Journal of Petroleum Science and Engineering 180 (2019) 518–525

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Journal of Petroleum Science and Engineering

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

An approach to evaluate polyacrylamide-type polymers' long-term stability T

under high temperature and high salinity environment
Xuan Zhanga, Ming Hana,b,∗, Alhasan Fusenib, Abdulkareem M. Alsofib
a
Beijing Research Center, Aramco Asia, Beijing, 100102, People's Republic of China
b
EXPEC Advanced Research Center, Saudi Aramco, Dhahran, 31311, Saudi Arabia

A R T I C LE I N FO A B S T R A C T

Keywords: Water-soluble polymers have been widely used in chemical flooding either independently or as part of surfac-
Polyacrylamide-type polymer tant-polymer (SP) and alkaline-surfactant-polymer (ASP) processes. The polymer viscosifies the injected water
Thermogravimetric analysis thereby reducing the displacing fluid's mobility and increasing sweep efficiency. The key to efficient sweep is
High salinity and high temperature attaining sustainable mobility control (i.e. maintenance of sufficient viscosity during propagation in the re-
Long-term stability
servoir). Long-term stability is therefore a crucial parameter in the screening of appropriate polymers for ap-
plication, especially in high temperature and high salinity reservoirs. In general, the evaluation of a polymer
solution's long-term stability is a very time-consuming process. There is a need to develop fast and reliable means
to assess the feasibility of polymers from a long-term stability standpoint. Different from conventional methods
posed in the literature, this paper presents a new facile approach to evaluate the polymers in powder form and
identify their molecular decomposition. The approach is correlated and confirmed against conventional long-
term stability results obtained from the evaluation of polymer solutions.
Thermogravimetric analysis (TGA) was used in this work to study the decomposition of polymers and their
individual constituents. The derivative of the TGA curve with respect to temperature, is known as the derivative
thermal gravimetric (DTG) thermogram, which can clearly identify differences in decomposition rates of
screened polymers. Furthermore, conventional long-term stability tests were performed on polymer solutions
prepared in synthetic seawater with a salinity of 57,670 ppm. The solutions were aged at a temperature of 95 °C
under anaerobic conditions and monitored by rheological measurements for viscosity loss, total organic carbon
(TOC) analyses for material loss, and gel permeation chromatography (GPC) for molecular weight loss.
The thermal stability of 12 commercial water soluble polymers was tested in this work. The long-term sta-
bility results are consistent with the TGA results. The two polymers showing good thermogravimetric stability
exhibited significant viscosity retention in conventional long-term stability tests. TOC and GPC results further
supported these TGA results. The developed method provides a fast approach to screen polymer candidates for
high temperature and high salinity reservoirs.

1. Introduction
In chemical flooding, water-soluble polymers are an important
component that provides fluid mobility control and improves the sweep
efficiency. In this respect, it is necessary to maintain the viscosity of a
polymer solution for a long period of time (generally 6–12 months)
throughout its propagation across the reservoir (Pye, 1964; Lake, 1989;
Sorbie, 1991).
Partially hydrolyzed polyacrylamide (HPAM) as a water-soluble
polymer has been widely used in field applications, since it has many
desirable properties such as its ease in forming hydrogen bonds with
water molecules and their large hydrodynamic volume which build up
high viscosity in aqueous environments (Han et al., 2006; Dong et al.,
2008). However, HPAM is susceptible to degradation due to chemical
hydrolysis at temperatures higher than 70 °C and salinities higher than
40,000 ppm (Moradi-Araghi et al., 1982; Levitt and Pope, 2008; Seright
et al., 2009). Sulfonated polyacrylamide (SPAM) and associative poly-
acrylamide (APAM) have been developed to solve the problems en-
countered in high temperature and high salinity reservoirs. SPAM is
usually synthesized by acrylamide and sulfonated monomers such as 2-
acrylamido-2-methylpropane sulfonic acid (AMPS), allyl sulfonate or
sulfonated styrene. Many researchers suggest that the incorporation of
sulfonated groups makes polymers stable at high temperature and high
salinity conditions, as these monomer structures can prevent

∗
Corresponding author. Beijing Research Center, Aramco Asia, Beijing, 100102, PR China.
E-mail address: ming.han@aramcoasia.com (M. Han).

