Construction and Building Materials 149 (2017) 279–288

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Construction and Building Materials

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Abnormal gelation phenomenon of Class G oil well cement incorporating

polycarboxylic additives and its countermeasures
Di Chen a, Jintang Guo a,⇑, Xiujian Xia a, Yongjin Yu a,b, Jianzhou Jin b, Ming Xu b, Shuoqiong Liu b, Yakai Feng a
a
School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China
b
Drilling Research Institute, China National Petroleum Corporation, Beijing 102206, China

h i g h l i g h t s

 Flash-setting or flocculation for carboxylic polymer modified cement happens around 120 °C.
 Cross-linking for polycarboxylic cement hydrates is the main reason of the abnormal gelation.
 Viscosity uprush of polymer solution occurred around 120 °C accelerates the abnormal gelation of slurry.
 Optimization of polycarboxylic structure and addition of special salts could eliminate the abnormal gelation phenomenon.

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

Article history: Cementing security is endangered by the abnormal gelation phenomenon of cement slurry incorporating
Received 10 November 2016 polycarboxylic additives occurred around 120 °C. The differences between gelatinous and non-gelatinous
Received in revised form 27 April 2017 sections were investigated through various techniques. The polymer structural change around 120 °C
Accepted 6 May 2017
could explain the abnormal gelation phenomenon by viscosity-temperature characterization. The other
Available online 22 May 2017
reasons are the polycarboxylic additives combine with Ca2+, SiO24 and aluminate hydrate by cross-
linking reaction. The cross-linking structure developed flocs which was embedded in calcium silicate
Keywords:
hydrate (C–S–H) gel and intertwined around stirring shaft. The practicable methods were proposed to
Abnormal gelation phenomenon
Polycarboxylic additive
relieve or solve the abnormal phenomenon of cement slurry.
Oil well cement Ó 2017 Elsevier Ltd. All rights reserved.
Solution methods
Cementing

1. Introduction
Cementing operation is one of the most important steps in the
process of oil and gas well development [1]. The cement slurry is
pumped down through a metal casing and back up the annular
space between the formation and metal casing to form a protective
sheath. The one objective is to reinforce the borehole wall and sup-
port the casing string. The other purpose is to ensure complete
sealing and integrated structural [2]. Specifically, it is able to pre-
vent the migration of formation fluid, and avoid the annular gas
migration in the cementing and production operations. The well
cementing operation is unrepeatable process which is important
for the whole processes of oil well construction. While easily-
exploited and recoverable reserves of onshore hydrocarbon
resources decrease significantly in China, the oil/gas exploration
and development tend to unconventional reservoir [3]. Facing
⇑ Corresponding author.
E-mail address: jtguo@tju.edu.cn (J. Guo).
more and more complex and difficult condition, both cementing
safety and zonal isolation quality are the main issues of well
cementing operation [4]. A large number of additives and admix-
tures are mixed into the cement system to adjust the performance
of cement slurry. Polymer-based additives are particularly used in
the well cementing operation over the past decades to meet the
special requirements in harsh borehole conditions including high
temperature, high pressure, and high salinity [5].
The retarder is used to ensure the cementing operation safety
by adjusting the setting time of cement slurry and improving its
rheological property at specified temperature. The synthetic
copolymers of 2-arcylamido-2-methylpropane sulfonic acid
(AMPS), itaconic acid (IA), acrylic acid (AA), maleic anhydride
(MAH), and their derivative are often used as retarder [6–8]. The
polymer fluid loss additive is used to prevent cement slurry from
losing water, protect the formation and the oil-gas reservoir
against contamination, and keep the pumpability of slurry to
ensure the safety of cementing operation. The polycarboxylic
fluid loss agent is mainly composed by AMPS, acrylamide (AM)

http://dx.doi.org/10.1016/j.conbuildmat.2017.05.062
0950-0618/Ó 2017 Elsevier Ltd. All rights reserved.
280 D. Chen et al. / Construction and Building Materials 149 (2017) 279–288

