SPE-176454-MS

Study on Effect of Low Calcium Fly Ash on Geopolymer Cement for Oil
Well Cementing
Maheswaren Sugumaran, Universiti Teknologi PETRONAS

Copyright 2015, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE/IATMI Asia Pacific Oil & Gas Conference and Exhibition held in Nusa Dua, Bali, Indonesia, 20 –22 October 2015.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
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Abstract
With the increasing awareness of global warming, geopolymer cement has been identified as one of the
methods in reducing the emission of CO2 during oil well cementing operation. However, it is important
that geopolymer cement can meet the specific requirement of oil well condition in order to be substitute
of current conventional cement system. The use of fly ash in geopolymer based cement can affect the
performance of the cement slurry by its properties which yet needs proper study to yield better advantages
of it.In this research, the main objective is to study the effect of fly ash in geopolymer cement, by varying
the properties which are thickening time, fluid loss and compressive strength. It is identified that the
current conventional cement slurry is not environmentally-friendly, and is energy intensive. It is also
identified that fly ash produced cannot be recycled and mostly being dumped. Thus, this study can provide
the solutions to the problems identified. It involves extensive laboratory work in order to identify the
properties of the cement.This project focused on the designation of fly ash based geopolymer cement
compositions, the testing of the prepared fly ash based geopolymer with different compositions and
different acid concentrations.This report comprises the literature review on the properties of geopolymers,
the experimental works and their results, as well as the discussion and recommendations of the project.The
tested parameters are water ratio, type and molarity of alkaline activator and alkaline activator ratio.The
water ratio is 0.4 with the use of 12M of Sodium Hydroxide and the alkaline activator ratio is 0.4. Sodium
silicate and silica fume was added to optimize the compressive strength which proved to have 31%
increase of strength. Under low concentration acid, the cement is able to withstand the reaction but failed
with higher concentration.The performance of the new blend will be analyzed.
Introduction
Portland cement is used as the conventional cement slurry in current oil and gas industry. However, the
Government of Canada has reported that the use of Portland cement has contributed to the biggest portion
of greenhouse gases emission. It is reported that the replacement of Portland cement is the most effective
means of reducing carbon dioxide emissions, and the new technology for replacement is actually based
on a geopolymeric cement system. It is highlighted that the geopolymeric materials contribute to the cost
saving (Amir H. M, 2008). Geopolymer can be manufactured from a variety of materials, such as fly ash,
blast furnace-slag, rice husk ash, and palm oil fuel ash. Asphaltene is defined as the heavy fraction of
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crude oil, which is soluble in aromatic solvent, but insoluble in normal heptanes. Further study of
geopolymer cement system is crucial so that application of geopolymer properties in oil well cementing
can be optimized. Fly ash; a stack emission from coal-fired thermal plants, can be an effective
supplementary cement material in replacing current conventional cement slurry. However, study must be
done to optimize the performance of geopolymer cement by understanding its properties (Seabrook P.,
2003). This research will focus on the effect of fly ash on geopolymer properties by studying the
properties of fly ash based geopolymer as well as investigating the advantages of fly ash based
geopolymer cement. This research involved laboratory experiment which will look into the compressive
strength of fly ash based geopolymer, as well as its acid resistance properties.
Geopolymer and Geopolymerization
Geopolymer is a type of amorphous aluminasilicate cementatious material that pose a high strength, with
good volume durability, stability and resistance to acids (Nasvi MCM, 2011). This amorphous solid phase
transforms into semi crystalline phase after a long curing period after undergoing the reaction with
alkaline activator. Davidovits (1991) highlighted that formation of geopolymer is due to reaction of base
material such as aluminum and silicate with high pHalkali metals found in alkali medium. The main
difference between OPC and Geopolymer cement is the way of getting its strength. OPC forms
calcium-silicate-hydrates (CSHs) to attain strength, while geopolymer cement uses the advantage of
polycondensation process of silica and alumina precursors and high alkali content. Rangan(2008) also
supported that polymerization is a process that cause quick chemical reaction under alkaline solution on
aluminasilicates resulting three dimensional structure.
Curing Temperature and Time
Previous research has found that temperatures in the range of 50 – 80°C are widely accepted values that
are used for successful geopolymer hydration. Geopolymer gains strength with curing temperature as
Silica and Aluminium readily dissolves from the source material with increasing temperature. However,
at very high curing temperature (⬎100°C), inter granular structure of geopolymer are possible to break
up which could reduce its strength (Nasvi, Ranjith, & Sanjayan, 2012). Previous research done discovered
that the strength values of pastes of the geopolymers on the basis of fly ashes show an increasing trend
with increasing external curing time (in days) from the moment of their preparation. The longer the time
of curing, the higher the strength is obtained.
Alkali Activator
The most used alkaline liquid activator is a mixture of s mixture of sodium or potassium hydroxide
(NaOH, KOH) with sodium waterglass (nSiO2Na2O) or potassium waterglass (nSiO2K2O) (Palomo et al,
1999), where it found agreement by Xu’s work that the most common alkaline liquid used in geopoly-
merization is a combination of sodium hydroxide (NaOH) and sodium silicate.The ratio of alkaline
activator to fly ash of 0.25, 0.30, 0.35, and 0.40 only are found to be workable (Joshi & Kadu, Role of
Alkaline Activator in Development of Eco-friendly Fly Ash Based Geopolymer Concrete, 2012). Previous
study has discovered that the alkaline activator/fly ash ratio of 0.4 has the optimum amount of alkaline
liquid, which could activate the fly ash in highest rate of geopolymerization comparing to other ratio
(Al-Bakari et al., 2012). Various molarity of NaOH solution affect the strength of geopolymer paste fly
ash. A study in 2011 revealed that a 12M NaOH solution produced the highest compressive strength for
the geopolymer (Abdullah, et al., 2011). Study on the effect of NaOH molarity on geopolymer compres-
sive strength also found that the compressive strength of geopolymer increases with increase in molar
concentration of sodium hydroxide and best suited concentration is 12 with respect to safety in handling
and the cost effectiveness as well. This shows agreement with a research finding which revealed that
concentration of 12M produced the highest compressive strength for all days of testing.
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Acid Resistance
Studies found by Thokchom et al in 2009 revealed even though the specimens of fly ash-based
geopolymer cement were fully dealkalizes, it still had substantial residual compressive strength, confirm-
ing its high resistance. According to BRE Digest 363, concretes made with combinations in Portland
cements and pulverized fly-ash has good Sulphate resisting properties when the combination is 25% to
40% (Ghosh, 2002). This has confirmed the ability of fly ash to improve conventional cement’s properties.
It is stated that class F fly ashes (low calcium fly ash) can improve the Sulphate resistance of concrete
while the situation with class C (high calcium fly ash) is unclear (Ghosh, 2002).