https://doi.org/10.1016/j.petrol.2019.04.092
Received 11 December 2018; Received in revised form 11 April 2019; Accepted 26 April 2019
Available online 27 April 2019
0920-4105/ © 2019 Published by Elsevier B.V.
X. Zhang, et al. Journal of Petroleum Science and Engineering 180 (2019) 518–525

acrylamide groups from hydrolysis (Audibert and Argillier, 1995; Table 2

Rashidi et al., 2010; Han et al., 2013). APAM is a copolymer that Polymer information.
contains a small number of hydrophobic groups (less than 1 mol %) No. Polymer Name Type
distributed along the hydrophilic chains in blocks or at random
(Jimenez-Regalado et al., 2000). Compared with HPAM, APAM forms 1 HPAM-Z1M Partially hydrolyzed polyacrylamide
2 HPAM-Z2M Partially hydrolyzed polyacrylamide
aggregates to minimize the exposure of molecules to the solvent, and
3 HPAM-N3L Partially hydrolyzed polyacrylamide
thereby exhibits favorable temperature and salt tolerance 4 HPAM-A4H Partially hydrolyzed polyacrylamide
(Lewandowska, 2007; Buchgraber et al., 2009; Pancharoen et al., 5 HPAM-A5H Partially hydrolyzed polyacrylamide
2010). In fact, SPAM and APAM have been successfully applied as a 6 HPAM-A6H Partially hydrolyzed polyacrylamide
mobility control agent field applications (Zhou et al., 2008; Seright and 7 SPAM-A1L Sulfonated polyacrylamide
8 SPAM-S2L Sulfonated polyacrylamide
Henricl, 1986).
9 SPAM-H3L Sulfonated polyacrylamide
Many commercial polymers are not applicable in high salinity 10 APAM-J1H Associative polyacrylamide
(above 50,000 ppm) and high temperature (above 90 °C) reservoirs due 11 APAM-G2L Associative polyacrylamide
to the precipitation, and significant degradation, of polymers. For such 12 APAM-G3L Associative polyacrylamide
reservoirs, it is essential for polymers to maintain stable viscosity at the
harsh conditions. Evaluation of a polymers’ long-term stability used to
be a very time-consuming process. It would take months or years to The polymer names and types are listed in Table 2.
monitor the variation of solution viscosity as a function of time to
evaluate the feasibility of certain polymers (Moradi-Araghi et al., 1982; 2.2. Thermal gravimetric analysis
Doe et al., 1985).
Thermogravimetric analysis (TGA) provides an important tool for The thermal behaviors of polymers were analyzed by thermal
investigating thermal stability of materials. The mass versus tempera- gravimetric measurements. The polymer sample in powder form was
ture or time results from TGA measurements can reveal the thermal encapsulated in a standard Al2O3 sample crucible and the sample was
behaviors of materials including the chemical and physical changes. heated to 650 °C with a heating rate of 10 °C/min. The tests were per-
The results indicate the response of the molecular structures to en- formed in a pure Nitrogen environment with a flow rate of 60 ml/min.
ergetic modification and provide valuable information that can be used The thermal gravimetric analysis (TGA) curve was recorded by com-
to select appropriate materials (Craig and Marcelo, 2002). The thermal puter. The derivative thermal gravimetric (DTG) curve with respect to
degradation of polyacrylamide polymers in solid-forms has been in- temperature obtained from TGA curve by software was used to distin-
vestigated by TGA (Grassie et al., 1978; Vilcu et al., 1985; Dyke and guish the point at which weight loss is significantly.
Kasperski, 1993; Elisa et al., 2000). However, these researches were
focused on the thermal degradation mechanism of polyacrylamide in 2.3. Polymer solution preparation
solid-form. There has been few research using the TGA degradation
results of polyacrylamide-type polymers in solid-form to correlate the 500 ml of the synthetic brine was added to a beaker while magne-
long-term stability of polymers in aqueous solutions. tically stirring at 500 rpm to ensure a good vortex. The calculated
In this study, we investigated the stability of 12 commercial poly- amount of the powdered polymer was sprinkled slowly into the brine
acrylamide-type polymers. TGA was used to investigate the decom- over 30 min. The stirring speed was then reduced to 200 rpm for 12 h.
position of the powder-form polymers and their individual constituents. All polymers were prepared at a concentration of 2000 mg/L; with
Conventional long-term stability tests were performed at a temperature exception to SPAM-S2L, which was prepared at 5000 mg/L.
of 95 °C in aqueous solutions prepared by synthetic seawater with a
salinity of 57,670 ppm. The long-term stability tests included mon- 2.4. Experimental procedure for long-term stability
itoring of viscosity losses by rheological measurements, material losses
by total organic carbon (TOC) analyses, and molecular weight losses by The prepared polymer solutions were distributed into 50 ml peni-
gel permeation chromatography (GPC). The polymer degradation re- cillin bottles. The bottles were put into a vacuum desiccator for de-
sults and mechanisms in the two forms (powder and solution) were also gassing to get rid of the dissolved oxygen in the polymer solution until
studied, compared and correlated. A fast and reliable way was estab- there were no obvious bubbles. It took approximately 30–120 min for
lished to evaluate the long-term stability of polyacrylamide-typed degassing. After that, nitrogen was introduced into the desiccator to
polymers. balance the pressure and the desiccator was degassed for 5 min. This
procedure was repeated 3 times. The penicillin bottles were quickly
sealed and the polymer solution was bubbled by N2 for 2 h under a
2. Experimental pressure of 0.02–0.04 MPa to get rid of the residual dissolved oxygen in
the polymer solution. The dissolved oxygen concentration was mea-
2.1. Material sured in a glove box and the indicator showed that the dissolved oxygen
concentration was less than 10 ppb. The penicillin bottles were placed
Brine. Synthetic Arabian Gulf seawater was used in the preparation into an oven at 95 °C for aging. The viscosity of the polymer solutions
of polymer solutions. The total dissolved solid (TDS) of the seawater is was measured at scheduled times.
57,670 ppm. The composition of the brine is listed in Table 1.
Chemicals. 12 polymer samples were selected for the test program. 2.5. Rheological measurement

