Construction and Building Materials 191 (2018) 1093–1102

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Construction and Building Materials

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

Experimental design of a well cement slurry for rapid gel strength

development
Lee Namkon a,1, Prabhakar Abhinav a, Ong Khim Chye Gary a, Moon Juhyuk a,2, Zhang Min-Hong a,
Cheng Chuen Hon Arthur a, Haugsted Klaus b, Kong Kian Hau a,⇑
a
Department of Civil and Environmental Engineering, National University of Singapore 117576, Singapore
b
NauticAWT Energy Solutions 627606 Singapore, Singapore

h i g h l i g h t s

Gelation time can be shortened with increased dosage of CSA cement.

Early age ettringite formation leads to rapid gel strength development.

Better Right-Angle-Set tendency observed on higher dosage of CSA cement and gypsum.

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

Article history: Hydration of calcium sulfoaluminate cement (CSA) yields mainly ettringite that supports high early-age
Received 7 May 2018 strength. The hydration characteristics of CSA can help to control gelation of a Portland cement slurry
Received in revised form 30 September such that fluid migration is mitigated. This paper reports on the performance of well cements incorpo-
2018
rated with CSA and gypsum on gel transition time and Right-Angle-Set (RAS) property for utilization
Accepted 11 October 2018
Available online 20 October 2018
in plugging oil wells. Rapid gel strength development is highly dependent on ettringite formation. It is
observed that gel transition time shortens with increasing additions of CSA. RAS property is more evident
with higher dosage of CSA regardless of retarder content.
Keywords:
Portland cement
Ó 2018 Elsevier Ltd. All rights reserved.
CSA cement
Ettringite
Static gel strength
Gel transition time
Consistency
Right-Angle-Set

1. Introduction§
Portland cement has been used in permanently sealing the
annular space in between the metal casing and surrounding rock
formations for the zonal isolation in the plugging of oil and gas
wells [1–3]. The primary function of well cementing is to isolate
⇑ Corresponding author.
E-mail address: ceekkh@nus.edu.sg (K.K. Hau).
1
Present address of author: Korea Institute of Civil Engineering and Building
Technology, Gyeonggi-do, Republic of Korea.
2
Present address of co-author: Department of Civil and Environmental Engineering,
Seoul National University, Republic of Korea.
§ closely associated with cement hydration behaviour at early age
This paper uses standard cement 
chemistry abbreviations, where CaO is denoted
as C; Al2O3 as A; SiO2 as S; SO3 as S; Fe2O3 as F, and H2O as H. Structural formulae for
non-stoichiometric products are written in hyphenated form, i.e., calcium silicate
hydrate as C-S-H.Other abbreviations are as follows: API – American Petroleum
Institute, OWC – Oil Well cement, SGS – Static Gel Strength, RAS – Right-Angle-Set,
BWOB – By Weight of Binder.
the different zones of rock formations and to protect the metal cas-
ing from corrosion as well as to prevent the fluid or gas migration
from one layer to another [4]. Oil well cements (OWC) should have
certain properties and characteristics to function downhole in
wellbores. The American Petroleum Institute (API) provides stan-
dards for testing and the associated special apparatus needed to
investigate most of the properties of oil well cements. Some of
the recommended tests in the API standards include slurry density,
compressive strength, thickening time, static fluid loss, free fluid
content, permeability, rheological properties, gel strength and
slurry stability [5]. Among the properties of oil well cement for
well cementing listed above, gel strength and thickening time are
(in a few hours).
Static gel strength (SGS) is defined as the shear stress induced
by a force needed to start the flow of a fluid [6]. It is also
known as the shear yield point [7]. The SGS of a cement slurry is