or N,N-dimethylacrylamide (NNDMA), vinyl pyrrolidone (N-VP),

IA, AA, MAH and so on [9,10]. Polycarboxylic cement additive is
one of the most common and important additives that has
attracted great interest of researchers in petroleum industry due
to their excellent performances [10,11].
Since the cement slurry contained polycarboxylic additives, the
abnormal phenomena have been occurred occasionally at high
temperature either in laboratory research or in field application.
As depicted in the thickening curves and diagrams of Fig. 1, the
abnormal phenomena are manifested as temperature and pressure
oscillations, flash setting and consistency jumping at bottom hole
circulating temperature (BHCT, about 120 °C). At the end of exper-
iment, it can be seen that partial cement slurry is wrapped around
the stirrer shafting, a gel state and obvious stratification can be
observed after setting. Furthermore, the gelatinous cement slurry
could adhere on the wall of borehole and casing, and even block
up the narrow annular area between the formation and metal cas-
ing during the pumping process, which is shown in Fig. 2(b). This
will bring risk to cementing operations, seriously affect the
cementing quality, and even lead to the cementing failure. The nor- Fig. 2. Schematic diagram of (a) the normal cementing process and (b) the
abnormal gelatinous phenomenon for polycarboxylic cement slurry.
mal cement slurry system and cementing process are also
described in Fig. 2(a) for comparison. The abnormal phenomena
2. Experimental
of cement slurry have been paid more attention to [12–14]. Guo
et al. presented the mechanism of the abnormal setting time of 2.1. Materials
class G oil well cement at elevated temperature based on the
experimental data and theoretical analysis [1]. Other researchers According to American Petroleum Institute (API) specification, Class G oil well
cement used in laboratory is provided from Jiahua Special Cement Co., Ltd (Sichuan,
discussed the mechanism of abnormal gelatinous phenomenon China). Its chemical compositions and physical properties are shown in Table 1,
for the cement slurry containing polycarboxylic additives which were measured by powder X-ray fluorescence (XRF-1800, Shimadzu, Japan)
[15–20]. However, the cause and mechanism of the abnormal phe- and laser-based particle size analyzer (LS-C (III), OMIEC). Besides, its mineralogical
nomena were rarely studied due to the complexity of cement phase compositions were also measured by Rietveld X-ray diffraction (Rietveld
XRD, Brook D8 Advance, Germany), presented in Table 2.
hydration, especially the reasons of abnormal gelatinous phenom-
Four polycarboxylic additives were used in the study and listed in the Table 3.
ena around 120 °C. These polycarboxylic additives were synthesized by aqueous free radical copoly-
It is an interesting work to study the reasons of abnormal gela- merization according to the method described in the literatures [21,22]. In particu-
tion phenomenon, which is caused by polycarboxylic additives lar, Sample II was synthesized using AMPS, octadecyl- dimethylallylammonium
around 120 °C. Hence, this paper explored the mechanism of the chloride (ODAAC) and IA. ODAAC is a reactive cationic surfactant with long
hydrophobic side-chain. Sample III is a zwitterionic copolymer which is a terpoly-
abnormal gelation phenomena happened from the perspective of mer of AMPS, diallyldimethylammonium chloride (DMDAAC) and IA [21]. Sample
microstructure. The structural differences between gelatinous IV was synthesized via the copolymerization of AMPS, DMDAAC, NNDMA and IA
and non-gelatinous parts from cement slurry were investigated [22].
by techniques such as Fourier transform infrared spectroscopy
(FTIR), X-ray powder fluorescence spectroscopy (XRF), scanning
2.2. Sample preparations
electric microscope (SEM) and energy spectrum analysis (EDS).
The mechanism and hypothesis of abnormal gelation phenomenon 2.2.1. Preparation of cement slurry
were discussed by simulated inorganic salt solution experiment, Oil-well cement slurry with standard density of 1.90 g/cm3 was used for this
and the solution methods were presented from the perspective study and prepared according to the procedures described in ‘‘Recommended Prac-
tice for Testing Well Cements,” API Recommended Practice 10B issued by the API
of molecular structure.
standard. Different kinds of liquid additives were completely dissolved in the mixing

Fig. 1. Abnormal gelatinous phenomena (a) without temperature and pressure oscillations and (b) with temperature and pressure oscillations (the illustrations are optical
images of gelatinous parts).
 D. Chen et al. / Construction and Building Materials 149 (2017) 279–288 281

Table 1
Chemical compositions and physical properties of Class G oil well cement (HSR).

Chemical compositions,% w.t. Physical properties

SiO2 Al2O3 Fe2O3 CaO MgO SO3 Na2O K2O L.O.I d50 Specific surface area, m2/g Density, g/cm3
18.689 3.115 4.338 55.111 1.558 2.868 0.557 0.596 2.92 14 lm 428.6 3.15

Note: HSR is high sulfate-resistant; L.O.I is loss on ignition; d50 is the average particle size.

Table 2
Phase compositions of Class G oil well cement (HSR).

C3S C2S C3A C4AF Free lime

53.29 21.17 6.34 8.97 0.18

The thickening time is the duration that the slurry remains pumpable, which is
recorded as the time between the initial application of temperature/pressure to
Table 3
the pressurized consistometer and at which a consistency of 100 Bearden units
Polycarboxylic additives used in the study.
(Bc) was reached. Bc represents the consistency of slurry with no direct conversion
Mark Polycarboxylic additives Phenomena factor to more common units of viscosity [24].

