Cement and Concrete Composites 68 (2016) 46e56

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Cement and Concrete Composites

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

A combined SEMeCalorimetric approach for assessing hydration and

porosity development in GGBS concrete
Azadeh Attari a, b, Ciaran McNally a, *, Mark G. Richardson a
a
UCD School of Civil Engineering, University College Dublin, Belfield, Dublin 4, Ireland
b
Gavin & Doherty Geosolutions, Beech Hill Office Campus, Clonskeagh, Dublin 14, Ireland

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

Article history: A combination of semi-adiabatic calorimetry and Scanning Electron Microscopy (SEM) is employed for
Received 25 August 2014 characterising the hydration process and pore structure development of cementitious pastes. The effi-
Received in revised form ciency of this method is investigated by obtaining hydration curve parameters for four different concrete
21 January 2016
mixes manufactured using varying combinations of limestone blended cement (CEM II/A-LL) and ground
Accepted 3 February 2016
Available online 16 February 2016
granulated blast-furnace slag (GGBS) over a period of six months after casting. Embedded thermocouples
recorded the internal temperature development associated with heat of hydration released in the first
hours after casting. Hydration monitoring was continued by analysing SEM images taken from broken
Keywords:
SEM
concrete specimens at various time intervals. Reliable hydration quantification using this approach re-
Image analysis quires the aggregate particles to be identified and filtered out of the image; this is achieved using a semi-
Aggregate segmentation automatic image processing methodology developed for detection and segmentation of aggregates from
Hydration curve the concrete paste. Grey-level thresholding and the inflection point method are employed to determine
Calorimetry the area fraction of the void space and assess porosity. Hydration degrees are then determined by
GGBS applying thresholding methods to distinguish the hydrated and anhydrous cement particles. Corre-
sponding hydration curve parameters were obtained based on the experimental data, and the resulting
curves were compared with those obtained based on commonly used cement composition models.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction
The degree of hydration (a) is an indicator of progress of the
reaction between cement grains and water, and is defined as the
ratio of hydrated cement grains to the original quantity of cement
grains available in the mix. Hydration curves are a useful tool for
characterizing the hydration behaviour of concrete mixes at a
reference temperature (Tr) [1].
1.1. Parametric modelling of hydration progress
The exponential formulation proposed in Equation (1) [2] is one
of the most commonly used models of hydration progress and
predicts hydration degree in terms of the equivalent rather than
chronological age of concrete. This is to account for the combined
* Corresponding author.
E-mail address: ciaran.mcnally@ucd.ie (C. McNally).
effects of time and temperature, and has been reported to accu-
rately represent the S-shape of hydration development curves [3].

 b 
t
aðte Þ ¼ au exp  Equation 1
te
In the above equation, a indicates the degree of hydration of the
mix, and te represents the equivalent age of a specimen cured at the
reference temperature (Tr). The hydration time parameter (t) and
hydration shape parameter (b) determine the acceleration, retar-
dation and rate of hydration in each mix [4]. The ultimate degree of
hydration (au) expresses the maximum hydration degree a given
mix is deemed to reach in practice. More information about these
parameters and the detailed calculations involved in obtaining
equivalent ages can be found in Refs. [1,5].
Considering the large number of influencing factors, e.g. water-
cement ratio, mix composition, compaction, curing temperature,
and humidity, degree of hydration of a mix at a certain age cannot
be easily estimated using a pure mechanistic model. In order to