https://doi.org/10.1016/j.conbuildmat.2018.10.074
0950-0618/Ó 2018 Elsevier Ltd. All rights reserved.
1094 L. Namkon et al. / Construction and Building Materials 191 (2018) 1093–1102
significant for the following two reasons: First, the development of
SGS is critical in deciding upon the safety factor against an unex-
pected shut down of a cementing job [7]. Second, SGS affects the
hydrostatic pressure in the cement slurry and the flow of fluids
or gases into the cement annulus. This is commonly referred to
as the fluid or gas migration pressure [7]. Fluid or gas migration
has been reported to cause serious problems, such as leakage in
shallow sands, undesirable interconnectivity between producing
zones, and uncontrolled gas flow to the surface [8,9]. API
Recommended Practice 10B-6 (R2015) utilises the concept of ‘gel
transition time’ based on SGS to mitigate gas migration [10].
The ‘gel transition time’ is defined as an intermediate period
during which the oil well cement acts, neither as a hydraulic fluid
nor as a solid under a static condition. During this period, oil well
cement slurry loses its capability to transmit hydrostatic pressure,
thus gas migration from formations may occur [8,9]. Cement slurry
transforms from a fluid state into a gelled state during hydration,
and pore pressure of the cement slurry then starts to decrease at
the gelled state. After a certain time of hydration, the pore pressure
becomes lower than the gas pressure. Consequently, gases or fluids
may invade the annulus. It is generally accepted that the gel tran-
sition time is the time interval required for the SGS of the cement
slurry to progress from 48 Pa (100 lbf/100ft2) to 240 Pa
(500 lbf/100ft2) [5,11]. At an SGS of 50 Pa, the slurry will not be
able to transmit any hydrostatic pressure, while at an SGS of
240 Pa the slurry will have sufficient gel strength to inhibit fluid
or gas migration into the cement column. In an earlier study
[12], it is proposed that the transition time between 50 Pa and
240 Pa be less than 40 min to lower the potential for fluid or gas
intrusion into the cement slurry. However, some studies show that
SGS is not critical in preventing gas migration based on simulated
tests conducted in the laboratory [11]. Although cement slurries
with short transition times have been shown to reduce the time
for gases or fluids to move up the annulus, this property alone is
not a guarantee of gas or fluid tightness [13]. Characteristics of a
cement slurry for controlling fluid/gas flows include density, excel-
lent fluid loss control (less than 50 ml), no free water/sedimenta-
tion, rapid setting, and short critical hydration period to maintain
hydrostatic pressure balance, low permeability and low shrinkage
to minimize gas entry [14]. Ideally, operators would like to have
the transition of cement slurry almost directly into a solid state
from a fluid state with negligible gelation. However, the transition
from gel to solid is normally a slow process and therefore, it is
desirable to shorten the gel transition time.
Another important property of well cement in relation to gas
migration is ‘Right-Angle-Set’ (RAS). The RAS property should not
be confused with the characteristic of having a short gel transition
time [11]. A ‘RAS’ cement slurry is defined as a well-dispersed sys-
tem which has no progressive gelation tendency, yet having the
ability to set very quickly due to rapid hydration reactions [15].
Consistency of a cement slurry is expressed in Bearden units of
consistency, BC. A RAS slurry retains low consistency values (<30
BC) for a period following which consistency increases to 100 BC
within a few minutes. Such a system will be able to maintain the
full hydrostatic pressure of cement column up to the beginning
of set, and subsequently transform into a very low-permeable
matrix, enough to prevent gas intrusion [15].
Gel transition time and RAS property of well cement slurries are
crucial to mitigate fluid or gas migration into annulus. The use of
mineral additives and chemical admixtures in OWC mixture could
be a solution for gas migration problems [16,17]. Calcium sulfoalu-

minate cement (CSA) consists of ye’elimite (C4A3S) and various
minor phases such as belite, anhydrite, calcium aluminate ferrite,
mayenite or gehlenite [18]. It is characterized by beneficial proper-
ties such as high early compressive strength, good expandability,
and high corrosion resistance [19]. The main applications of CSA
cements are as expansive additives in shrinkage-compensated
cements or as additives to special concretes for high early com-
pressive strength, self-levelling or high-performance fibre-
reinforced composites [20–22]. In addition, due to the low pH
and low porosity of the CSA paste and the capability of ettringite
and AFm phases to bind heavy metals, CSA cements have been
investigated for use as a mean to hazardous waste encapsulation
[23,24].
CSA cement has also been used as additives in Class G cements
to adjust thickening time, setting time and expandability of the
cement slurry for the purpose of deep water-well applications
under low-temperature environments [19]. The addition of gyp-

sum (C S H) to CSA cement is also reported to be effective in pre-
venting gelation problems arising from a premature increase in
viscosity or an unstable gel strength build-up of the cement slurry
[20]. The hydration kinetics of CSA cements depends mainly on the
amount and reactivity of the added gypsum [24,25]. The main
hydration reactions of the ye’elimite phase in CSA cements are as
shown below [26,27]:
 