Table 1 The rheological properties of the polymer solutions were measured

Chemical composition of seawater. by a rheometer. The apparent viscosity was measured at 90 °C at shear
Seawater Cations Anions Total rates ranging from 0.1 to 100 s−1.
salinity
Na+ Ca2+ Mg2+ CI− HCO3− SO42- 2.6. Polymer concentration determination
Concentration 18,300 659 2,110 32,200 120 4,290 57,670
(ppm) The TOC values of polymer solutions were analyzed to determine
the concentration. The calibration curves of benchmark polymer

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solutions were constructed using 6 concentrations ranging from 10 mg/
L to 200 mg/L. The polymer samples were diluted 10 times by deio-
nized (DI) water before measurement. Each sample was measured 3
times to get an average value.
2.7. Polymer molecular weight analysis
The GPC method was used for characterization of the polymers in
solution. The temperature of column and detector were both set at
45 °C. The equipment was calibrated with a standard PEO sample with a
molecular weight of 71,250 Da. All samples were diluted to an appro-
priate concentration by GPC mobile phase and stirred overnight to
ensure complete dissolution before the analysis.
3. Results and discussions
3.1. Thermal gravimetric analysis
TGA is a useful way to describe the thermal degradation of polymers
through the quantitative calculation of weight loss as a function of
temperature. The thermal stability of polymers in powder form was
investigated using TGA. 12 commercial polymers were tested. The
curves of HPAM-A4H, APAM-J1H, SPAM-A1L, and SPAM-S2L are
shown in Fig. 1.
Fig. 1a and b demonstrate that the samples exhibit three steps of
weight loss, which represents the typical thermal behaviors of poly-
acrylamide (Fig. 2). In the first region (below 200 °C), polymers are
thermally stable and have a slight weight loss due to the absorbed water
from environment and other volatile impurities. The weight loss is
about 10%, which corresponds well with the previous data collected of
the solid contents of polymers (Grassie et al., 1978; Vilcu et al., 1985;
Dyke and Kasperski, 1993; Elisa et al., 2000). In the second region
(200°C-300 °C), polymers undergo irreversible intra- and inter-
molecular imidization reactions at the amide group with the releasing
Fig. 1. Thermal gravimetric curves of polymers: a) HPAM-A4H; b) APAM-J1H; c) SPAM-A1L d) SPAM-S2L.
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of NH3, H2O and minor quantities of CO2 (Grassie et al., 1978; Vilcu
et al., 1985; Dyke and Kasperski, 1993; Leung et al., 1987). The third
one occurs in the range of 300°C–500 °C. The imides begin to be de-
composed to form CO2 and H2O, and the predominant reactions are
random degradation of the polymeric main chain at higher tempera-
tures (Dyke and Kasperski, 1993; Leung et al., 1987). The results are
consistent with the observations for polyacrylamide-type polymers.
As many weight loss curves look similar, a derivative thermal
gravimetric (DTG) curve with respect to temperature is used to distin-
guish the point at which weight loss is most apparent. The peak of DTG
means the reaction rate is at maximum in this region and the original
polymer structures had been significantly changed to generate new
structures or destroyed. Peak degradation temperature 1 (Tp1) indicates
the amide groups had been changed at maximum reaction rate in the
second region. Peak degradation temperature 2 (Tp2) implies the gen-
erated structures in the second region was destroyed in the third region.
Table 3 shows the peaks of the degradation temperature (Tp1) for most
polymers except SPAM-A1L and SPAM-S2L are below 300 °C. The sul-
fonated polymers SPAM-A1L and SPAM-S2L display better thermal
stability than others as shown in the DTG thermograms in Fig. 1c and d.
This demonstrates that the degradation of sulfonated polymers occurs
above 300 °C. This improved thermal stability is due to the sulfonated
groups acting as steric hindrance groups across the copolymer back-
bone, enhancing the rigidity of the backbone and interrupting the in-
tramolecular and intermolecular imidization reactions between amide
groups and the dehydration of amide groups in the polymer chain
(Fig. 3). In addition, introducing the groups with steric hindrance re-
sults in more intramolecular and intermolecular hydrogen bonding with
surrounding amide groups that can further prevent the amide groups
from hydrolysis and the macromolecular chains from decomposition.
(μ−μ )
3.2. Aging time dependence of polymer viscosityln ⎡ (μ − μs ) ⎤ = −t/τ
⎣ 0 s⎦
Polymers present different performances under the same reservoir
X. Zhang, et al. Journal of Petroleum Science and Engineering 180 (2019) 518–525

