In the
7 d materials, porosity grew with the replacement ratio. At later
ages, porosity in 20% AC and 30% AC was similar to the reference
value, although somewhat lower in the 20% material. In contrast,
total porosity in the 50% AC mortars was 24%–30% higher than in
the reference OPC. Fig. 9. Correlation between compressive strength and total porosity.
 M. Frías et al. / Construction and Building Materials 184 (2018) 11–19 17

observed between compressive strength and total porosity in the 7

Fig. 10. 7 d and 180 d pore size distribution curves.
(<100 nm) grew. The effect was most visible in the 50% AC mortar,
where the highest peak was located at 0.07 mm (70 nm), compared
to 0.17 mm (170 nm) in the OPC material. A linear relationship was
d, 90 d and 180 d mortars, with R2 = 0.82 (Fig. 10). That rather low
correlation coefficient was consistent with Feldman and Beau-
douin’s [47] contention that, whilst porosity is the factor with
the heaviest impact on mechanical strength, sight cannot be lost
of particle morphology and density. In that same vein, Goñi et al.
[48] observed a good correlation between C-S-H gel nanostructural
characteristics and compressive strength.
The CT-determined volume of macropores in the ranges >0.09
mm3, 0.09 mm3 to 0.001 mm3 and <0.001 mm3 is plotted against
time for 0% AC, 30% AC and 50% AC in Fig. 11. Although pore vol-
ume remained practically constant in the reference mortar
between 7 d and 90 d, after 180 d the number of intermediate
pores grew at the expense, primarily, of the smallest pores
(<0.0001 mm3). The 30% AC mortar also evolved toward pore sizes
between 0.09 mm3 and 0.001 mm3, whereas the 50% AC material
exhibited substantial changes in pore volume with hydration time,
with most of the pores under 0.001 mm3 (87% in the 7 d mortar)

Fig. 11. Computed tomography quantification of macroporosity.

Fig. 12. Macroporosity in (left) 7 d and (right) 180 d 50% AC mortar.

18 M. Frías et al. / Construction and Building Materials 184 (2018) 11–19
developing into intermediate pores (78%) in the 180 d mortar. The
bar graph in Fig. 12 shows the substantial difference in the pore
size distribution between the 7 d and 180 d 50% AC mortar. That
rise in macroporosity with replacement ratio and curing time
was wholly consistent with the decline in compressive strength
discussed above.
4. Conclusions
The conclusions to be drawn from this study are listed below.
1. Blended cements prepared with 20%–50% AC meet the chemical
requirements for use in the manufacture of type II and type IV
cements, with the exception of the reactive silica content,
which at 22% is slightly lower than the 25% recommended
by the standards in place.
2. Activated carbon waste is highly reactive in the cement med-
ium, with the 90 d materials absorbing 90% of the free lime.
The reaction rate constant for AC is of the same order of magni-
tude (103) as (likewise metakaolinite-based) activated paper
sludge, and one order of magnitude higher than the value for
fired clay-based waste (104).
3. Water demand is higher in the blended cements than in the
reference and rises with the replacement ratio, to 31% in
50% AC pastes. The incorporation of high AC contents does
not affect practically to the cement paste expansion and ini-
tial setting time. Setting time is slightly shorter in the 50%
AC due to the presence of limestone in its mineralogy. The
additioned cements meet the requirements in place for both
parameters.
4. The additioned cement mortars retard the appearance of the
peak temperature (by up to 5 h) and lower heat of hydration
by up to 27%, depending on the pozzolan content. As the 50%
AC mortar can be categorised as a low heat cement, it would
be ideal for applications where that characteristic is a key
concern.
5. Drying shrinkage is 11% greater in the 20% AC and 18% greater
in 50% AC than in the reference OPC mortar. Whilst in the first
27 h, the higher the pozzolan content the more intense the
shrinkage, after that age shrinkage is slightly greater in the
20% AC than in the 50% material.
6. The inclusion of AC induces a decline in compressive strength at
all ages, but particularly in the 1 d materials where the loss is
greater than the replacement ratio. These differences with the
reference OPC narrow with reaction time, to 10% (20% AC),
21% (30% AC) and 38% (50% AC) in the 180 d mortars.
7. The mortars prepared with 20% and 30% AC cement exhibit
medium- and long-term total porosity very similar to the refer-
ence: except in the 7 d mortars, porosity rises with the AC con-
tent. In the 50% AC mortars, porosity is greater than in the other
materials. Nonetheless, the mean pore diameter and pore size
distribution curves denote refinement to pore sizes under
100 nm in the AC-bearing mortars.
8. CT analysis of mortar macroporosity reveals a substantial rise in
the volume of pores in the 0.09 mm3 to 0.001 mm3 range with
pozzolan content, mainly at 180 d of hydration.
9. Compressive strength is closely correlated (R2 = 0.95–0.97) to
heat of hydration, and acceptably correlated (R2 = 0.81) to total
porosity.
As a summary of all the above, it can be highlighted that the
incorporation of high AC contents into a cement matrix ( 50%)
is scientifically, technically and environmentally viable as an eco-
efficient future pozzolan. The ideal percentage of replacement of
cement by AC waste will depend directly on the needs, applications
and the minimum requirements to be met the future structure in
service.
Conflict of interest
None.
Acknowledgements
This research was funded by the Spanish Ministry of Economy
and Competitiveness (BIA2015-65558-C3-1-2-3R) (MINECO/
FEDER)). The assistance received for this study from Sociedad
Anónima Hullera Vasco-Leonesa, SIKA (Madrid, Spain) and the
Spanish Cement Institute (IECA) is gratefully acknowledged.
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