C4 A3 S þ18H ! C3 A:C S :12H þ 2AH3 ð1Þ
  
C4 A3 S þ2C S H2 þ 34H ! C3 A:3C S :32H þ 2AH3 ð2Þ
  
C4 A3 S þ6CH þ 8C S H2 þ 74H ! 3C3 A:3C S :32H þ 2AH3 ð3Þ
According to Eq. (1), the hydration of ye’elimite results in the
formation of AFm and amorphous aluminium hydroxide. If there
is sufficient sulfate in the form of gypsum or anhydrite, ettringite
(AFt) is produced instead of monosulfate, according to Eq. (2)
[28]. The hydration of ye’elimite in the presence of portlandite is
based on Eq. (3) rather than Eq. (2). A higher amount of portlandite
accelerates the ye’elimite hydration at a very early age and reduces
the induction period [26,29]. In general, Eqs. (1) and (2) are pre-
dominant at a gypsum/Ye’elimite molar ratio <2.0 whereas only
Eq. (2) is predominant at a gypsum/Ye’elimite molar ratio >2.0.
In this study, mineral additions are utilized to control gel tran-
sition time and the consistency of the cement slurry under ambient
temperature and pressure conditions. In particular, CSA cement
and gypsum are added to API Class G cement at various mix ratios
to produce ettringite and other hydration products at very early
age for controlling the gel transition time and Right-Angle-Set
behaviour of the OWC slurries. The SGS and consistency were mea-
sured to investigate gel transition time and RAS properties of the
well cement slurries. Hydration behaviour is discussed based on
analyses of hydration heat flow and qualitative X-ray diffraction
(XRD) analyses.
Typically the hydration process of Portland cement is divided
into five periods as shown in Fig. 1(a): (I) initial reaction period;
(II) induction period; (III) acceleration period; (IV) deceleration
period; (V) stabilization period (not shown) [30]. Fig. 1(b) shows
the relationship between the SGS, hydrostatic pressure, and com-
pressive strength of fresh and hardened OWC slurry versus post-
placement time. In Fig. 1(a), the start point on the X-axis is when
anhydrous cement comes into contact with water. The start point
on the X-axis in Fig. 1(b) is shortly after an OWC slurry reaches
the plugging location of the wellbore. The starting points in Fig. 1
(a) and in Fig. 1(b) thus occur at different times. However, the rhe-
ological state of the OWC slurry immediately after reaching the
plugging location of the wellbore (corresponding to the start point
in Fig. 1(b)) is expected to be during Stage II (Fig. 1(a)), the induc-
tion period. The OWC slurry shows high fluidity during placement
due to the effect of added retarders. In the case of hydration heat
for C3S, Stage II ends when the rate of nucleation and growth starts
 L. Namkon et al. / Construction and Building Materials 191 (2018) 1093–1102
(a)
Fig. 1. Early-age behavior of a typical OWC slurry (a) Typical isothermal calorimetry curve of cement slurry [30] (b) Relationship of static gel strength, hydrostatic pressure,
and compressive strength of OWC slurry versus post-placement time. [6].
to accelerate [31,32]. In the case of the C3A, Stage II ends when the
sulfate ions can no longer disrupt the hydration of C3A as the added
calcium sulfate is consumed during the ongoing hydration reaction
[31]. Hydration products of the OWC slurry are not likely to grow
during pumping and casting operations since the slurry is under
constant shear force agitation. Thus, Stage II in Fig. 1(a) includes
both ‘‘Fluid” and ‘‘Gelled” cement states in Fig. 1(b), both of which
occur before setting at point E. The start point of Stage III at point E
is when the hydration starts to accelerate and initial setting occurs.
It corresponds to the ‘‘Solid” cement state. During this period, the
OWC slurry transforms to an interconnected solid matrix phase
with a percolating solid network [33].
Fig. 1(b) also presents the gel strength development versus
post-placement time. During the ‘‘Fluid” stage, the slurry has suffi-
cient fluidity to be pumped and thus the slurry maintains hydro-
static pressure which is typically higher than the formation gas
pressure. As the slurry gels progressively during the ‘‘Gelled” stage,
the hydrostatic pressure of the slurry gradually decreases with a
simultaneous increase in SGS. If the hydrostatic pressure reduces
below the formation gas pressure, gas migration may occur at
point A. The SGS at point ‘B’ is generally about 50 Pa [10]. In gen-
eral, when the slurry reaches a SGS of about 240 Pa at point ‘C’,
gas migration can be reasonably mitigated. Once gelling is com-
plete the cement starts to develop compressive strength at point
‘E’ [10]. Thus, gel transition time may be defined as the time taken
to reach ‘C’ from ‘B’. If the gel transition time is reduced, the poten-
tial for gases or fluids to infiltrate a cemented annulus may be
reduced. However, the effect of gel transition time on gas migra-
tion is still not fully understood as mentioned earlier.
Typical SGS of OWC slurries during the ‘‘gelled” stage register
magnitudes in the Pascal (Pa) range while the corresponding com-
pressive strengths of OWC slurries during the ‘‘solid” stage is in the
mega Pascal (MPa) range. During the period from ‘C’ to ‘E’, the OWC
slurry transforms into a coagulated network and its gel strength
increases significantly. This period is highly dependent on the type
and quantity of retarder, superplasticizer, mineral additions and
the chemical composition of the cement. The time taken to pro-
gress from ‘C’ to ‘E’ may take several minutes to a few hours. Dur-
ing this stage, the OWC slurry loses fluidity for pumping and
consists of a continuous network of solids arising from the forma-
tion of hydration products. As a result, the compressive strength
becomes measurable. The hardening and densification of the
OWC matrix can prevent gas migration. However, this stage falls
outside the scope of this paper. The aforementioned theoretical
background may help in understanding the relationships between
the gel transition time, hydration heat flow, and the thickening
1095
(b)
time of OWC slurry, which are of importance in controlling gas
migration and maintaining well integrity.
2. Materials and methods
2.1. Materials and mixture proportions
API Class G oil well cement (OWC) was used in this study. Cal-
cium sulfoaluminate (CSA) cement and gypsum were introduced as
mineral additions. A synthetic powder retarder and a melamine
formaldehyde-based powder superplasticizer (SP) were used as
chemical additives. The chemical composition of the cements used
are given in Table 1. The C3S, C3A, and SO3 contents of the Class G
cement used in this study are 62.6%, 1.4%, and 2.5%, respectively,
and the C2S, C2F, and MgO contents are 23.2%, 7.0%, and 0.1%,
respectively. The cement satisfies the chemical requirements
(C3S  65%, C3A  3.0%, SO3  3.0%) of Class G cement specified in
API Specs 10A [34].
The mixture proportions of the OWC slurries are summarized in
Table 2. The API Class G standard slurry was prepared with a w/b of
0.44 as specified in API Specs 10A [34]. Slurries with two water-to-
binder (w/b) ratios, 0.32 and 0.40, were prepared for static gel
strength tests and to compare their gel transition time in order
to evaluate which w/b is more suitable for the targeted application
as a plugging material. For all other tests, a w/b of 0.40 was used
for practical considerations of workability and shorter test dura-
tions. The sum of CSA cement and gypsum is 1, 3 or 5 percent by
weight of binder (%BWOB). The ratios of CSA cement to gypsum
are 100:0, 70:30, or 50:50. While the dosage of retarder was varied
to adjust for consistency, SP dosage was held at 0.5 %BWOB. The
following notations are used to identify samples throughout this
paper: ‘APIG’ refers to an API Class G standard cement slurry with-
out superplasticizer or retarder. ‘C’ followed by a number indicates
the total weight of CSA cement and gypsum in %BWOB. ‘H’ and ‘L’
indicate a CSA cement to gypsum ratio of 50:50 and 100:0, respec-
tively. Samples without ‘H’ or ‘L’ have a CSA cement to gypsum
ratio of 70:30. The last number denotes the retarder dosage in %
BWOB.
2.2. Methods
The OWC slurries were prepared using a high-speed shear blen-
der (Model #M7000) manufactured by Cement Test Equipment,
Inc. (CTE, USA), in accordance with procedures outlined in API
Specs 10A [34]. A dry blend containing the Class G cement, CSA
cement and gypsum was prepared. The retarder and SP powder
1096 L. Namkon et al. / Construction and Building Materials 191 (2018) 1093–1102