Experimental Methodology

All slurries were prepared according to API-10A standards. Several experiments were conducted to
achieve the project’s objectives. Thus, tow experiments were designed, which are firstly; to determine the
compressive strength, while the other one aims to determine the acid resistance behaviour of fly ash-based
geopolymer cement. For the compressive strength test, four experiments need to be conducted by varying
the properties affecting geopolymer compressive strength, which is listed below:
● Experiment 1 aims to find the effect of curing temperature on the cement compressive strength
● Experiment 2 aims to find the best water ratio needed for the geopolymer cement
● Experiment 3 aims to find the effect of alkaline activator to fly ash ratio on the cement compressive
strength
● Experiment 4 aims to find the effect of sodium hydroxide molarity on cement compressive strength

All the experiments are tested on different curing period which are 3, 7, 14, and 21 days, to
simultaneously study the effect of different external exposure curing time. For all experiment, sodium
silicate to sodium hydroxide ratio of 2.5 has been used. The design parameters as well as the procedures
for each experiment are as attached in the appendix. For the acid resistance test, two sulphuric acid with
different concentrations are prepared, which are 2%, and the more concentrated one, 10% sulphuric acid.
The cement specimen designed for this acid resistance testing is designed using all the value of parameters
that produced the highest compressive strength for each test, which means, the best result for each
experiment tested in compressive strength testing. Thus, this experiment is done at the end of the
experimental work for this project.