http://dx.doi.org/10.1016/j.cemconcomp.2016.02.001
0958-9465/© 2016 Elsevier Ltd. All rights reserved.
 A. Attari et al. / Cement and Concrete Composites 68 (2016) 46e56
obtain representative hydration curve parameters for defining the
early age behaviour of a certain mix, the parametric model of
Equation (1) should be fitted with a number of data points, and the
mix-specific parameters determined. One of the approaches to
obtain the data points in order to calibrate the curve, is direct
measurement of the amount of cement gel that has formed in the
paste over time. However application of this method is not always
possible due to the equipment reqiured. Therefore, indirect ap-
proaches are often used, with estimation being based on the
amount of chemically bound water or the heat released during
hydration [1].
There are however difficulties in assessing degree of hydration
based on the released heat of hydration. Total heat of hydration
can be determined using adiabatic calorimetry, but that requires
specialist equipment that is not commonly available. Alternately,
knowledge of the exact cement composition is required, as is
concrete temperature monitoring using embedded sensors.
Furthermore, this method is only applicable before the internal
concrete temperature has stabilised with the ambient temper-
atureea condition that only pertains to a few days after casting;
any hydration progress beyond this period cannot be captured
using this approach. Although this approach is unlikely to pro-
vide a precise estimate of the degree of hydration [1], it is still
widely used. The need for a direct approach based on assessment
of the amount of cementitious gel formed in the pore structure
becomes more pronounced if hydration is used in predicting the
secondary characteristics of the mixes, e.g. diffusivity and
permeability.
Application of adiabatic calorimetry in assessing the hydration
progress of the mixes requires measurement of mix-specific data
points. This is most effective during the first few days after casting
of the specimens, when the internal temperature is considerably
different to the ambient surroundings, allowing clear calculation of
the heat generated. On the other hand, this is the period when
direct assessment of the cementitious pore structure is of less in-
terest, since the concrete microstructure is far from its final
configuration. The aim of this study is to propose a methodology for
combining the indirect and direct methods, in order to monitor the
pore structure development of mixes over a six months period after
casting, with the indirect method being employed during the early
age and the direct method covering the later stages of hydration
and pore structure refinement.
Semi-adiabatic calorimetry and Scanning Electron Microscopic
investigation of concrete specimens were adopted as the testing
methodologies. The data points corresponding to the early age of
specimens are obtained using calorimetry; while SEM has been
employed for determining the amount of cement gel formed in
the pore structure over an extended period of time up to six
months after casting. A method has been introduced for deter-
mination of the hydration curve parameters to provide a suitable
fit to the above data. The efficiency and constraints of this
approach are explained and investigated through an experimental
program.
Mixes of blended limestone cement (CEM II/A-LL) and Ground
Granulated Blast-furnace Slag (GGBS) were considered in the ex-
periments, since limited guidance is currently available for char-
acterising the hydration behaviour of these mixes. The
experimental data obtained from investigation of the selected
mixes with the direct and indirect approaches are combined and
used in developing characteristic hydration curves. The appropriate
parameters resulting in the best-fit mathematical model for each
mix are then calculated using a nonlinear multivariate regression.
The resulting hydration characterisation curves are then compared
with those obtained using a numerical model based on the cement
composition.
47
1.2. Scanning Electron Microscopy (SEM)
SEM images are monochromatic displays of the difference in the
electron flux of the backscattered signals that indicate the atomic
number of the material under investigation [6]. This allows com-
ponents of the concrete matrix to be distinguished and identified
on a micro scale, based on the grey colour level they display. SEM is
also capable of radiating X-ray signals, which may be collected
using an Energy Dispersive X-ray Spectroscopy (EDX) system. The
resulting image can be represented in the form of either a map of
element distribution or a continuous spectrum, and is capable of
displaying both the location and concentration of the elements
present in the corresponding frame [7]. The elemental distribution
maps provide an informative analysis tool that can be used together
with the SEM images in the interpretation of the material under
study.
Analysis of SEM images has frequently been employed to
investigate various characteristics of cement and concrete paste,
including investigation of the pore structure [8e10], quantification
of porosity and phases such as anhydrous and hydrated cement
paste [8,11e14], detection of cracks [15], determination of degree of
hydration [16e18] and characterization of the structure of fresh
cement paste [19].
1.2.1. Pore size distribution
Porosity of concrete influences both strength and transport
properties. Pores, other than air voids, range in size from <10 nm
(e.g. gel pores mainly contained within the hydrated cement paste)
to 10 mm (e.g. capillary pores) [20].
The range of pore sizes detectable by SEM imaging is mainly a
function of image resolution, with the smallest detectable size
being in the range of 0.2 mm, dependent on equipment and setting
conditions [21]. This method however is quite efficient in detecting
the larger capillary pores and air voids, which are considered to be
the more influential phase when it comes to modelling the trans-
port properties of concrete [20].
1.2.2. Hydration assessment
SEM can be used for assessing the degree of hydration of con-
crete at any age, and contrary to the indirect method of heat evo-
lution monitoring, does not require previous knowledge of the
exact concrete composition. The difference in the mean atomic
number of hydrated and anhydrous cement particles allows the
user to determine the surface area corresponding to each phase on
the SEM image. An estimate of the degree of hydration of the
concrete samples can then be made based on the ratio of the area of
hydrated cement to the total cement area in the image. The accu-
racy of this method depends on the quality of sample preparation
and image acquisition, efficiency of the methodologies employed
for aggregate segmentation, image processing and threshold
determination among others.
2. Experimental program
In this study, four different concrete mixes were investigated.
Each contained limestone aggregates and limestone blended
cement (CEM II/A-LL) as the basic cementitious material. Varying
GGBS replacement levels were employed (0, 30, 50 and 70% of the
total binder content), and water-cement ratios in the range of
0.5e0.56.
2.1. Indirect assessment: semi-adiabatic calorimetry
Profiles of temperature build-up in the concrete mixes under
investigation were monitored, utilising embedded thermocouples
48 A. Attari et al. / Cement and Concrete Composites 68 (2016) 46e56
for recording the internal temperature of mixes at regular time
steps. Concrete slabs of dimension 300  300  150 mm were