Fig. 2. Proposed reaction scheme for thermal pyrolysis of polyacrylamide (Caulfield et al., 2002).

Table 3 line, and the half time period (T1/2) can be calculated by equation (2).
Peaks of polymers from DTG curves.
T1/2 = ln2*τ (2)
No. Polymer Name Peak Degradation Temperature (°C)

Tp1 Tp2
Table 4 shows the long-term stability of the polymers in solution
with respect to viscosity, precipitation time, the decay constant, and
1 HPAM-Z1M 271.62 379.34 half-life times. Viscosity versus time is plotted in Fig. 4.
2 HPAM-Z2M 235.05 378.02 Table 4 demonstrates that most of the polymers present poor sta-
3 HPAM-N3L 212.50 330.93
4 HPAM-A4H 216.40 321.90
bility at high salinity and high temperature conditions and lose the
5 HPAM-A5H 216.20 336.90 viscosity in the first 7 days. The half-lives of these polymers in solution
6 HPAM-A6H 210.03 334.30 are less than 20 days. The precipitations occur in 50 days. This is due to
7 SPAM-A1L 333.03 380.43 the chemical hydrolysis of polyacrylamide-type polymers which in-
8 SPAM-S2L 328.50 405.10
creases the susceptibility to precipitation with divalent cations (Mg2+
9 SPAM-H3L 228.09 332.37
10 APAM-J1H 218.93 373.16 and Ca2+) and leads to a corresponding drop in viscosity or pre-
11 APAM-G2L 243.33 330.40 cipitations as described by Muller et al. (1980). However, sulfonated
12 APAM-G3L 226.92 330.25 polymers SPAM-S2L and SPAM-A1L in seawater exhibit half-life times
of more than 90 days and there was no precipitation after 120 days.
This observation supports the fact that sulfonated groups retard the
conditions, owing to differences in their molecular structure, molecular hydrolysis of amide groups along polymer chains. It appears that sul-
weight, and degree of hydrolysis. In order to evaluate the long-term fonated groups act as large steric hindrance groups within the polymer
stability of polymers, the dependence of polymer solutions viscosity on chain increasing the rigidity of polymer chains and improving the
aging time was studied. As the viscosity of polymer solution is asso- thermal stability of the polymer. It is known that the hydrogen bonding
ciated with shear rate, the exponential decay model was selected to between amide groups and N-vinylpyrrolidone (NVP) groups prevent
describe the kinetics of polymer degradation as shown in equation (1) intra-molecular interactions and postpone pyrolysis (Fernandez, 2005).
(Seright and Henricl, 1986), The sulfonated groups lend similar mechanisms to inhibit the hydrolysis
(μ−μ )
of amides. In brine, water molecules create hydrogen bonds with the
ln ⎡ (μ − μs ) ⎤ = −t/τ carbonyl and sulfonated groups. This would increase the stiffness of
⎣ 0 s⎦ (1)
polymer chain owing to the formation of a good framework (Ma et al.,
where μ is the viscosity of the polymer solution, μ0 is the original 2015). In addition, the hydrogen bridging between amide and sulfo-
viscosity of polymer solution, μs is the solvent viscosity, τ is the decay nated groups increases the amide group's resistance to hydrolysis as the
constant, which is the time for the specific viscosity (μ-μs) to fall to divalent ions that catalyze the hydrolysis of amides are shielded
(μ 0 − μs)
. From regression analysis of ln [(μ-μs)/(μ0-μs)] versus time, the (Jeevananda and Siddaramaiah, 2001) (Fig. 5). It is interesting to note
e
viscosity decay constants can be obtained from the slope of regression that SPAM-S2L presents better thermal stability than SPAM-A1L, which