Sample I AMPS-co-AA-co-IA Abnormal gelatinous

2.3.4. Viscosity-temperature characteristic
Sample II AMPS-co-ODAAC-co-IA Relieve effectively
HTHP Rheometer (Model 7500, Chandler, USA) was used to investigate the
Sample III AMPS-co-DMDAAC-co-IA Relieve effectively
viscosity- temperature characteristic of polymer samples. Polycarboxylic additives
Sample IV AMPS-co-DMDAAC-co-NNDMA-co-IA Normal
were added to distilled water and shaken to ensure a homogenous test solution
of concentration 100 g/L. The apparent viscosity of the polymer at different temper-
atures was measured over a wide temperature range from 23 °C to 150 °C with rota-
water in a consecutive way. Class G Cement was added within 15 s at 4000 ± 100 rpm tion speed of 150 rpm and test pressure of 21 MPa.
and then mixed for 35 s at 12,000 ± 250 rpm in model OWC-2000D Waring blender.
Cement slurry compositions were prepared comprising Class G Cement, water (0.42, 3. Results and discussion
by weight of cement, BWOC) and retarder (2% BWOC). All slurries were mixable,
pourable, and with no evidence of settling.
3.1. Chemical composition analysis of gelatinous and non-gelatinous
2.2.2. Preparation of gelatinous and non-gelatinous samples samples
Sample I was dissolved in water respectively and then mixed with oil well
cement using Waring blender, maintaining the water-cement ratio (W/C) of 0.44. The abnormal gelatinous phenomena happens around 120 °C,
High temperature thickening experiment of cement slurries mixed with different
which is caused by polycarboxylic additives (Sample I). In this sec-
polycarboxylic additives were measured by Chandler 8040D high-temperature
and high-pressure (HTHP) consistometer at 130 °C and 65 MPa. When the abnormal
tion, FTIR, XPS, XRF, XRD, SEM and EDS were used to investigate
gelatinous phenomenon occurred, the gelatinous slurry and non-gelatinous one the chemical composition differences and micromorphology of
were separated and then transferred into vacuum drying oven at 60 °C. gelatinous part and non-gelatinous one.