Table 1
Chemical oxide composition of cements used.

(wt%) SiO2 Al2O3 Fe2O3 CaO MgO TiO2 K2O SO3 Na2O
Class G cement 17.5 3.7 4.1 66.2 2.2 0.2 1.2 2.5 0.1
CSA cement 9.1 36.2 – 45.5 – – – 7.4 –

Table 2
Mix proportions of OWC slurries.

Sample name %BWOB w/b Retarder %BWOB SP %BWOB

G cement CSA cement Gypsum
APIG 100 – – 0.44 0 0
C1-0.2 99 0.7 0.3 0.40 0.2 0.5
C1-0.5 0.40a 0.5 0.5
C3-0.2 97 2.1 0.9 0.40 0.2 0.5
C3-0.3 0.40 0.3 0.5
C3-0.4 0.40 0.4 0.5
C3-0.5 0.40a 0.5 0.5
C5-0.5 95 3.5 1.5 0.40a 0.5 0.5
C5H-0.1 95 2.5 2.5 0.40 0.1 0.5
C5H-0.5 0.40 0.5 0.5
C5L-0.1 95 5 – 0.40 0.1 0.5
C5L-0.5 0.40 0.5 0.5
a
Sample with a water/binder ratio of 0.32 was also prepared for SGS tests.

additives were pre-dissolved in the mix water before adding in the
dry blend. In the procedure adopted for OWC slurry preparation,
the dry blend was added to the mix water in the blender cup
within 15 s at 4000 rpm and then mixed at 12000 rpm for a further
35 s. After mixing, the OWC slurry sample was transferred into the
vessel for the measurement of the SGS and consistency. All exper-
iments were conducted at ambient temperature (25 °C ± 1 °C) and
ambient pressure.
2.2.1. Hydration heat analysis
Isothermal conduction calorimetry was conducted according to
ASTM C 1679 [35] using a TAM Air calorimeter (TA Instruments) at
25 °C ± 1 °C for 172 h. A 10 g sample of the OWC slurry was por-
tioned as quickly as possible into the ampule with sample mass
recorded. After capping the ampoule, the sample and reference
ampoules were inserted into the calorimeter. The early thermal
response (approximately 10 min) of the samples could not be mea-
sured due to external mixing method. The total heat of hydration
after 172 h was calculated by integration of the heat flow curve
between 10 min and 172 h.
2.2.2. Static gel strength
Static gel strength (SGS) analyser (Model # 15–400, CTE corp.,
USA) was used to measure the SGS of the OWC slurry samples.
The paddle was rotated at a speed of 0.1825°/min (0.0005 rpm)
using a stepper motor drive and the torque on the paddle derived
from the gel strength is measured. The speed of rotation of the pad-
dle was adjusted to be slightly below the rate of development of
defined as ‘‘time elapsed from the initial application of pressure
and temperature to the time at which the slurry reaches a consis-
tency deemed sufficient to make it unpumpable (eg. 70 Bc or 100
Bc).”
2.2.4. X-ray diffraction
XRD tests were performed using a SmartLab device (Rigaku,
Japan). A CuKa radiation at 45 kV and 200 mA, a step size of
0.01° and 0.2 s per step were employed with a 2h scanning range
of 5°–70°. The diffraction data provided by the Inorganic Crystal
Structure Database (ICSD) was used for phase identification of
the test samples.
3. Results and discussion
3.1. Isothermal calorimetry
Fig. 2 illustrates heat flow of the OWC slurries. While the heat
flow was measured for 172 h, the patterns are displayed for a dura-
tion of 144 h only for greater clarity in distinguishing between the
thermal responses of the OWC slurries (Fig. 2(a)). The second peak
of heat flow occurred at different times depending on the amount
of CSA cement and gypsum incorporated. The second peak of sam-
ple C1-0.5 reached a maximum at 64 h, and that of samples C3-0.5
and C5-0.5 are 20 h and 17 h, respectively. As the amount of CSA
cement increases, the acceleration period (corresponding to Stage
III in Fig. 1(a)) begins earlier. For the samples C3-0.5 and C5-0.5,