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Fig. 3. Interputed imidization of amide groups with large steric hinderance groups and hydrogen bonding interactions between adjacent amide groups and large
steric hinderance groups for polyacrylamide-type polymer with good thermal stability.

can be explained by the presence of NVP groups in SPAM-S2L which act

as another kind of steric hindrance inhibiting the hydrolysis of amide
groups. Another interesting result is that sulfonated polymer SPAM-H3L
with a Tp1 below 300 °C in TGA exhibits unsatisfactory long-term sta-
bility, which is probably due to the low content of sulfonated groups.

3.3. Classification of half-life by TGA data

TGA is a way to investigate the thermal stability of polymers

(Jeevananda and Siddaramaiah, 2001; Pashaei et al., 2010; Wang et al.,
2013). The thermal stability of polymers can be estimated by com-
paring the decomposition temperatures corresponding to initial weight
loss. Those decomposition temperatures can serve as key parameters to
indicate the thermal stability of the composites. Generally, polymers
with high decomposition temperatures display good thermal stability.
In this study, the TGA results were correlated to decomposition
temperatures corresponding to initial weight loss, including T5 (tem-
Fig. 4. Viscosity of polymer solutions vs. aging time at 95 °C in seawater.
perature for 5% weight loss), T10 (for 10%), T15 (for 15%), T20 (for
20%), T30 (for 30%), and T50 (for 50%). Table 5 summarizes the results.
SPAM-A1L and SPAM-S2L display higher decomposition temperatures illustrates the correlation between half-life and decomposition tem-
than other samples. This is consistent with the half-life obtained from peratures. The 7 polymers with half-lives less than 10 days have T15
the long-term rheological stability tests. values of less than 250 °C. The 3 polymers with half-lives between 10
Fig. 6 presents cross plots of decomposition temperatures and half- and 50 days exhibited T15 values between 250 and 300 °C. SPAM-A1L
life for the different test samples. We observe clustering of polymers in and SPAM-S2L the most stable polymers, with half-lives exceeding 90
specific areas. The cross plot at T15 displays three areas. Fig. 6c clearly days, exhibited T15 values above 300 °C. Fig. 6d demonstrate similar

Table 4
Long-term stability results of polymer solutions.
No. Polymer Name Viscosity (mPa·s) Precipitation Time (day) τ T1/2 (day)

Day 1 Day 7 Day 14 Day 49

1 HPAM-N3L 8.81 6.98 ↓ × 14 11.49 7.97

2 HPAM-A5H 29.01 8.13 ↓ × 14 3.07 2.14
3 HPAM-A6H 31.51 13.65 ↓ × 14 4.24 2.94
4 APAM-J1H 23.25 16.14 ↓ × 14 11.63 8.06
5 APAM-G2L 94.86 8.11 ↓ × 14 6.14 4.26
6 APAM-G3L 10.53 4.07 ↓ × 14 6.33 3.02
7 HPAM-Z1M 36.1 32.91 29.37 ↓ 42 22.32 15.47
8 HPAM-Z2M 33.67 46.82 42.5 ↓ 49 66.23 45.90
9 HPAM-A4H 31.5 14.87 11.7 ↓ 21 5.7 3.95
10 SPAM-H3L 24.19 20.01 12.76 ↓ 28 17.61 12.31
11 SPAM-A1L 23.07 25.74 25.08 27.24 - 140.84 97.63
12 SPAM-S2L 25.49 22.91 21.67 20.87 - 625 433.22

Notes: the viscosity was measured at 25 °C.