2.3. Characterizations 3.1.1. FTIR analysis

2.3.1. Compositions of gelatinous and non-gelatinous samples
The chemical compositions of gelatinous and non-gelatinous samples were
recorded by Bio-Rad FTS 3000 Fourier Transforms Infrared Spectrometer (FTIR, Bru-
ker Daltonic Inc, America). 1 mg paste powder was mixed with 100 mg KBr to make
slices. The measured spectral range was from 400 cm 1 to 4000 cm 1 [23].
The cement powders of gelatinous and non-gelatinous were used for the X-ray
photoelectron spectroscopy (XPS) measurement. XPS analysis was carried out on a
Thermo Scientific Escalab 250Xi instrument (USA) using Al Ka radiation. The data
were imported into XPSPEAK software package for data manipulation and curve
fitting.
The composition differences of gelatinous and non-gelatinous samples were
also discussed by powder X-ray fluorescence (XRF-1800, Shimadzu, Japan).
Crystal structures in the hydration product of samples were also investigated by
powder X-ray diffraction (Rietveld XRD, Brook D8 Advance, Germany) with Cu Ka
radiation. Samples were scanned from a 2h of 5°–70° at the rate of 7°/min and a step
size of 0.02°.
The microstructures of the gelatinous and non-gelatinous samples were
observed by Field Emission Scanning Electron Microscope (Model S-4800, Hitachi,
Japan) and Energy Dispersive Spectrometer (EDS). The dried samples were treated
by gold sputtering for good electrical conductivity.
2.3.2. Polymer morphology
The influences of various ions and mineral salt on the morphological character-
istics of polymer solution were evaluated by intuitive forecasting method. Polycar-
boxylic additives were added to distilled water to prepare the solution of
concentration 50 g/L. CaCl2, Na2SiO4, Al2(SO4)3 and Na2Al2O4 were used to simulate
the ionic environment of cement pore solution. The inorganic salts were succes-
sively added into the polymer solution to observe the changes of polymer solution.
2.3.3. Thickening experiment of cement slurry
The thickening property of cement slurries mixed with different polycarboxylic
additives were measured by using HTHP consistometer (8040D10, Chandler, USA).
It is important to ensure the cementing safety and improve the cementing quality.
Fig. 3 shows the FTIR spectra of gelatinous and non-gelatinous
samples of cement slurries containing Sample I. From Fig. 3(a),
the bands at 3640 cm 1 appeared to be due to the O–H stretching
of Ca(OH)2 [23,25]. The stretching vibration peaks of Si-OH
occurred around 3430 cm 1. The peaks at 2927 cm 1 were the
asymmetric stretching of C–H bond present in organic compound
[25]. The bands observed at 1640 cm 1 were the bending vibration
of water in sulphates. The peaks around 1455 cm 1 resulted from
the C O vibrations of carbonates. In unhydrated cement powders,
several bands were present between 1106 cm 1 and 1152 cm 1,
which was considered to be the early formation of ettringite. The
intense peaks in the range from 925 cm 1 to 970 cm 1 belong to
the Si–O asymmetric stretching vibration, which is considered
the polymerization of the SiO24 units during C–S–H formation
[26,27].
As we know, the absorbance (A) in IR spectrum is proportional
to the lg (1/T), where T is transmittance. The greater the absor-
bance is, the stronger the adsorption. According to the Lambert-
Beer law, the absorbance of component is proportional to its con-
tent. Hence, the amount of various ingredients can be quantita-
tively determined by the characteristic peak amplitude in FTIR
spectra.
The fitting curves are shown in Fig. 3(b) and (c). The peak area
ratio of the asymmetric H C mode and the O–H stretching of Ca
(OH)2 (AC H/AO H) can be used to estimate the amount of polycar-
boxylic additives from this fit [25]. The intensity ratio (AC H/AO H)
is used for estimating the amount of polycarboxylic additives.
The AC H/AO H in gelatinous sample was 2.714, and the value in
282 D. Chen et al. / Construction and Building Materials 149 (2017) 279–288
non-gelatinous sample was 0.560. Thus, the gelatinous part con-
tains more polycarboxylic additives, and the non-gelatinous one
has a large number of Ca(OH)2.
3.1.2. XPS analysis
The surface compositions of gelatinous and non-gelatinous
samples were displayed in Table 4, which only listed the most
important elements including carbon, oxygen, calcium and silicon.
Fig. 4(a) demonstrates the XPS and Ca 2p spectra of gelatinous
and non-gelatinous samples. The XPS spectra were mainly consti-
tuted of oxygen, carbon, calcium and silicon. Furthermore, the XPS
and Ca 2p spectra were similar with each other. As shown in Fig. 5
(b) and (c), the Ca 2p peaks of samples were fitted into five compo-
nents, which were corresponding to CaCO3, Ca(OH)2, CaO and Ca
(HCOO)2 respectively. Obviously, the Ca(HCOO)2 was the product
from the reaction of polycarboxylic additives and cement, which
the peak was at 347.40 eV [23,28]. The content of Ca(HCOO)2
was represented by the peak area ratio of Ca(HCOO)2 and Ca (ACa
(HCOO)2/ACa). The ACa(HCOO)2/ACa of gelatinous sample was 30.5%,
but the non-gelatinous one was 19.7%. Similarly, the ACa(OH)2/ACa
of gelatinous sample was 10.3%, and the same value of non-
gelatinous part was 12.7%.
Fig. 3. (a) FTIR spectra of gelatinous and non-gelatinous samples of cement slurries containing Sample I. (b) Peak fitted of gelatinous sample. (c) Peak fitted of non-gelatinous
sample.
The analyses showed that the different chemical compositions
between gelatinous and non-gelatinous parts. As shown in Table 4
and Fig. 4, the content of polycarboxylic additives in the gelatinous
part was more than the non-gelatinous one. However, the Ca(OH)2
in gelatinous sample was less than the other one. This analysis is
consistent with the results of FTIR spectra.
3.1.3. XRF analysis
X-ray fluorescence is a quantitative analysis technique which
was applied to further investigate the difference between the
gelatinous and non-gelatinous samples [29]. Table 5 showed the
mass percentages of oxides in Class G oil well cement, gelatinous
and non-gelatinous samples of cement slurries incorporating Sam-
ple I. The results described that the percentages of components in
the three samples are different, and the differences mainly focused
on calcium oxide (CaO), silicon dioxide (SiO2), and aluminum
sesquioxide (Al2O3). In detail, the Si/Ca mass ratio of gelatinous
part was 34.71%, which was more than twice the value of the
non-gelatinous one (15.86%). The Si/Ca mass ratio of Class G oil
well cement was between gelatinous and non-gelatinous parts.
Moreover, there was a similar consequence of the amount of alu-
minum sesquioxide in three samples. It has been quantitatively
 D. Chen et al. / Construction and Building Materials 149 (2017) 279–288 283

Table 4
Surface composition (atomic%) of gelatinous and non-gelatinous samples.