thermally isolated when casting in order to provide semi-adiabatic
conditions. This was achieved by surrounding the concrete speci-
mens with 20 mm thick insulation boards to prevent any heat loss.
The effect of this treatment is to ensure that all parts of the concrete
experience a similar temperature history. These were maintained
until the concrete temperature equalised with the ambient condi-
tions, usually about 5 days. It be noted that full isolation cannot be
easily achieved. More detailed information on the test set up can be
found in Ref. [22]. Temperature monitoring was continued until the
internal concrete temperature stabilized with the ambient tem-
perature. Temperature profiles up to this point were utilised for
quantifying the heat loss, which was then employed in determining
the net heat responsible for the internal temperature rise at
discrete times after casting. The sum of these two values is the total
heat generated in the hydration process. In this indirect approach to
determining the degree of hydration, the ratio of total heat of hy-
dration generated up to a certain time, H(t), to the total ultimate
heat of hydration of the mix, HT, is considered to equate to the
hydration degree, as shown in Equation (2).
HðtÞ
aðtÞ ¼ Equation 2
HT
The procedure suggested by Schindler and Folliard [1] was
adopted to calculate HT for the mixes of this study. In this method,
HT is a function of the cement chemistry, and can be estimated
knowing the exact concrete composition and the ultimate heat of
hydration of each component in the mix, by following Equations
(3)e(5).
X
Hcem ¼ Hi $pi Equation 3
Where, Hcem is the total heat of hydration of cement; pi is the
weight ratio of the i-th compound of the cement mix, and Hi is the
heat of hydration per unit weight of the cement compound.
Hu ¼ Hcem $pcem þ HGGBS $pGGBS Equation 4
HT ¼ Hu $cc Equation 5
Where, Hu is the heat of hydration per unit weight of the
cementitious material, Cc is the total cementitious content of the
mix, and HGGBS is the heat of hydration per unit weight of the slag.
More detailed information about the model and the numerical
values employed can be found in Refs. [1] and [22].
In order to utilise the data obtained by Equation (2), the actual
age should be converted to equivalent age. This was done using the
maturity method and equivalent age function developed by Freie-
sleben, Hansen and Pedersen [23]. It is noted that temperature
development inside the concrete slabs is not uniform, which will
lead to some uncertainty in the results produced.
2.2. Direct assessment: SEM image analysis
Microscopic images were taken from crushed concrete speci-
mens at 6 pre-set intervals between 1 week and 6 months after
casting. This range was selected to allow the hydration reaction to
sufficiently progress, leading to a refinement of the pore structure.
2.2.1. Sample preparation
Various preparation methods have been suggested in the liter-
ature and detailed step by step descriptions are provided in
Refs. [18,24,25]. Specimen preparation in this study involved the
three steps of drying, resin impregnation and grinding/polishing.
As this study is focussed on degree of hydration, a measure is
required to ensure that the specimens are preserved at the target
level of maturity and their degree of hydration does not change. In
this study, the specimens have been taken from across the concrete
samples in order to allow for capturing the spatial variability in the
pore characteristics. These specimens were then immersed in
acetone for several hours before being placed in a desiccator with
anhydrous calcium chloride particles, and under a vacuum pressure
of approximately 70 Pa overnight [26], to ensure that water was
extracted completely from the pore structure. Resin impregnation
was conducted while the specimens were held under vacuum. The
vacuum is essential to assure that the air voids and pores are filled
with resin, preventing the collapse of air void walls during grinding
and hence preserving the original microstructure of the paste. Once
the resin hardened and the moulds removed, the specimens were
ground using Silicon Carbide sheets with grits sizing from 220 to
1000. Polishing was conducted using Silicon Carbide papers of size
2400 and a fine polishing paper.
2.2.2. Image acquisition
Several parameters in the image acquisition system affect the
reliability of information conveyed by microscopic images, namely
the accelerating or working voltage of the microscope, beam cur-
rent, working distance of the lens and magnification level. More
information about these parameters and their effect on the quality
of images can be found in Refs. [26,11]. In this study, images were
obtained at an accelerating voltage of 30.0 kV, and magnification of
500X. Images were 172 ppi, with a pixel resolution of 1024  943;
whereby, each pixel represented 0.3 mm of the specimen surface. At
each test point 5 frames were imaged (as suggested in Ref. [7]), on
an arbitrary basis, along with the corresponding elemental maps of
the same frame. The EDX images were taken simultaneously and
from the same frame as the SEM images, to allow for joint analysis
of the results.
3. Interpreting SEM images
The image processing and analytical steps of this study were
conducted using the ImageJ open-access software and MATLAB
image processing toolbox. Quantitative analysis of the images by
determining the area fraction corresponding to each phase requires
an efficient feature segmentation technique [27]. Since various
phases of concrete display different grey colour intensities in SEM
images, segmentation by grey level thresholding is one of the most
commonly employed methods [28]. In an ideal case, each phase in
the concrete paste represents a separate peak in the grey level
histogram, and the minima between the two adjacent peaks is
considered to be the brightness threshold separating the features of
interest [29]. For determining the threshold either manual or
automatic thresholding can be used. Automatic thresholding can be
performed using methods such as the tangent slope [13], entropy
maximisation based on measuring and maximising the information
content of the image [30e32], inflection point [27] or others [33].
However, brightness thresholding is not always applicable since
pixel brightness does not necessarily represent a single phase.
There are always inter-phase pixels, displaying grey colour values
that average those of two separate phases, making it increasingly
difficult to determine a unique threshold [27]. It should also be
noted that selection of appropriate thresholding methods is an
active research area in other diverse fields such as ceramics [34],
fuel cells [35], food science [36], and archaeology [37].
Segmentation by brightness thresholding is particularly more
difficult when aggregates are present in the image. The colour in-
tensity of aggregates very often overlaps those of other concrete
phases. For example, siliceous aggregate displays colour intensity
 A. Attari et al. / Cement and Concrete Composites 68 (2016) 46e56
similar to that of hydrated cement paste. The bright colour of some
aggregates can also overlap those of anhydrous cement grains.
Some of these bright areas might appear due to poor polishing of
the specimen, rather than presence of elements with high back-
scattering coefficients in the aggregate or paste. Since the aggregate
surface is generally much harder than the hardened cement paste,
uniform polishing of the surface during preparation stage can lead
to aggregates with a convex surface, displaying a wider range of