the SGS of the samples.
2.2.3. Thickening time
Consistency and thickening time of the OWC slurries were mea-
sured using a fully automatic consistometer (Model # M22-400-
Auto, CTE corp., USA) in accordance with procedures outlined in
API RP 10B-2 [5]. The slurry cup rotates at 150 rpm ± 15 rpm and
the torque, exerted on the paddle attachment, is measured in BC
[5]. The time taken to reach 30 BC is commonly considered as the
time available for pumping and placing an OWC slurry in the well-
bore. In a cementing operation, the value of 70 BC is generally
accepted as the maximum consistency for the OWC slurry to be
pump able. According to API RP 10B-2 [5], thickening time is
the main phases (C4 A3 S, C2S and C12A7) of CSA cement contributed
to the rapid formation of ettringite and monosulfate. This is why
the acceleration period of C3-0.5 and C5-0.5 occurred earlier. The
second peak, corresponding to reaction of C3S in the Class G
cement was observed earlier in C3-0.5 and C5-0.5 as compared
to C1-0.5. This indicates that the effect of the retarder on the C3S
hydration is less significant in C3-0.5 and C5-0.5 than in C1-0.5.
Most of the retarder added to C1-0.5 delayed the hydration of
C3S so that the acceleration period of C1-0.5 began much later.
On the other hand, the second peak of C3-0.5 and C5-0.5 appeared
earlier when compared to C1-0.5 due to the rapid hydration reac-

tion of C4 A3 S and C12A7 in the CSA cement which reduced the
effect of added retarder. Fig. 2(a) also shows the effect of added
 L. Namkon et al. / Construction and Building Materials 191 (2018) 1093–1102
Fig. 2. Heat flow of OWC slurries with 0.5% bwoc of superplasticizer and 0.5% bwoc of retarder in comparison to that of APIG: (a) 0 to 144 h, (b) 0 to 36 h, (c) 0 to 6 h, (d) 0 to
192 h.
CSA cement and gypsum on hydration heat flow. The samples C5-
0.5 and C5L-0.5 show second peaks at similar times while C5H-0.5
shows a later second peak although with higher intensity than that
in C5-0.5 and C5L-0.5. As the gypsum amount increases relative to
cements, formation of ettringite and C-S-H are delayed possibly
due to gypsum’s adsorption onto the surfaces of Class G and CSA
cement particles, retarding hydration of the cements [36].
Fig. 2(b) shows the heat flow for a time duration of 36 h. The
APIG slurry registered a second peak at an earlier time when com-
pared to the C-series slurries which had CSA cement and gypsum.
This is because there was no retarder and SP in the APIG slurry. A
small peak preceding the second peak was observed in C5-0.5 and
C5L-0.5 at 8 h and 12 h, respectively. These peaks are associated
with the formation of ettringite, as reported in literature [37]. In
C5H-0.5 sample with a higher amount of gypsum than the other
samples, some unreacted gypsum might have disrupted the hydra-
tion of CSA cement and the formation of ettringite, and accordingly
no small peak associated with ettringite formation was observed.
This effect is clear when comparing the second peaks of C5-0.5
and C5H-0.5 in Fig. 2(b). The second peak is related to development
of early-age compressive strength. However, it has no relationship
with SGS and consistency of OWC slurry since they occur during
Stage II (Fig. 1(b)) before the second peak. In other words, despite
the second peak occurring at an earlier time, it does not always
lead to a shorter gel transition time and a more predominant
RAS property. Rather, the gel transition time and RAS property
seem to be associated more with the induction period of heat flow
than the acceleration period (see Section 3.3).
Fig. 2(c) shows the hydration heat flow for a total time duration
of 6 h. This clearly represents the induction period. The acceleration
period of the APIG slurry began after about 3 h, which was very dif-
ferent from the C-series slurries. A small peak was observed at 0.5 h
1097

in the case of C5L-0.5, probably due to fast dissolution of C4 A3 S and
C12A7 phases or during formation of ettringite [38]. Since no gyp-
sum was added to C5L-0.5 sample, ettringite might not be formed
due to insufficient amount of sulfate present, and lack of additional