“↓” means precipitation occurred.
“×” means the test had already been stopped.
“-” means no precipitation formed in the test.

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Fig. 5. The mechanism of polyacrylamide hydrolysis and proposed interactions between polymer molecule existing hindrance groups and water molecule with the
present of divalent ions.

clustering trends with a slight change of decomposition temperature
thresholds. Three areas are distinguished: 1) Area I: 200 °C <
T20 < 280 °C, T1/2 < 10 days; 2) Area II: 280 °C < T20 < 320 °C, 10
days < T1/2 < 90 days; 3) Area III: T20 > 320 °C, T1/2 > 90 days.
However, it is interesting to note that the cross plots at T5, T10, T30 and
T50 don't demonstrate clear clustering; in other words, those decom-
position temperatures cannot provide clear boundaries as T15 and T20.
As was noted earlier, polymers exhibit three steps of weight loss on
the thermal gravimetric curves. In the first region (below 200 °C),
polymers are generally stable and the weight loss is about 10%. Hence,
the data at T5 and T10 reflects the reduction of volatile impurities rather
than the polymer thermal stability. In the second region (200°C-300 °C),
the weight loss is about 20%. The data at T15 and T20 describes the
destruction of amide groups by the intra- and intermolecular imidiza-
tion, and therefore indicates the start of polymer decomposition. In the
third region (300 °C–500 °C), the corresponding data at T30 and T50
reflect the decomposition of imides and the random backbone scission.
Therefore, it is the T15 and T20 parameters that can provide reliable
criteria to evaluate the thermal stability of polymers and echo the
polymer's stability in aqueous solutions.
The cross plots at T15 and T20 can be used to develop a correlation
between those degradation temperatures and the half-life of polymers
in aqueous environments under harsh conditions. The long-term sta-
bility evaluation of polymers is an essential and time-consuming re-
search work as it takes several months for researchers to verify and
screen suitable polymers with good long-term stability. Although in-
creasing the temperature for the aging test can shorten the test time,
owing to the acceleration of polymer hydrolysis (Moradi-Araghi et al.,
1982; Doe et al., 1985), several weeks are still needed to complete such
accelerated evaluations. In comparison, the values of T15 and T20 can be
obtained in hours. They are shown to reflect the polymers’ long-term
stability behavior. Therefore, the TGA method can be used to efficiently
screen polymer candidates, especially for high temperature and high
salinity conditions.
3.4. Variation of polymer concentrations with aging time
As polymers in solution degrade into smaller molecules, despite the
associated viscosity reduction, the polymer's concentration remains
constant. Fig. 7 plots measured variations in polymer concentrations
with aging time, as inferred from TOC analyses. With the exception of
SPAM-A1L and SPAM-S2L, we observe significant reduction in polymer
concentrations. The reduction of polymer concentrations is caused by
precipitation. Those polymers, regardless of viscosity degradation, are
no longer applicable for the studied conditions. Based on the results in
Table 6, we can group the polymers into 3 categories according to the
precipitation time. Those results are consistent with the long-term
stability results (refer to Table 4). Once again, the results confirm the
potential of SPAM-A1L and SPAM-S2L and their capacity to withstand
high salinity and high temperature environments.
The long-term stability of the polymers was further confirmed by
measuring the molecular weights using GPC. Fig. 8 presents the var-
iation of molecular weights of polymers SPAM-S2L, SPAM-A1L, and
HPAM-A4H. The results indicate that SPAM-S2L has excellent long-
term stability in high temperature and high salinity conditions. Its
molecular weight remains the same over the period of testing, which is
consistent with TGA results and viscosity measurements. The molecular
weight of SPAM-A1L decreased only slightly in the first 60 days. The
molecular retention rate was 86.7% at Day 56, indicating slow polymer
degradation. After 60 days, the molecular weight decreased sharply and