grey level intensities, and causing even more overlaps [38].
A two-fold conclusion can be drawn: firstly, prior aggregate
segmentation from images is essential for determination of
porosity and anhydrous cement content, and secondly, an aggre-
gate segmentation method cannot only be dependent upon the
peaks in a brightness histogram. In order to fulfil aggregate seg-
mentation it would be better to rely on characteristics of the phases
rather than the grey colour intensity thresholding [27,38].
The methodology employed in this study involves three distinct
steps to identify the aggregates, pores, and hydrated cementitious
component. Whenever automatic thresholding is required, it is
performed using the inflection point method, as proposed by Wong
et al. [27] as it is reported to be more consistent and reliable than
other methods.
3.1. Automatic identification of pores
The inflection point of a cumulative brightness histogram rep-
resents a critical grey level, where a small increase in brightness
threshold can create a sharp increase in the total segmented area
(Fig. 1). This value can be considered as the target brightness
threshold after being decreased by a modification factor of 0.9,
following the recommendation of Wong et al. [27].
In order to find the corresponding inflection point, a set of
predefined brightness thresholds are considered and applied to
each image. As illustrated in Fig. 2, an increase in the applied
threshold results in a decrease in the uncovered area. A pixel count
of the images has shown that the ratio of uncovered to covered
pixels has decreased from 0.41 (at the threshold level 95) to 0.33 (at
the threshold level 115) and 0.19 (at the threshold level 135).
At this stage, sensitivity curves, similar to that of Fig. 1, can be
obtained for each image by plotting the resulting value of the target
parameter (porosity, hydration degree, etc.) against the corre-
sponding brightness threshold. The curve's inflection point shows
the grey colour level that should be considered as the separating
threshold.
3.2. Manual image processing
Existing approaches to aggregate segmentation rely heavily on
either brightness thresholding or the difference in texture of
100
Calculated Porosity (%)
80
60
40
20
0 lapping between the colour intensities.
0 40 80 120 160 200
Threshold levels considered
Fig. 1. Assessing porosity threshold level using the inflection point method.
49
aggregates and cementitious paste. The term ‘texture’ refers to the
local variation in brightness between neighbouring pixels. If the
brightness of a pixel varies significantly from adjacent pixels, that
region is described as ‘highly textured’ [20]. Cement paste exhibits
frequent and sharp local variation of grey colour intensity [21] due
to the high variation of its chemical composition and internal
porosity, while the texture fluctuation is much gentler in an
aggregate particle [20,38], as illustrated in Fig. 3. Segmentation
based on the difference in texture [19,20,38] uses mathematical
operations to separate the highly textured cementitious matrix
from the low textured smooth regions representing aggregates and
air voids. It should be noted that segmentation using this method
cannot be easily achieved for dense concrete [38].
The methodology developed in this study is based on the
method proposed in Refs. [39], and employs information obtained
from EDX elemental maps. This allows the user to differentiate
aggregate from the paste not only based on visual dissimilarities,
but also by giving consideration to their different overall chemical
compositions. Data obtained from EDX analyses can be used along
with the features and morphological characteristics observed in the
SEM images to aid in phase identification.
The most common elements in cement paste are Silicon and
Calcium, while aggregates commonly present in concrete are Cal-
cium or Silicon based (but usually not both). Porous areas are high
in carbon content, since they are resin filled prior to imaging. In this
study, elemental maps of Calcium and Silicon were turned into
binary images, and a combined image of the two was built, showing
only the common pixels, as shown in Fig. 4.
By combining this information with feature recognition
methods, (e.g. Ref. [21]), aggregates can be identified by the oper-
ator and manually removed from the image. The resulting
segmented image can then be used for quantitative analysis of
cement paste features, such as porosity and degree of hydration as
illustrated in Fig. 5.
3.2.1. Identification of pores
Since pores and air voids are pre-treated with epoxy filling, they
appear as the darkest phase in the image, with the majority being
scattered in the paste. Pore segmentation was performed using the
automatic thresholding method of inflection point [27]. Manual
thresholding typically results in higher values of porosity,
compared to the inflection point method. However, this has been
attributed to the human bias, which normally tends to overestimate
the area fraction corresponding to the features of interest [27,40].
There are possible sources of error in assessing porosity using
the described method. Some of the pores located in the interface
transition zone (ITZ) around the aggregates in the paste can be
eliminated from the image during manual segmentation of aggre-
gates. Also, the apparent diameter of pores on the image depends
on where the cut has intersected the pore sphere, resulting in
underestimating the actual diameter of the pore.
3.2.2. Determination of anhydrous cementitious component
Once the porous area is detected and removed from the image,
the hydrated and anhydrous cement pastes can be identified using
a combination of the existing brightness thresholding techniques,
since anhydrous cement grains usually appear as the brightest
phase of the image. However, the diverse chemical composition of
(hydrated) cement paste results in sharp local variation and non-
uniformity of cement texture, and leads to a large degree of over-
240 Hydration products mainly consist of Calcium Silicate Hydrates
(CSH gel), Calcium Hydroxide (CH), and smaller quantities of
Ettringite and mono-sulphate. While the irregular deposits of CH
are usually brighter than the CSH gel, the gel itself is comprised of a
50 A. Attari et al. / Cement and Concrete Composites 68 (2016) 46e56
Fig. 2. Influence of varying threshold levels (95; 115; 135) on porosity assessment for an aggregate-segmented image.
Fig. 3. Different textures of aggregate and cement particles in a concrete specimen.
range of quasi-amorphous particles with slight differences in
chemical composition and colour intensity [21]. The two varieties
of CSH gel (inner products, contained within the boundaries of the
cement grain; outer products, formed by through-solution depo-
sition of cement during hydration, and its penetration into the
originally water-filled spaces), also exhibit different grey colour
intensities [41].
Predefined threshold values for distinguishing the two phases
have been occasionally reported, (e.g. Ref. [11]); however, these are
only applicable if brightness and contrast are being kept consistent
in all the images. If these values are to be used, the exact
Fig. 4. Superposition of a) Silicon and b) Calcium elemental maps to produce c) binary display of common pixels.
preparation method and image acquisition system must be strictly
adhered to. Automatic thresholding was employed in Ref. [18] using
the tangent slope method, but the results are reported as not being
reliable, and manual thresholding is encouraged.
In this study, automatic thresholding was conducted using the