gypsum might delay the hydration of C4 A3 S and C12A7. A small peak
was not detected in the case of C5H-0.5 which seemed to have suf-
ficient amount of gypsum. During the induction period, occurring
approximately between 0.5 and 3 h, the C-series slurries showed
higher heat flow than the APIG slurry. This supports the contention
that considerable amounts of ettringite or monosulfate might be
formed in the C-series slurries during the first 3 h.
Fig. 2(d) illustrates cumulative heat flow of the slurries. The
APIG slurry, without retarder and SP, had the highest cumulative
heat flow among the slurries. The hydration delay induced by the
addition of retarder is the highest in C1-0.5 due to the lowest
amount of CSA cement and gypsum among all the C-series slurries,
thus showing the lowest cumulative heat flow. As mentioned
above, the retarder effect was diminished with the increasing
amount of CSA cement in the slurries.
3.2. X-ray powder diffraction (XRD)
Fig. 3(a) shows XRD patterns of Class G and CSA cements used in
the OWC slurries. The crystalline phases present in the anhydrous
Class G cement were C3S (Hatrurite), C2S (Larnite), C2F (Brownmil-
lerite), calcium sulphate anhydrate, gypsum and minor quantity of
phases MgO (Periclase) and C3A. The main phase of the CSA cement

was Ye’elimite (C4 A3 S) and C2S (Larnite) and C12A7 (Mayenite) and
a minor quantity of CT (Perovskite).
Fig. 3(b)–(e) show XRD patterns of the C-series slurries. The
XRD pattern of C1-0.5 at Day 1 was not recorded since it was not
1098 L. Namkon et al. / Construction and Building Materials 191 (2018) 1093–1102
Fig. 3. XRD patterns of raw cements and OWC slurries with CSA cement and gypsum [P: Ca(OH)2, E: Ettingite, A: C3S, B: C2S, F: C2F, C-S-H]: (a) Raw materials (b) C1-0.5 (c)
C3-0.5 (d) C5H-0.5 (e) C5-0.5 (f) C5-0.5 early age.
hardened. In Fig. 3(c) and (e), the presence of ettringite was
observed at Day 1, and the intensity of the peaks corresponding
to ettringite was similar between 3 and 28 days. This indicated that
most of ettringite was formed within 1 day. Although the total
amount of CSA cement and gypsum was increased from 1 to 5%,
intensity of the peaks related to ettringite formation was not sig-
nificantly changed. Chemical and mineralogical changes of the
OWC slurries with CSA cement occurred mostly within 1 day.
Meanwhile, intensity of the peaks associated with portlandite
(CH), C3S, and C2S were significantly changed with time. As curing
age increased from 1 to 28 days, intensity of the peaks related to
portlandite gradually increased and that of the peaks related to
C3S and C2S decreased. The broad peak corresponding to C-S-H at
29–30 ° increased with time. In particular, intensity of the peaks
related to C3S reduced significantly between 1 and 3 days, as
shown in Fig. 3(c), (d) & (e), which indicates that most of C3S phase
was hydrated during this period.
Fig. 3(f) shows XRD patterns of C5-0.5 measured at 3 h and
1 day. Hydration of C5-0.5 was stopped by using isopropanol as
soon as consistency of the slurry reached 100 BC, 3 h after begin-
ning the test. Intensity of the peak at 18.1° assigned to portlandite
in C5-0.5 was very weak at 3 h, while that of the peak assigned to
ettringite at 3 h is almost the same as that at 1 day. It may be

attributed to fast dissolution of C4 A3 S and C12A7 phases in the
CSA cement sample and the resulting precipitation of ettringite.
Intensity of the peaks corresponding to C3S were much lower at
1 day than at 3 h. This result confirmed that reaction of CSA cement
and gypsum are predominant compared to hydration of the C3S
phase in the Class G cement at a early age (within a few hours).
 L. Namkon et al. / Construction and Building Materials 191 (2018) 1093–1102 1099