Element C O Ca Si
Gelatinous 44.0 44.8 8.4 2.8
Non-gelatinous 30.2 53.6 11.0 5.2

proved that more silicate hydrate and aluminate compounds are

gathered in the gelatinous part.
Furthermore, it is also obvious that the total amount of metal-
oxide in gelatinous sample is less than the others, inducing that
there are more organic compounds in the gelatinous slurry. The
difference of oxides in the cement slurries might be attributed to
the chelation and chemisorption of polycarboxylic additives pre-
sented in cement system.

3.1.4. XRD analysis
The compositions and phase differences of the cement slurry
with gelatinous and without gelatinous were analyzed by XRD
method. Fig. 5 described the X-ray diffraction patterns of both sys-
tems. The crystallization compositions of the cement hydration are
represented by ettringite (AFt, JCPDS 41-1454) with the peaks at
2h = 1500B0 and 41°, portlandite (Ca(OH)2, JCPDS 44-1481) with
the strong peaks at 18°, 34° and 47°, C–S–H (Ca2SiO4
3H2O,
JCPDS 29-0374) with the range from 26° to 32° [29,30], and unhy-
drated minerals (belite, C2S, JCPDS 49-1672) with the strong peak
at 32°.
As demonstrated in Fig. 5, the intensity of Ca(OH)2 in gelatinous
sample was obviously lower than the non-gelatinous one, while
the signal intensities related to AFt, C–S–H and C2S of the former
Fig. 5. X-ray diffraction patterns of non-gelatinous (a) and gelatinous (b) samples, A
represents AFt, B represents Ca(OH)2, C represents C–S–H, D represents C2S.
are higher than the latter. Combined with the results in 3.1.1 and
3.1.2, the non-gelatinous sample contained less polycarboxylic
additives, AFt and C–S–H, but a large amount of Ca(OH)2, as
opposed to that of gelatinous one. Hence, more silicate and alumi-
nate hydrate gathered in the gelatinous samples, which was in
accordance with the experimental results of the gelatinous and
non-gelatinous samples as described above.
3.1.5. SEM and EDS elemental analysis
SEM micrographs of gelatinous and non-gelatinous samples
were taken to characterize their surface morphologies. Fig. 6(a)

Fig. 4. (a) XPS spectra of gelatinous and non-gelatinous samples containing Sample I. (b) Ca2p peak fitted of gelatinous sample. (c) Ca2p peak fitted of non-gelatinous sample.
284 D. Chen et al. / Construction and Building Materials 149 (2017) 279–288

Table 5
Component and its content of different samples characterized by XRF analysis (mass fraction, %).

Items CaO SiO2 Al2O3 Fe2O3 MgO SO3 Na2O K2O Total
Gelatinous slurry 44.18 23.47 4.75 3.98 1.39 2.77 0.88 0.57 81.99
Non-gelatinous slurry 58.19 14.13 2.57 3.78 1.29 2.60 1.00 0.56 84.11
Class G oil well cement 55.11 18.69 3.12 4.34 1.56 2.87 0.56 0.60 86.83

Fig. 6. SEM images and EDS analysis of gelatinous (a, b) and non-gelatinous (c, d) samples.

Table 6
Various element content (wt%) of gelatinous and non-gelatinous samples measured by EDS.

Element CK OK NaK MgK AlK SiK SK KK CaK FeK Total

Gelatinous 7.36 38.62 0.72 1.65 2.42 5.62 2.70 1.00 36.54 2.30 100.00
Non-gelatinous 1.40 45.48 0.23 0.48 1.66 5.39 1.04 0.48 42.56 1.28 100.00

shows the SEM images of gelatinous cement sample, indicating
that the surface of sample has been covered with a large amount
of irregular-structured calcium silicate hydrate (C–S–H) gels and
non-uniform area of porous matrix [31]. However, more calcium
hydroxide crystals and less C–S–H gels are located on the surface
of non-gelatinous sample, which is shown in Fig. 6(c).
The quantitative EDS element analysis with line-scan technique
was also performed to determine the chemical compositions and
their concentration distribution. The results were showed in
Fig. 6(b),(d), and Table 6. The main hydration products of cement
are C–S–H and Ca(OH)2. There was a large amount of C–S–H in
gelatinous sample, showing a higher Si/Ca mass ratio. However,
the non-gelatinous one has more Ca(OH)2 crystals. The results
were in accordance with the surface morphologies in Fig. 6
(a) and (c). Moreover, Table 6 also reveals that there were greater
amount of organic carbon enriched in the gelatinous part than that
in non-gelatinous part, as well as Si and Al elements. Thus, it can be
concluded that there might be some chemical reaction between
polymer additives and hydrated minerals through chemical
adsorption, chelation, or cross-linking action.
The above analyses have shown that the content of polycar-
boxylic additives in the gelatinous part was more than the non-
gelatinous one, as well as AFt and C–S–H, however, the non-
gelatinous one had a large amount of Ca(OH)2.
3.2. Mechanism of the abnormal gelatinous phenomena
3.2.1. Gelatinous hypothesis
It can be seen that the polymers, silicate and aluminate hydrate
were easily gathered in the gelatinous part by the qualitative and
 D. Chen et al. / Construction and Building Materials 149 (2017) 279–288 285