inflection point method for determining the higher level threshold
of hydrated cement paste. It has been suggested [28] that a
comparative investigation be conducted prior to automatic thresh-
olding, in order to confirm the compatibility of results with those
obtained by manual thresholding, considering the particular con-
dition of specimens under investigation. Therefore, thresholds ob-
tained using the described method, were later evaluated by visual
judgement and adjustments were made when required for selecting
a criterion that covers the hydrated cement particles as precisely as
possible. Based on these criteria, the hydration degree of specimens
can be assessed, and hydration progress curves built. Results were
then compared with those obtained by manual thresholding, and a
decision was made on which method to rely upon.
4. Results and discussion
4.1. Porosity assessment (using SEM)
Brightness thresholds for porosity are obtained using the in-
flection point method. The automatically determined thresholds
were then verified with manual observation, and it was found that
in 45% of cases, further adjustment was required (in addition to the
10% reduction specified in Section 3.1). Only in 31% of these cases
(14% of the total number of images investigated), the initial 10%
reduction should have been reversed, while the rest required
further reduction, in some cases as low as 50% of the automatically
detected threshold to be approved by manual thresholding. The
average threshold of porosity obtained from analysis of 120 images
was found to be 60 using automatic, and 56 using manual methods.
Fig. 6 summarises the curves of porosity covering the first six
 A. Attari et al. / Cement and Concrete Composites 68 (2016) 46e56
Fig. 5. Segmentation process for removing aggregate particles from a BSE image: a) before, b) after.
16
14
12
Porosity (%)
10
4
0 4
Fig. 6. Porosity developed in the tested concrete mixes over time.
months age of the specimens that were obtained using the final
adjusted thresholds.
Although there are points of inconsistency in the diagrams, a
general decreasing trend is observable in the diagrams of porosity
of Mixes 1, 3, and 4. It is observed that the porosity of the GGBS
concrete mixes initially lie between 10 and 13%, before reducing to
a range of 5e7%, The mix with a plain CEM II binder shows slightly
higher initial porosity values (around 15%) before stabilising in the
range 7e8%. The values reported for Mix 3 however show an in-
crease in porosity after 8 weeks. Analysis of the data suggests that
this is a result of some high variability in these samples, where the
average values have been somewhat skewed. Overall however, a
trend can be seen, and this is consistent with previous findings,
stating that application of GGBS results in reduced porosity and a
finer pore structure in the concrete mix [42].
It should be noted that in assessing porosity using SEM image
analysis, some of the pores located in the ITZ around the aggregates
in the paste can be eliminated from the image during aggregate
segmentation as they are not representative of the overall porosity
of the cementitious matrix. Additionally, the apparent diameter of
pores on the image depends on where the cut has intersected the
pore sphere, resulting in an underestimation of the actual diameter
of the pore.
51
CEM II CEM II+30%GGBS
CEM II+50%GGBS CEM II+70%GGBS
8 12 16 20 24
Age (weeks)
4.2. Hydration assessment (using calorimetry)
The diagrams of hydration degree obtained using calorimetry
are presented in Fig. 7. The exact experimental procedure and
involved calculations are reported elsewhere [22]. Comparison of
the hydration curve parameters obtained using calorimetry with
those reported in the literature, e.g. Refs. [1], for mixtures based on
CEM I show a considerable divergence.
It is observed that after a certain amount of time has elapsed, a
plateau region forms in these diagrams. The hydration curves ob-
tained by early-age temperature monitoring for the mix of plain
CEM II start to flatten before the equivalent age of 50 h; the
apparent ultimate hydration degree (au) estimated using this
method is in the range of 0.3e0.4, which is not realistic. These
values are much lower than the degree of hydration usually ach-
ieved in practice. Comparison of the hydration curves obtained for
the different mixes shows that in the case of the mix with 70%
GGBS, the S-shape hydration curve obtained from the results of
temperature monitoring has not even yet completely formed. These
are indicators that the hydration reactions have not completed by
the end of the monitoring period.
This can be attributed to the fact that measuring the generated
heat over the whole period that the hydration process continues is
52
0.5
0.4
Degree of Hydration ( ) 0.3
0.2
0.1
0
0.1
Fig. 7. Diagrams of hydration progress, determined using the direct method of heat monitoring.
not possible using the available equipment. While there is still heat
produced due to continued hydration, the thermal sensors are not
capable of registering the small differences between the internal
concrete temperature and the ambient temperature. This lack of
sensitivity erroneously suggests that the hydration reaction has
completed and stopped, mandating the hydration monitoring to be
continued using another method. This was achieved by using
microscopic images of concrete and analysing them to assess the
hydration degrees at later ages.
4.3. Hydration rate assessment (using SEM)
Brightness thresholding for determining the hydration degree
was conducted using both automatic and manual thresholding as
outlined in Section 3.2.2. This resulted in a distribution of grey
colour intensities for the 120 images processed, which is presented
in Fig. 8. The average value of grey colour intensity separating hy-
drated and anhydrous cement phases was found to be 116 and 111
using automatic and manual thresholding, respectively.
25
20
15
Frequency
10
0
20
Fig. 8. Distribution of hydrated cement grey level thresholds obtained using automatic and manual methods.
A. Attari et al. / Cement and Concrete Composites 68 (2016) 46e56
CEM II CEM II+30%GGBS
CEM II+50%GGBS CEM II+70%GGBS
1 10 100
Equivalent Age (Hours)
Fig. 9 (a) to 9 (d) provide a graphical comparison between of
hydration development determined using manual and automatic
brightness thresholding. Comparison of the two sets of curves in
each mix shows a considerable disparity in the shape of hydration
curves. This is in contrast to the data presented in Fig. 8, where the
average values and distribution shape obtained from manual and
automatic methods suggest similar values. When the results from
Figs. 8 and 9 are considered together, it can be seen that automatic
thresholding usually results in higher hydration degrees than those
obtained by manual thresholding. The scatter in the results is more
pronounced when using manual thresholding, which can be justi-
fied considering the subjectivity of the process. However, manual
thresholding results in more consistent trends in the hydration
progress, with the curves increasing almost uniformly over time.
Therefore, manual selection of threshold values is preferred,
despite being subjective and time consuming.
Based on the manual thresholding data presented in Fig. 8, it can
be stated that by the end of the first week after casting, mixes have
a hydration degree of approximately 50%. By the end of the
Automatic Manual
30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 More
Grey Levels
 A. Attari et al. / Cement and Concrete Composites 68 (2016) 46e56 53