Results and Discussion

Results obtained are arranged in chronological order of experiment. Each experiment result will lead to
the ratios used in the latter experiment, thus each experiment is related to each other.
Compressive Strength Testing
Label from each specimen are presented in the table of experiment design which is attached in the
appendix. Results from Experiment 1 presented that for curing period of 3 days until 14 days, cement
cured at 60°C possessed higher compressive strength as compared to the one cured at 100°C. Even though
after 21 days curing period cement sample 1B4 (cured at 100°C) possessed higher compressive strength
compared to sample 1A4 (cured at 60°C), cement sample 1A4 is preferable because cracks are observed
on cement sample 1B4 and other samples cured at 100°C after it is taken out of the oven. This cracks
showed that 100°C curing temperature is not suitable for fly ash-based geopolymer cement heat-curing.
This finding shows agreement with previous study by Nasvi that at very high curing temperature
(⬎100°C), inter granular structure of geopolymer are possible to break up which could reduce its strength
(Nasvi, Ranjith, & Sanjayan, 2012). Optimum curing temperature for higher strength of geopolymer
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cement is found to be lying between 55– 60°C (Nasvi et al., 2012). Thus, curing temperature of 60°C in
the oven is accepted, and is used for the next experimentation design.
For Experiment 2, results for sample 2B1, 2B2, 2B3, and 2B4 are taken from Experiment 1A as all the
properties are the same, and due to limited time. Results from Experiment 2 revealed that 40gram water,
which the water ratio is 30% of the fly ash mass possessed the highest compressive strength as compared
to 40% (60gram) and 50% (80gram) water content. Besides, the difference of compressive strength value
of sample 2A, 2B, and 2C is significant which samples from 2A experiment possessed more than 5MPa
compressive strength. Thus, water to fly ash ratio of 0.3 is concluded more far superior than another two
ratios. It is concluded that decreasing water to fly ash ratio will increase the compressive strength of fly
ash-based geopolymer cement. This finding confirms previous finding that the compressive strength of
geopolymer concrete is inversely proportional to the water-to-geopolymer binder ratio similar to that of
water-to-cement ratio in cement concrete (Patankar, Jamkar, & Ghugal, 2013).
For Experiment 3, results showed that the optimum alkaline activator to fly ash ratio is 0.4. This result
confirmed the previous finding which has discovered that the alkaline activator/fly ash ratio of 0.4 has the
optimum amount of alkaline liquid, which could activate the fly ash in highest rate of geopolymerization
comparing to other ratio (Al-Bakari et al., 2012). The changing ing the alkaline activator content effect
on the (Si) species content, based water content, and on thesodium ions content. Increasing alkaline
activator form 0.3 to 0.4 increases the geopolymer strength; however, increasing it again to 0.5 seems to
reduce the performance of the cement’s strength. The increasing in alkaline activator/fly ash ratio
increases water content, affect the workability of the prepared geopolymer. It is concluded that ratio of
alkaline activator/fly ash ratio above 0.4 is not preferable as water content exceed 0.3 of total mass of fly
ash will reduce the specimen’s compressive strength as what is founded in experiment 2.
For Experiment 4, the result presented that the optimum sodium hydroxide molarity to be used as part
of the alkaline activator is 12M. It also shows that increasing the molarity from 12M to 15M decreased
the compressive strength. This confirmed the previous finding from literature review that research has
discovered strength decreased when the concentration was increased from 12M to 14M. This is due to an
excess of OH- concentration in the system involved a strength decrease in the alkali cement. However,
10M sodium hydroxide molarity seems no ample to be as the binder for the cement. It may be due to the
lower rate of polymer formation resulting in the decrease of strength (Nuruddin et al., 2011).

Acid Resistance Testing

Observation shown that just a trace amount of deposits found at the bottom of the beaker for cement that
is immersed in 2% Sulphuric acid solution for a period of 24 hours. Thus, the durability of the fly ash
geopolymer cement is proved for this level of acid concentration. Hence, for subsurface formation that is
found to be containing acid solution or the sulphate attack of this less concentrated acid, fly ash can be
the alternative for the oil well cement. Figure 5 shows corrosion occurred with a significant effect even
though the period of immersion is only 24 hours. It is concluded that large volume of fly ash are needed
when the cement is to be exposed to a concentrated acid environment, such as this concentration of 10%
Sulphuric acid, so that it can be retained for a longer period. However, this situation might permit the
invasion of gas as into the wellbore as its physical has been destroyed. Thus, the durability of fly ash to
acidic environment is concluded as not up to 10% acid solution, however, it can be the resistant to 2% acid
solution.
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Table 1—Experimentation Design for Experiment 1

Table 2—Experimentation Design for Experiment 2

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Table 3—Experimentation Design for Experiment 3

Table 4 —Experimentation Design for Experiment 4

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Figure 1—Graph Result of Experiment 1

Figure 2—Graph Result of Experiment 2

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Figure 3—Graph Result of Experiment 3