quantitative analyses of FTIR, XPS, XRF, XRD, SEM and EDS tech-
nologies. Furthermore, the reasons were proposed from two per-
spectives based on the laboratory research and field applications.
(1) Cross-linking hypothesis. The carboxylic groups in polymer
additives are intensively clinched on the surface of cement
grains or hydration productions by polymer chemisorption
and ion chelation, especially the combination of polycar-
boxylic substances and cations (Ca2+, Al3+, etc.), silicate, or
aluminate hydrate. Simultaneously, the gelatinous structure
is developed through the cross-linking reaction among alu-
minate hydrate, linear polymer and C–S–H gel. Moreover,
the cross-linking structure could also be embedded into
the C–S–H gel to develop a gelatinous 3-D space-strip floc,
which would be intertwined on the axis of stirring paddle
under the shearing force from the macro perspective.
(2) Molecular morphology transition hypothesis. The polymer
molecular morphological structure changes internally under
high temperature (e.g. around 120 °C) and the extended lin-
ear polymer main chain can also be intertwined on stirring
paddle. This phenomenon will cause the rapid increase in
its viscosity and consistency.
Al2(SO4)3 and Na2Al2O4were used to simulate the ionic environ-
ment of cement pore solution. Inorganic salts and Sample I were
dropped into water under constant stirring in a certain order.
rWhen CaCl2, Na2SiO4 and Al2(SO4)3 were added to the poly-
mer solution alone, the solutions were homogeneous liquid
phases. However, Na2Al2O4 induced the polymer solution to form
flocculate. It was obvious that carboxylic groups (–COO ) could
integrate with Al2O24 to form flocculate with space cross-
linking net structure. Furthermore, the experiments of two or
more inorganic salts were also tested. Table 7 shows the results
and Fig. 7 exhibits the optical photographs of Sample I in differ-
ent inorganic salt solutions. It is concluded that (1) –COO in the
aqueous solution can combine with Ca2+ and SiO24 to develop an
ionic complex structure; (2) Al3+ is regarded as an acceleration
additive in the cross-linking reaction and gel formation due to
its coordination behavior with other ion compounds. Thus, the
cross-linking hypothesis was verified.
All of these inorganic ions could exist in the cement slurry
phase. Polycarboxylic cement slurry has great potential risk to
develop flocculates, which could be intertwined around the case
strings in the process of cementing operation and endanger the
cementing security seriously.

The two mechanisms have synergistic effects, which would be
reinforced mutually, collectively inducing the severe problem of
obvious abnormal gelation phenomena for cement slurry around
120 °C.
3.2.2. Effect of ions on the morphology of polymer solution
In this section, a series of inorganic salt solutions were used to
simulate the partial chemical compounds or hydrated products in
cement slurry system embracing silicate hydrate and aluminate
compound to prove the two hypotheses above. CaCl2, Na2SiO4,
3.3. Solution methods
3.3.1. Functional structure optimization of polycarboxylic additives
According to the analyses, the cross-linking reaction between
the polycarboxylic additives and the ionic components of cement
is the main reason of the abnormal gelatinous phenomenon of
cement slurry. The molecular structure of polycarboxylic additives
was changed to reduce the chelating effect of the carboxylic acid
groups. Thus, several polycarboxylic additives were synthesized
using the free-radical aqueous polymerization method to intro-

Table 7
Dynamic dissolution characteristic of Sample I in the inorganic salt solution.