Hydration progress (CEM II) Hydration progress (CEM II+30% GGBS)

0.9 0.9
std=0.02
std=0.02 std=0.03 std=0.04
0.8 std=0.01 std=0.08 0.8

Hydration degree (α)

Hydration degree (α)

std=0.06 std=0.07 std=0.14 std=0.04
std=0.10
0.7 std=0.05 0.7 std=0.07
std=0.22 std=0.06 std= 0.11 std=0.15
std=0.05 std=0.12
0.6 0.6 std=0.09
std=0.14
std=0.13
0.5 std=0.05 Inflection point method 0.5 Inflection point method
Manual thresholding std=0.11 Manual thresholding
0.4 0.4
0 4 8 12 16 20 24 0 4 8 12 16 20 24
Age (weeks) Age (weeks)

0.9 Hydration progress (CEM II+50% GGBS) Hydration progress (CEM II+70% GGBS)
0.9
std=0.05 std=0.13
std=0.13
Hydration degree (α)

std=0.03

Hydration degree (α)

0.8 std=0.03 0.8 std=0.02
std=0.09
std=0.03 std=0.04 std=0.14
0.7 0.7 std=0.05
std=0.11 std=0.12 std=0.17 std=0.03
std=0.08
std=0.06
0.6 std=0.16 0.6 std=0.07
std=0.06
std=0.05
std=0.09 std=0.07
0.5 Inflection point method 0.5 Inflection point method
std=0.15 Manual thresholding
Manual thresholding
0.4 0.4
0 4 8 12 16 20 24 0 4 8 12 16 20 24
Age (weeks) Age (weeks)

Fig. 9. Hydration curve developments obtained by automatic and manual thresholding methods (std ¼ standard deviation for each data point).