Figure 4 —Graph Result of Experiment 4

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Figure 5—Result of immersion in different acid concentration solution (From left: 2% & 10%)

Figure 6 —Result of immersion in different acid concentration solution (Top View) (From left:10% & 2%)

Conclusion
The ultimate objectives to assess the effect of fly ash in geopolymer properties are achieved. Previous
studies mentioned that new cement slurries have reduced the effect of greenhouse gases, and less energy
intensive. The abundant available resources of fly ash in Malaysia made the project relevant to be
implemented. Thus, this object aims to find the benefits that can be derived from the properties of fly ash
geopolymer cement. From the experiment conducted, the optimum curing temperature and water to fly ash
ratio for fly ash geopolymer cement can be identified. It is concluded that curing temperature of 60oC
generate cement cube with higher compressive strength and temperature of 100oC will produced cement
cube that is physically cracked. Furthermore, water to fly ash ratio of 0.3 is the best ratio that produces
highest compressive strength of fly ash geopolymer cement, while alkaline activator to fly ash ratio is
optimum at 0.4. Significant increase in compressive strength is observed when water to fly ash ratio is
reduced from 0.4 to 0.3. Whilst, 12M of sodium hydroxide molarity found to be the best. All of the results
obtained have been presented and discussed. Fly ash geopolymer cement is found to be resistant to acid
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solution of less than 10% concentration. It is proved when little deposits are observed when the cement
is immersed in the 2% solution for one day. However, exposing the fly ash cement to 10% acid solution
is not recommended as it is not really physically durable to that level of concentration. On top of that, it
is proved that longer curing time increases the compressive strength of the cement. Overall, fly ash-based
geopolymer cement seems to be a good potential as the alternative to current oil well cement, the Portland
cement. Fly ash-based geopolymer cement contributes to the reduction of the emissions of greenhouse
gases, and improves the performance of geopolymer cement in well cementation. It also provides the key
to fly ash dumping issues.

Acknowledgement
I would like to express my deepest gratitude to all parties that involve in making this project very
interesting and meaningful for me. Deepest gratitude goes to Universiti Teknologi PETRONAS for
permission to publish the paper and Ms Raja Rajeswary, for supervising the research yet not to forget
family members for their endless support.

References
Abdullah, M., Kamarudin, H., BnHussain, M., Nizar, I. K., Rafiza, A., & Zarina, Y. (2011). The
Relationship of NaOH Molarity, Na2SiO3/NaOH Ratio, Fly Ash/Alkaline Activator Ratio, and
Curing Temperature to the Strength of Fly Ash-Based Geopolymer. Advanced Materials Research,
pp. 1475–1482.
Al-Bakari, A. M., Kareem, A., & Myint, S. (2012). Optimization of Alkaline Activator/Fly Ash Ratio
on the Compressive Strength of Fly Ash-Based Geopolymer. Kangar: Universiti Malaysia Perlis
(UniMAP).
Ghosh, S. (2002). Advances in Cement Technology. New Delhi: Tech Books International
Joshi, S., & Kadu, M. (2012). Role of Alkaline Activator in Development of Eco-friendly Fly Ash
Based Geopolymer Concrete. International Journal of Environmental Science and Development,
417–421.
Nasvi, M., Ranjith, P., & Sanjayan, J. (2012). Comparison of Mechanical Behaviors of Geopolymer
Cement and Class G as Well as Cement at Different Curing Temperatures for Geological
Sequestration of Carbon Dioxide. Melbourne: American Rock Mechanics Association (ARMA).
Nuruddin, M. F., Dernie, S., Ahmed, M. F., & Shafiq, N. (2011). Effect of Superplasticizer and NaOH
Molarity on Workability, Compressive Strength and Microstructure Properties of Self-Compacting
Geopolymer Concrete. Perak: World Academy of Science, Engineering and Technology
Palomo, A., Grutzeck, M., & Blanco, M. (1999). Alkali-activated Fly Ashes, A Cement for the Future.
Madrid: Pergamon
Patankar, S. V., Jamkar, S. S., & Ghugal, Y. M. (2013). Effect of Water-to-Geopolymer Binder Ratio
on the Production of Fly-ash Based Geopolymer Concrete. International Journal of Advanced
Technology in Civil Engineering, 79 –83.
Seabrook, P., & Campbell, K. (2003). Sustainability in Construction: Using Fly Ash as a Cement
Replacement. Richmond: Levelton Engineering Ltd.