Solution types Solubility Solution types Solubility

CaCl2 ++ CaCl2 + Sample I ++
Na2SiO4 ++ Na2SiO4 + Sample I ++
Al2(SO4)3 ++ Al2(SO4)3 + Sample I ++
Na2Al2O4 ++ Na2Al2O4 + Sample I
CaCl2 + Na2Al2O4 + CaCl2 + Sample I + Na2Al2O4 –
Na2SiO4 + CaCl2 + Na2SiO4 + CaCl2 + Sample I +
Na2SiO4 + CaCl2 + Na2SiO4 + Sample I + CaCl2 +
CaCl2 + Na2SiO4 ++ CaCl2 + Na2SiO4 + Sample I –
Na2SiO4 + CaCl2 + Na2Al2O4 + Na2SiO4 + CaCl2 + Sample I + Na2Al2O4 –
Na2Al2O4 + CaCl2 + Na2SiO4 + Na2Al2O4 + CaCl2 + Na2SiO4 + Sample I ++
Na2Al2O4 + CaCl2 + Na2SiO4 + Al2(SO4)3 + Na2Al2O4 + CaCl2 + Sample I + Na2SiO4 + Al2(SO4)3

Note: (1) + + represents excellent solubility; + represents homogeneous dissolution and shows milk white; – for slight flocculation; for a strong gelatinous state. (2) The
order of inorganic salt and Sample I listed in Table 7 indicates the feed order in the experiment.