monitoring period (24th week), the degree of hydration reaches three mixes and te ¼ 24e25 h in the mix with 70% GGBS replace-
around 80% in the mixes containing GGBS, and 70% in the mix with ment level. The difference in the timing of occurrence of inflection
only CEM II. It is also observed that the initial rate of hydration is point can be attributed to the slower hydration rate of GGBS in the
much steeper in the mixes with lower GGBS contents. The mixes early age.
containing 0 and 30% GGBS replacement reach a hydration degree The considerable difference in the number of data points ob-
of 60% between the 1st and 4th week after casting. This degree of tained from the two methods should be addressed before the data
hydration occurs in mixes with 50 and 70% GGBS replacement level sets can be combined effectively. The embedded thermocouples
after 8 weeks. This is consistent with the lower initial hydration were set to record temperature samples every 5 min, while SEM
rate expected in concrete mixes incorporating GGBS. images were taken only at 6 points between 1 week and 6 months
Fig. 10 shows the correlation between the manually and auto- after casting. Although the data obtained from temperature
matically detected threshold values. The equation obtained from monitoring represents the behaviour of concrete over a very short
regression of the data (from all 4 mixes) in a linear trend shows that period of time, the rate of change in this region of hydration curve is
manual thresholds can be predicted by multiplying a small modi- much higher and hence the shape of curve more sensitive. How-
fication factor close to unity to the automatically detected ever, in order to prevent the sampling sizes to influence the final
threshold. However, due to the presence of a considerable scatter in hydration curves, equal number of data points from each source
the correlated parameters, this approach is not recommended. It is should be incorporated in the final model.
also observed on this diagram, that the scatter exists in all the four In order to decide on the number of data points to include in the
mixes under consideration, and does not pertain to a specific mix or final model, various datasets were built and compared with
a certain age. different number of data points. It was observed that while the
resulting hydration curve parameters are slightly different, the
4.4. Processing the experimental data sensitivity of results to the sampling size becomes negligible in
datasets with more than 200 samples. Therefore, 200 samples were
The importance of information obtained through calorimetry randomly selected from the truncated calorimetry dataset. At the
should not be underestimated, since early age hydration consid- same time, the bootstrapping method was used to expand the
erably influences long term concrete durability. Given the rapid sampling size of the SEM-covered region artificially, through
hydration changes in the first hours after casting, obtaining realistic repeated generation of data points by random resampling from the
hydration characterization curves is not possible without taking original data [43].
into account the behaviour of mix in the early age. In this section, Three-variate nonlinear regression analysis was performed and
hydration degrees determined using SEM image analysis were hydration curve parameters determined by fitting the parametric
combined with those estimated using calorimetry, and hydration model of Equation (1) to the combined datasets generated. In order
characterization curves were developed based on the combined to minimize the error resulting from the random selection and
data sets. generation of the datasets, the procedure of randomly constructing
In order to combine the two data sets and obtain representative the datasets and performing the regression analyses was repeated
trends in hydration progress, the influence of data in the plateau 10,000 times for each mix, and the average values were reported.
region observed in Fig. 7 should be eliminated. Therefore, the data The resulting hydration curve parameters are presented in Table 1.
points are considered only up to the inflection point of graphs of The table also contains hydration curve parameters estimated using
Fig. 7, corresponding to an equivalent age of te ¼ 13e14 h in the first the equations proposed in Ref. [44].
54 A. Attari et al. / Cement and Concrete Composites 68 (2016) 46e56

180

160 y = 0.9569x
R² = 0.5747

140
Manual Thresholds

120

100

80
CEM II CEM II+30% GGBS

CEM II+50%GGBS CEM II+70%GGBS

60

40
50 70 90 110 130 150 170 190
Automatic Thresholds

Fig. 10. Correlation of manual and automatic thresholds obtained for hydrated cement paste.

The accuracy of the experimentally determined parameters can less investigated cement types.
be confirmed by comparing the results with those reported in The comparison also shows that the model based on cement
Ref. [45] based on an experimental study of the hydration behav- composition overestimates the maximum degree of hydration of
iour of a mix of CEM II with 50% GGBS replacement, and a water- the mixes (au ¼ 1.0) in all the four mixes, while the experimentally
cement ratio of 0.54 which was conducted using semi-adiabatic determined au values were in the range of 0.8e0.9. It should be
calorimetry of laboratory-cast specimens. In that case the calcu- noted that au in the experimentally determined model did not
lated parameters were found to be: au ¼ 0.8, t ¼ 40.58, and exhibit strong dependence on the GGBS content of the mix.
b ¼ 0.562, which compare very well with the values presented in The hydration time parameters (t) obtained from the two
Table 1 for the mix with 50% GGBS replacement. methods also showed significant difference. Although both
Fig. 11 provides a graphical comparison of the accuracy of the methods predicted an increase in the hydration time parameter as
two sets of hydration curve parameters listed in Table 1, in pre- the GGBS content increases, the experimentally determined t
dicting the experimental hydration degrees obtained for each of the parameters were much closer in the mixes with 0, 30, and 50%
mixes of this study. The first set of parameters in Table 1 (the model GGBS replacement, only showing a visible jump in the mix with
proposed in this study) have been obtained by curve-fitting to the 70% GGBS replacement, confirming that the retarding effect of
experimental data gathered by combined SEM monitoring and GGBS is much more pronounced when incorporated at higher
calorimetry. replacement levels.
The comparison shows that in the mixes with intermediate A decreasing trend was observed in the experimentally deter-
levels of GGBS replacement, the two models show an acceptable mined shape parameters (b), as the GGBS content of the mix in-
level of consistency within the period of monitoring. However for creases. This can be justified considering the retarding effect of
the mixes with zero and 70% GGBS replacement levels, the GGBS, and that all the four mixes have relatively similar au values.
formulation based on cement composition is not capable of This shows that the mix with higher GGBS content must exhibit a
modelling the experimental data with an acceptable degree of ac- steeper slope, and hence a higher b, during the acceleration stage.
curacy. This highlights the need for more refined models and more The scatter in the experimentally determined b values was much
accurate approaches for determining the hydration characterisa- smaller than that predicted by the parametric model. The b
tion curves of mixes with high cement replacement levels or for parameter in the experimental model ranges between 0.319 and
0.360, and is in the range of 0.114e0.549 in the parametric model.
This indicates that the experimental model is more consistent with
Table 1
the findings of Folliard et al. [4] stating that the influence of GGBS
Comparison of the hydration curve parameters obtained using different approaches.
replacement levels is significant only on the hydration time pa-
Hydration curve parameters (based on) rameters (t). The difference in the hydration shape parameter (b) of
Mix composition Temperature Cement compound the two sets of parameters can be attributed to the difference in
monitoring and SEM composition [1] total cementitious contents of the mixes, in addition to different
image analysis sources of cement and GGBS.
au t b au t b In interpreting the comparative graphs, it should be noted that
CEM II 0.89 33.77 0.319 1.00 18.63 0.549 the hydration characterisation model proposed in Ref. [44] were
CEM II þ 30% GGBS 0.90 34.18 0.326 1.00 57.36 0.325 originally developed for mixes of CEM I, and their accuracy can be
CEM II þ 50% GGBS 0.82 36.60 0.368 1.00 138.18 0.208 compromised when applied for predicting the hydration behaviour
CEM II þ 70% GGBS 0.90 74.03 0.360 1.00 418.50 0.114 of mixes utilising CEM II as the main cementitious material.
 A. Attari et al. / Cement and Concrete Composites 68 (2016) 46e56 55