3.3. Static gel strength
The SGS results of APIG slurry and OWC slurry samples incorpo-
rating CSA cement and gypsum with a w/b ratio of 0.40 are shown
in Fig. 4(a). The consistency of the slurry was measured for the first
10 min to simulate pumping of the cement slurry under typical
wellbore conditions, and thereafter the SGS was measured. A SGS
of 50 Pa corresponds to a condition when the OWC slurry begins
to transition from a fluid state into a gelled state and gradually
loses hydrostatic pressure during the gelation stage.
It is clear that a higher amount of CSA cement led to a more
rapid development of SGS. The hydration of CSA cement and gyp-
sum may lead to the formation of an ettringite network. The ettrin-
gite network in the OWC slurry samples resulted in a loss in
physical plasticity of the OWC slurries, and increased the SGS.
The SGS development between 10 and 40 min was slightly higher
in C3-0.5 than in C5-0.5 although C5-0.5 had a higher amount of
CSA cement. This was also observed in the C3-0.5 and C5-0.5 sam-
ples with a lower w/b ratio of 0.32 (Fig. 4(b)). This indicates that an
increase in the SGS might depend not only on the amounts of CSA
cement and gypsum, but also on the competitive hydration
between Class G and CSA cement. Table 3 shows the gel transition
times of the OWC slurries tested. The gel transition times of C1-0.5,
C3-0.5 and C5-0.5 with a w/b ratio of 0.40 were 36.0, 28.5, and
21.0 min, respectively. These are much shorter than those reported
in previous studies [7,13,16]. The sample C5-0.5 had the shortest
gel transition time justifying the high dependency of gel transition
time on the CSA cement amount incorporated. It must be noted
that the gel transition times of the OWC slurries with a lower w/
b ratio of 0.32 also follow a similar trend, confirming the predom-
inant effect of CSA cement in early-age gel strength development.
A comparison between the gel transition time for C5-0.5 and
C5H-0.5 (Table 3), shows that although the time taken for SGS to
reach 50 Pa differs, the gel transition time is relatively unchanged.
Some sulphate from gypsum might have remained unreacted in
the C5H-0.5 sample, and the unreacted sulphate is likely to have
retarded the hydration of CSA cement. From Fig. 4(a) and Table 3,
it can be observed that the gel transition time of the APIG slurry
sample was the longest among all the samples (68 min) despite
not containing any retarder or SP additive. Ettringite or monosul-
fate could not form rapidly in the APIG slurry due to lack of CSA
cement. As a result, development of SGS in the APIG slurry was slo-
wed down considerably.
3.4. Consistency
Fig. 5(a) shows the consistency results of the OWC slurry sam-
ples with CSA cement and gypsum. It was desired to limit the
thickening time test duration of the OWC slurries to about 5 h
for realistic application. C1-0.5 and C3-0.5 OWC slurries could
not reach 100 BC within a 5 h duration with a 0.5 %BWOB retarder
dosage due to very significant retardation effect. Therefore, the
retarder dosages were readjusted accordingly such that consis-
tency of the test samples could reach 100 BC within 5 h. The pur-
pose of this test was to study the thickening time profile of the
OWC slurries for a desirable RAS property. The RAS property can
be understood as the time taken for consistency to increase from
30 to 100 BC. In Fig. 5(a), the C-series samples show different initial
consistency behaviour. This can be attributed to several factors.
Both the retarder and SP additives possess mildly dispersing prop-
erties imparting fluidity to the slurry on preparation. Gypsum,
introduced as a mineral addition, lowers the initial consistency
drastically and delays the hydration of CSA cement thus slowing
down the formation of ettringite. The SP and increasing amounts
of retarder and gypsum disperse the slurry resulting in lower con-
sistency for a considerable period. As a result, C5-0.5 showed the
lowest initial consistency in comparison to the other C-series
slurries due to the highest dosages of retarder and gypsum. The

Fig. 4. Static gel strength (SGS) results of OWC slurries with 0.5% bwoc of superplasticizer and 0.5% bwoc of retarder in comparison to that of APIG: (a) w/b ratio = 0.40 (w/
b = 0.44 for APIG sample), (b) w/b ratio = 0.32.

Table 3
Gel transition times of OWC slurries.

Sample %BWOB w/b Time to reach Time to reach Gel transition

50 Pa (A), min 240 Pa (B), min time (B-A), min
G cement CSA cement Gypsum
APIG 100 – – 0.44 48.0 116.0 68.0
C1-0.5 99 0.7 0.3 0.40 47.0 83.0 36.0
C3-0.5 97 2.1 0.9 29.5 58.0 28.5
C5-0.5 95 3.5 1.5 34.0 55.0 21.0
C5H-0.5 95 2.5 2.5 51.0 72.5 21.5
C1-0.5 99 0.7 0.3 0.32 41.5 66.5 25.0
C3-0.5 97 2.1 0.9 24.0 49.5 25.5
C5-0.5 95 3.5 1.5 28.5 49.5 21.0
1100 L. Namkon et al. / Construction and Building Materials 191 (2018) 1093–1102

Fig. 5. Consistency results of OWC slurries (a) Effect of CSA cement and gypsum (b) Effect of retarder dosage (c) Comparison of C5-0.5 and APIG.

consistency of C1-0.2 was initially high, at about 30 BC, and contin-
ued to increase over the next 4 h. CSA cement content in C1-0.2
may not be enough for quick gel coalescence within the first few
hours and the combined effect of the retarder and gypsum further
delayed cement hydration. The initial consistency of C3-0.2 was
5 BC, increasing steadily to reach 100 BC after 125 min. Here, it is
apparent that an increase in CSA cement content resulted in steady
ettringite formation in a few hours opposing the influence of the
retarder. The consistency of C5-0.5 remained low for 135 min
and after about 140 min, the consistency began increasing quickly
to reach 100 BC within a few minutes, appearing to be analogous to
RAS behaviour. Delayed increase in consistency can be attributed
to higher gypsum content that slowed down hydration of CSA
cement. Upon hydration, the ettringite formation occurred rapidly
due to higher CSA cement content in C5-0.5 compared to C1-0.2
and C3-0.2. Shorter TRAS of the C5-0.5 sample (Table 4) indicates
that loss of fluidity and formation of a hydrated gel occurred within
a few minutes. It is possible that with increasing amounts of CSA
cement and gypsum, the OWC slurry is more likely to show RAS
behaviour due to rapid ettringite formation. From Fig. 5(c) and
Table 4, it is clear that C5-0.5 has a much faster TRAS (17 min) than
that of APIG (104 min), showing closer RAS tendency with shorter
overall thickening time. This shows the significant effect of the
mineral additions on RAS property.
The amount of chemical retarder significantly affected the over-
all thickening time, but had little effect on RAS behaviour. This is
supported by the consistency results shown in Fig. 5(b). The thick-
ening time of C3-0.2 was 124 mins and that of C3-0.3 was about
340 mins, while the consistency of C3-0.4 was less than 10 BC dur-
ing the first 5 h due to the retardation effect. This demonstrates
that the retardation effect in measuring thickening time is highly
sensitive to retarder dosage. It can be observed that TRAS consis-
tency profile of C3-0.2 is very similar to C3-0.3 (Fig. 5 (b)). TRAS
in C3-0.2 and C3-0.3 was 70 and 60 min respectively, although
C3-0.2 and C3-0.3 had different amounts of retarder (0.2 %BWOB
and 0.3 %BWOB, respectively). This suggests that the retarder does
not greatly influence RAS property although it extends overall
thickening time. A major factor which enhanced RAS tendency of
the samples tested was found to be the mineral additions, CSA
cement and gypsum.