Fig. 7. Resulting diagrams of polycarboxylic additive (sample I) doped in different inorganic salt solutions, (a) Na2SiO4 + Sample I + CaCl2; (b) Na2Al2O4 + Sample I; (c)
Na2Al2O4 + CaCl2 + Sample I + Na2SiO4 + Al2(SO4)3.
286 D. Chen et al. / Construction and Building Materials 149 (2017) 279–288
Fig. 8. Thickening curves of cement slurry containing (a) Sample II, (b) Sample III, (c) Sample IV, (d) Sample III and 15% NaCl at 130 °C and 65 MPa for 65 min.
duce the special functional groups. Meanwhile, we investigated the
high temperature thickening performance of cement slurry con-
taining these samples, especially when BHCT was over 120 °C.
(1) Incorporation of vinyl monomers with long lateral chain
A functional monomer with a long side chain would improve
the steric hindrance effect. At the same time, when the polymer
adsorbed on the surface of the cement particles, the static repul-
sion among long lateral chains increased the intermolecular dis-
tance and hindered the contact between cement particles and
polymers. Some vinyl monomers with hydrophobic long side-
chain were incorporated into the polymer molecular structure,
such as ODAAC, hexadecyl dimethyl allyl ammonium chloride (C16-
DMMAC) and their derivatives.
Polycarboxylic additives with outstanding properties can be pre-
pared by controlling the dosage of vinyl monomers and adjusting the
polymerization conditions. The Sample II replaced AA in Sample I
with ODAAC and retained IA. The representative thickening prop-
erty of cement slurry containing Sample II was exhibited in Fig. 8
(a). Compared with Sample I, which thickening curves were shown
in Fig. 1, Fig. 8(a) revealed that the consistency curve of cement
slurry was smooth, and the development trend of temperature and
pressure curves were close to normal level. There was no flash-
setting phenomenon occurred at 120 °C and no gelatinous slurry
intertwined on the stirrer shaft, which can be observed from the
image in Fig. 8(a). The excellent performance of Sample II was the
result of synergistic effect between steric hindrance and lubrication
of long hydrophobic side-chains [32]. The synergistic effect pre-
vented the polycarboxylic additive from adsorbing the cement
grains and combining with -O-Si-O- or aluminate hydrate to pro-
duce flocs.
(2) Introduction of cationic vinyl monomers
The excellent amphoteric ionic polymer additives were devel-
oped through the introduction of quaternary ammonium cationic
vinyl substances, such as DMDAAC, methacryloxyethyltrimethyl
ammonium chloride (DMC), allyltrimethyl ammonium chloride
(DTAC), octadecyldimethylallyl ammonium chloride (OTDAC), etc.
Sample III and IV also retained IA, but replaced AA in Sample I with
DMDAAC, DMDAAC and NNDMA, respectively, which were shown
in Table 3. The molecular weight and distribution of Sample III and
IV were adjusted through changing the synthetic conditions.
The thickening curves of cement slurries containing Sample III
and IV were presented in Fig. 8(b) and (c). The cement slurries con-
taining Sample III had slight gelatinous phenomena, which can be
seen from the image in Fig. 8(b). And the cement slurries contain-
ing Sample IV had no abnormal phenomena. There was no fluctu-
ation of temperature and pressure in Fig. 8(b) and (c). Hence, the
abnormal gelatinous phenomena of cement slurry can be relieved
or eliminated by incorporating cationic vinyl monomers into poly-
mer backbone.
3.3.2. Effect of special inorganic salt on the thickening property of
cement slurry
The abnormal gelatinous phenomenon of cement slurry is hap-
pened in different batches of oil well cement around 120 °C, which
is a potential risky problem in field application. Therefore, some
measures should be taken to relieve or eliminate the abnormal
problem [33]. Special inorganic salts can change the polymer
molecular morphology and break the cross-linking structure
between polycarboxylic groups and -O-Si-O-. Hence, the special
salts added into cement slurry system might prevent the formation
of gelatinous flocs.
 D. Chen et al. / Construction and Building Materials 149 (2017) 279–288
Fig. 9. Influence of temperature on the apparent viscosity of polymer solutions.
Sodium chloride solution (15 wt%) and Sample III were added
into the cement slurry. Fig. 8(d) shows the thickening curve of
the system at 130 °C (BHCT) and 65 MPa (terminal pressure) for
65 min (ramp time). It is not shown that flash setting phenomenon
and fluctuation of temperature and pressure happened at 120 °C.
Meanwhile, it can be seen that no gelatinous slurry intertwined
on the stirring paddle. The reason for this advantageous phe-
nomenon might be that special salt ions could change the polymer
molecular conformation and break the flocculent cross-linking
structure. In fact, the definite mechanisms of special inorganic salt
need further investigation.
3.4. Viscosity-temperature characteristic of polycarboxylic additives
In addition, the effect of temperature on the apparent viscosity
of different polymer samples in aqueous solutions was investi-
gated. The results were displayed in Fig. 9, which were consistent
with the thickening curves. It is popular believed that the apparent
viscosity of polymer solutions decreases as the temperature
increases [34]. It was clear that the apparent viscosity of Sample
I gradually decreased with the increase of temperature, but there
was a sharp rise when the temperature reached 120 °C. Then it
decreased with further temperature increasing. The reason for this
abnormal phenomenon in viscosity might be the structural trans-
formation happened at approximately 120 °C, which is character-
ized by viscosity uprush in macroscopic scale and state changes
from the transparent to turbid. Due to the adsorption of polycar-
boxylic additives onto the cement particles, the viscosity perfor-
mance of polymer solutions has a direct influence on the
consistency of cement slurry. Hence, the sharp rising viscosity of
polymer solutions could be the source of abnormal gelatinous phe-
nomenon of cement slurry at 120 °C, which is in accordance with
the second gelatinous hypothesis in Section 3.2.1.
Sample II, III and IV were also investigated, and there was no
sharp rising phenomenon in aqueous solutions with the same con-
centration. The molecular structure of three samples contains a
large number of quaternary ammonium salt or hydrophobic long
side chains. These structures could improve the steric hindrance
of polymer molecular, and then the molecular chain became hard
to tangle, which is characterized by stable viscosity in macroscopic
scale, or viscosity decreased gradually.
Because of the positive charges on the surface of cement grains
and C–S–H gel, the polycarboxylic additives which have abundant
negative charge (–COO ) are easily to be adsorbed on the surface of
cement grains and hydration products. The electrostatic repulsion
287
and steric hindrance of polymer samples will prevent the strong
adsorption of carboxylic groups on the cement grains and hydra-
tion products. Consequently, the copolymerization of vinyl mono-
mers with hydrophobic long side-chain and cationic vinyl
monomers is expected to relieve or eliminate the abnormal gelati-
nous problem.
4. Conclusions
In this article, the mineralogical composition difference
between gelatinous and non-gelatinous sample of cement slurry
containing polycarboxylic additives was characterized by FTIR,
XPS, XRF, XRD, SEM and EDS techniques. Moreover, the effect of
ions on the morphology of polymer solution, and the viscosity-
temperature characteristic of polycarboxylic samples in aqueous
solution were investigated. Based on the analyses, the main rea-
sons of abnormal gelatinous phenomenon of cement slurry con-
taining polycarboxylic additives happened around 120 °C include
three points. First, the thickening performance of cement slurry
has been directly influenced by the viscosity-temperature property
of polymer solutions, while the apparent viscosity of polymer sam-
ples would rapidly increase near 120 °C. Second, the polycarboxylic
substances react with calcium ions and SiO24 to form flocs, leading
to the gelatinous slurry in the interior. The last, the flocs are pro-
duced through the cross-linking reaction between the carboxylic
polymer and silicate or aluminate solutions, which could be inlaid
into the C–S–H gel.
The effective measures have been taken to relieve or eliminate
the abnormal gelatinous phenomenon of cement slurry. One is the
functional structure optimization of polycarboxylic additives. The
molecular structure contains quaternary ammonium salt or
hydrophobic long side chains. These structures could improve the
steric hindrance of polymer molecular, and then the molecular
chain became hard to tangle. The other is the incorporation of spe-
cial inorganic salts into cement slurry system. The results will be of
great significance in the development of high temperature cement-
ing technology and can also play important roles in the develop-
ment of polycarboxylic additives.
Acknowledgments
This study was supported by National Science and Technology
Major Project of China (Grant No. 2016ZX05020-004).
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