1 CEM II 1 CEM II+30%GGBS

Cement composition model
0.8

Hydration degree (α)

0.8 (Schindler & Folliard 2005)

Hydration degree (α)

Measured
0.6 0.6 hydration degrees
Measured
0.4 hydration degrees 0.4 Proposed model

Proposed model
0.2 0.2 Cement composition model
(Schindler & Folliard 2005)
0 0
0.1 1 10 100 1000 10000 0.1 1 10 100 1000 10000
Equivalent age (hr) Equivalent age (hr)

1 CEM II+50%GGBS 1 CEM II+70%GGBS

0.8 0.8
Hydration degree (α)

Measured

Hydration degree (α)

hydration degrees
0.6 0.6 Measured
hydration degrees
0.4 Proposed model 0.4
Proposed model
0.2 0.2
Cement composition model Cement composition model
(Schindler & Folliard 2005) (Schindler & Folliard 2005)
0 0
0.1 1 10 100 1000 10000 0.1 1 10 100 1000 10000
Equivalent age (hr) Equivalent age (hr)

Fig. 11. Comparison of hydration curves obtained using two different approaches with the experimental data.

5. Conclusion differences between the two sets of hydration curve parameters.

The graphical comparison of the hydration curves also reveals that
An experimental program was reported for monitoring the hy- the difference is more noticeable in the mixes of plain CEM II and
dration progress and determining the hydration curve parameters the mix with 70% GGBS replacement. This can be inferred as an
of four mixes containing CEM II and various replacement levels of indicator of the need for improved tools to capture the hydration
GGBS over a period of 6 months after casting. Hydration degree and progress of the mixes with large contents of admixtures or with
porosity after the first few days of casting was assessed using a less-investigated cement types. The hydration curve parameters
direct approach, by analysing the microscopic images taken from obtained based on the results of this study showed acceptable
crushed samples of concrete at various time intervals to reflect consistency with those predicted for a mix of CEM II and GGBS
their desired level of maturity. reported in another experimental study.
In order to make reliable estimates of the concrete pore The parametric values of hydration shape parameter (b) in-
structure using SEM images, the aggregate particles were identi- creases with increasing GGBS content of the mix. However, the
fied and separated from the image. A methodology was developed, influence of GGBS content was more noticeable in the hydration
combining the data obtained from EDX analyses with those of SEM time parameter (t). Increasing the GGBS content of the mix in-
images, to identify and differentiate aggregates from cement paste, creases the retardation effect and leads to higher t values. This is
based on the difference in chemical composition. A semi- particularly the case, when higher replacement levels of GGBS are
automatic procedure was also developed for determining present in the mix.
porosity and for distinguishing hydrated versus anhydrous cement
paste. Acknowledgement
Both manual and automatic methods were employed for
determining the grey level threshold between the hydrated and the The TEAM project is a Marie Curie Initial Training Network and
anhydrous cement paste. Hydration curves obtained using both of is funded by the European Commission 7th Framework Programme
these methods show that automatic thresholding using the in- (PITN-GA-2009-238648).
flection point method is not a reliable method for assessing degree The authors wish to acknowledge Dr Ian Reid from UCD Nano
of hydration. The values should instead be verified by a human Imaging and Material Analysis Centre (NIMAC) for his assistance in
operator, both during aggregate segmentation and when deciding image acquisition, and Mr Derek Holmes for his support and
on the thresholds, to maximize accuracy. assistance in conducting the experimental part of this study.
Although it was found that there exists a linear relationship
between the values of automatic and manual thresholds obtained
on a specific image, there is also a considerable scatter in these References
results. Investigation of the threshold values obtained in the study [1] A.K. Schindler, K.J. Folliard, Heat of hydration models for cementitious mate-
for various specimens did not reveal the dependence of thresholds rials, ACI Mater. J. 102 (2005) 24e33.
on either the age or the mix composition of specimens. [2] P.F. Hansen, E. Pedersen, Curing of concrete structures, in: BKI, 1985, p. 42.
[3] I. Pane, W. Hansen, Concrete hydration and mechanical properties under
The employed method was capable of predicting both the lower
nonisothermal conditions, ACI Mater. J. 99 (2002).
porosity and slower initial hydration rates expected in GGBS con- [4] K.J. Folliard, M.C. Juenger, A.K. Schindler, K.A. Riding, J.L. Poole, L.F. Kallivokas,
crete mixes. Comparison of the hydration curve parameters ob- S. Slatnick, J. Whigham, J. Meadows, Prediction model for concrete behav-
tained by curve-fitting to the experimental data with those iordfinal report, in: Center for Transportation Research, The University of
Texas at Austin, 2008.
obtained using the formulation proposed in the literature (based on [5] A.K. Schindler, Effect of temperature on hydration of cementitious materials,
the cement composition) shows that there exist considerable ACI Mater. J. 101 (2004) 72e81.
56 A. Attari et al. / Cement and Concrete Composites 68 (2016) 46e56
[6] U. Angst, Chloride Induced Reinforcement Corrosion in Concrete, Department
of Structural Engineering, Norwegian University of Science and Technology,
2011.
[7] P. Stutzman, Scanning electron microscopy imaging of hydraulic cement
microstructure, Cem. Concr. Compos. 26 (2004) 957e966.
[8] D.A. Lange, H.M. Jennings, S.P. Shah, Image analysis techniques for charac-
terization of pore structure of cement-based materials, Cem. Concr. Res. 24
(1994) 841e853.
[9] S. Diamond, M.E. Leeman, Pore size distributions in hardened cement paste by
SEM image analysis, in: Materials Research Society Symposium Proceedings,
Cambridge Univ Press, 1995, pp. 217e217.
[10] D. Darwin, M.N. Abou-Zeid, Application of automated image analysis to the
study of cement paste microstructure, in: MRS Proceedings, Cambridge Univ
Press, 1994.
[11] H. Zhao, D. Darwin, Quantitative backscattered electron analysis of cement
paste, Cem. Concr. Res. 22 (1992) 695e706.
[12] K.O. Kjellsen, R.J. Detwiler, O.E. Gjørv, Backscattered electron image analysis of
cement paste specimens: specimen preparation and analytical methods, Cem.
Concr. Res. 21 (1991) 388e390.
[13] K. Scrivener, P. Pratt, The characterization and quantification of cement and
concrete microstructures, in: Proceedings, Pore Structure and Material Prop-
erties, 1987, pp. 61e68.
[14] Y. Wang, S. Diamond, An approach to quantitative image analysis for cement
pastes, in: Materials Research Society Symposium Proceedings, Cambridge
Univ Press, 1995, pp. 23e23.
[15] D. Darwin, M.N. Abou-Zeid, K.W. Ketcham, Automated crack identification for
cement paste, Cem. Concr. Res. 25 (1995) 605e616.
[16] S. Igarashi, M. Kawamura, A. Watanabe, Analysis of cement pastes and mor-
tars by a combination of backscatter-based SEM image analysis and calcula-
tions based on the powers model, Cement and Concrete Composites 26 (2004)
977e985.
[17] V. Kocaba, Development and evaluation of methods to follow microstructural
development of cementitious systems including slags, in: Ecole Polytechnique
Federale de Lausanne, 2009.
[18] M.M. Canut, Pore Structure in Blended Cement Pastes, Department of Civil
Engineering, Technical University of Denmark, 2011.
[19] M. Barrioulet, R. Saada, E. Ringot, A quantitative structural study of fresh
cement paste by image analysis part 1: Image processing, Cem. Concr. Res. 21
(1991) 835e843.
[20] A.M. Werner, D. Lange, Quantitative image analysis of masonry mortar
microstructure, J. Comput. Civil Eng. 13 (1999) 110e115.
[21] S. Diamond, The microstructure of cement paste and concreteeea visual
primer, Cem. Concr. Compos. 26 (2004) 919e933.
[22] A. Attari, Probability-based Modelling of Chloride-induced Corrosion in CEM
II/A-LL and GGBS Concrete, PhD Thesis, submitted to University College
Dublin, Ireland, 2013.
[23] P.F. Hansen, E.J. Pedersen, Maturity computer for controlled curing and
hardening of concrete, in: Nordisk Betong, 1977, pp. 21e25.
[24] K. Kjellsen, A. Monsøy, K. Isachsen, R. Detwiler, Preparation of flat-polished
specimens for SEM-backscattered electron imaging and X-ray micro-
analysisdimportance of epoxy impregnation, Cem. Concr. Res. 33 (2003)
611e616.
[25] P.E. Stutzman, J.R. Clifton, Specimen preparation for scanning electron mi-
croscopy, in: Proceedings of the International Conference on Cement Micro-
scopy, International Cement Microscopy Association, 1999, pp. 10e22.
[26] K.O. Kjellsen, R.J. Detwiler, O.E. Gjørv, Development of microstructures in
plain cement pastes hydrated at different temperatures, Cem. Concr. Res. 21
(1991) 179e189.
[27] H. Wong, M. Head, N. Buenfeld, Pore segmentation of cement-based materials
from backscattered electron images, Cem. Concr. Res. 36 (2006) 1083e1090.
[28] P. Soroushian, M. Elzafraney, A. Nossoni, Specimen preparation and image
processing and analysis techniques for automated quantification of concrete
microcracks and voids, Cem. Concr. Res. 33 (2003) 1949e1962.
[29] K.R. Castleman, Stereometric Ranging, Digital Image Processing, Prentice-Hall,
Inc, Englewood Cliffs, New Jersey, 1979, pp. 364e369.
[30] N.R. Pal, S.K. Pal, Entropic thresholding, Signal Process. 16 (1989) 97e108.
[31] T. Pun, A new method for grey-level picture thresholding using the entropy of
the histogram, Signal Process. 2 (1980) 223e237.
[32] J. Kapur, P.K. Sahoo, A. Wong, A new method for gray-level picture thresh-
olding using the entropy of the histogram, Comput. Vis. Graph. Image Process.
29 (1985) 273e285.
[33] M. Coster, J.L. Chermant, Image analysis and mathematical morphology for
civil engineering materials, Cem. Concr. Compos. 23 (2001) 133e151.
[34] Y. Zou, J. Malzbender, Development and optimization of porosity measure-
ment techniques, Ceram. Int. 42 (2) (2016) 2861e2870.
[35] E.A. Wargo, T. Kotaka, Y. Tabuchi, E.C. Kumbur, Comparison of focused ion
beam versus nano-scale X-ray computed tomography for resolving 3-D mi-
crostructures of porous fuel cell materials, J. Power Sour. 241 (2013) 608e618.
[36] G. Impoco, N. Fuc a, L. Tuminello, G. Licitra, Quantitative image analysis of food
microstructure, Curr. Microsc. Contrib. Adv. Sci. Technol. 2 (2012) 903e911.
[37] G. Eramo, A. Aprile, I.M. Muntoni, A. Zerboni, Textural and morphometric
analysis applied to holocene pottery from takarkori rock shelter (SW Libya,
Central Sahara): a quantitative sedimentological approach, Archaeometry 56
(S1) (2014) 36e57.
[38] R. Yang, N. Buenfeld, Binary segmentation of aggregate in SEM image analysis
of concrete, Cem. Concr. Res. 31 (2001) 437e441.
[39] P.E. Stuzman, Cement clinker characterisation by scanning electron micro-
scopy, J. Cem. Concr. Aggreg. 13 (1991) 109e114.
[40] J.C. Russ, The Image Processing handbook, CRC press, 2002.
[41] H.F.W. Taylor, Cement chemistry, Thomas Telford, 1997.
[42] P. Basheer, P. Gilleece, A. Long, W. Mc Carter, Monitoring electrical resistance
of concrete containing alternative cementitious materials to assess their
resistance to chloride penetration, Cem. Concr. Compos. 24 (2002) 437e449.
[43] B. Efron, R.J. Tibshirani, An Introduction to the Bootstrap, Chapman & Hall,
New York, 1993.
[44] A.K. Schindler, K.J. Folliard, Influence of supplementary cementing materials
on the heat of hydration of concrete, in: Advances in Cement and Concrete IX
Conference, Colorado, 2003, pp. 10e14.
[45] A.K. Schindler, T. Dossey, B.F. McCullough, Temperature Control During Con-
struction to Improve the Long Term Performance of Portland Cement Con-
crete Pavements, FHWA/TX-05/0-1700-2, Center for Transportation Research,
the University of Texas, Austin, 2002.