Table 4
Thickening times of OWC slurries.

Sample w/b %BWOB Chemical Time to reach Time to reach 100 BC (B), TRAS (B-A), min
additives 30 BC (A), min min (Thickening time) (for RAS property)
(%BWOB)
G cement CSA cement Gypsum Retarder SP
APIG 0.44 100 – – – – 197.0 301.0 104.0
C1-0.2 0.40 99 0.7 0.3 0.2 0.5 7.5 250.0 242.5
C3-0.2 97 2.1 0.9 0.2 0.5 54.0 124.0 70.0
C3-0.3 0.3 0.5 281.0 341.0 60.0
C3-0.4a 0.4 0.5 – – –
C5-0.5 95 3.5 1.5 0.5 0.5 181.0 198.0 17.0
a
TRAS of C3-0.4 sample could not be calculated since consistency of the sample did not reach 30 BC within the test duration limit of 5 h.
 L. Namkon et al. / Construction and Building Materials 191 (2018) 1093–1102
4. Summary and conclusions
Improper plugging of oil and gas wells has been reported to
result in migration of reservoir fluids to the surface over extended
periods after a well’s operational life, posing environmental con-
cerns. This creates the need for cement-based plugging materials
with improved physical properties and encourages investigation
into developing a new well cement slurry. An important consider-
ation for field application is the workability of the slurry.
Operators prefer cement slurries that are pump able on
preparation and can set within a few hours, especially for a
non-profitable operation such as plugging and abandonment of
an oil or gas well.
This study investigated hydration and gelation behaviour of
OWC slurries incorporated with mineral additions, CSA cement
and gypsum. The C-series OWC samples were designed with an
objective to enhance key physical properties of gel transition time
and Right-Angle-Set tendency under certain test conditions. The
addition of CSA cement and gypsum to Class G cement led to the
formation of ettringite, CH and C-S-H through the hydration pro-
cesses with most of the ettringite forming within a day. Isothermal
calorimetry results show that hydration of OWC slurries was accel-
erated by the addition of CSA cement and the dormant period was
accordingly shortened.
The static gel strength of OWC slurries was rapidly increased on
addition of CSA cement such that the gel transition time was short-
ened. RAS property of the OWC slurries was more evident with
increasing amounts of CSA cement regardless of the amount of
retarder. This behaviour can be attributed to the coalescence of
the ettringite networks, which results in a loss of physical plasticity
of the OWC slurry and an increase in consistency. The sulphate in
the gypsum prevented quick setting of the OWC slurry and helped
to maintain desirable fluidity. It is common practice in laboratory
tests to determine the thickening time based on 100 Bc. As the
thickening time largely depends on the well depth and downhole
temperature and pressure, the requirements on the time to reach
30 Bc and overall thickening time may differ with each well. The
authors are not aware of any requirement for the thickening time
in API standards. In practice, operators can design cement slurries
with a thickening time that meets their requirements based on well
conditions.
Sample C5-0.5 exhibited the most superior gel strength devel-
opment and Right-Angle-Set tendency in comparison to the stan-
dard APIG and other C-series OWC samples. While this is an
advantageous characteristic, further development is envisaged
to enhance other physical properties such as compressive
strength and shrinkage resistance. It must be noted that while
the other C-series OWC slurries did not display the same level
of performance as C5-0.5 under the test conditions, they could
show potential for field application under varied conditions, for
instance, higher temperature and/or pressure. The experiments
in this paper were conducted at ambient temperature and pres-
sure conditions. However, it is expected that at higher tempera-
tures the superplasticizer and/or retarder dosages and mixtures
may need to be adjusted in order to obtain required fluidity of
the OWC slurries.
5. Funding and acknowledgments
This work was supported by the Singapore Maritime Institute
(ID: SMI-2016-OF-05). Grateful acknowledgment is made to Nau-
ticAWT Ltd for collaborative support with access to the company’s
OWC laboratory, equipment and materials. The authors would like
to acknowledge key personnel from NauticAWT: Dr Kok-Seng Chia,
and Mr Elo Yde, for their advisory role in this project.
1101
Conflict of interest
The authors declare that they have no conflict of interest.
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