Table 5
Thermal data from TGA thermograms and half-life from long-term stability test.
No. Name T1/2 (day) T5 T10 T15 T20 T30 T50

1 HPAM-N3L 7.97 132.96 188.29 211.58 250.03 318.84 399.84

2 HPAM-A4H 3.95 154.46 205.96 216.45 216.45 225.3 355.32
3 HPAM-A5H 2.14 138.82 193.9 237.82 279.43 333.03 426.06
4 HPAM-A6H 2.94 144.26 192.38 227.45 227.45 291.87 386.88
5 APAM-J1H 8.06 152.64 206.13 250.79 282.62 340.9 391.06
6 APAM-G2L 4.26 133.35 177.31 221.06 246.51 309.98 411.67
7 APAM-G3L 3.02 153.49 204.85 237.8 266.74 318.43 409.36
8 HPAM-Z1M 15.47 138.7 217.74 266.84 300.92 352.2 431.64
9 HPAM-Z2M 45.90 156.64 215.74 257.28 291.02 336.98 387
10 SPAM-H3L 12.31 131.59 183.98 232.85 272.3 330.2 393.28
11 SPAM-A1L 97.63 161.06 292.32 333.2 334.22 339.38 390.35
12 SPAM-S2L 433.22 169.07 305.41 325.09 327.4 332.84 404.29

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Fig. 6. The classification of half-life by decomposition temperatures at different percentage weight loss.

Table 6
Precipitation Time based on the TOC Measurement.
Category No. Polymer Precipitation Time Remark
(days)

1 HPAM-N3L 14 Poor stability

HPAM-A5H 14
HPAM-A6H 14
APAM- J1H 14
APAM-G2L 14
APAM- G3L 14
2 HPAM-Z1M 42 Stable in short period of
HPAM-Z2M 49 time
HPAM-A4H 21
SPAM-H3L 28
3 SPAM-A1L > 110 Good stability
SPAM-S2L > 110

the molecular retention rate was 50.4% at Day 96. These results further
Fig. 7. Concentration as a function of aging time for polymers in seawater at support the fact that the hindrance groups can inhibit the hydrolysis of
95 °C. amide groups to improve the polymer stability under high temperature
and high salinity conditions. The molecular weight variation of two
polymers displays good consistency with the viscosity results in Fig. 4,

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Fig. 8. Molecular weight as a function of aging time for polymers in seawater at
95 °C.
which implies the viscosity reductions of the two polymers are owning
to the molecular weight reduction. It is worth noting that while TGA
results indicate the two polymers (SPAM-S2L, and SPAM-A1L) show
good thermal stability, SPAM-S2L exhibits minute changes in viscosity
and molecular weight while SPAM-A1L exhibits slight reductions in
both viscosity and molecular weight.
Compared with SPAM-A1L and SPAM-S2L, the molecular weight of
polymer HPAM-A4H reduces sharply in the first week. Then, it exhibits
slight reduction with aging time before precipitation in 3 weeks. Such is
the typical behavior for polymers with poor stability.
4. Conclusions
1) Twelve commercial polyacrylamide-type polymers in powder
form were evaluated by TGA. The thermal stability of the polymers was
identified by DTG curves via temperatures at maximum decomposition
rate. Polymers with high values of T15 or T20 can be good candidates for
high temperature and high salinity conditions.
2) The long-term stability of polymers in aqueous solution at high
temperature and high salinity conditions can be estimated by TGA
results. The correlation is well established by identifying the half-life
according to the T15 or T20 values.
3) The long-term stability of the polymers was confirmed by TOC tests
for polymer material loss and GPC analysis for molecular weight
loss.
4) Two sulfonated polymers SPAM-S2L and SPAM-A1L were singled
out owing to their excellent thermal stability. Those two polymers
can withstand high temperature and high salinity environments for
more than 90 days without significant polymer degradation.
5) The method of correlating the long-term stability in aqueous en-
vironments to the thermal stability in powder form provides a fast
and reliable means of screening polymer candidates for high tem-
perature and high salinity reservoir conditions.
Acknowledgement
The authors are grateful to Dr. Jian Hou for the evaluation of the
polymer properties using GPC and Dr. Xi Wu for helpful discussion and
support in this study.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
525
Journal of Petroleum Science and Engineering 180 (2019) 518–525
doi.org/10.1016/j.petrol.2019.04.092.
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