Carbon capture and sequestration (CCS) has been employed to reduce global warming, which is one of the critical environ- mental issues gained the attention of scientific and industrial communities worldwide. Once implemented successfully, CCS can store at least 5 billion tons of C O per year as an effective and technologically safe method. However, there have been a few issues raised in recent years, indicating the potential leakages paths created during and after injection. One of the major issues might be the chemical interaction of supercritical C O with the cement, which may lead to the partial or total loss of the cement sheath. There have been many approaches presented to improve the physical and mechanical properties of the cement against CO attack such as changing the water-to-cement ratio, employing pozzolanic materials, and considering non- Portland cements. However, a limited success has been reported to the application of these approaches once implemented in a real-field condition. To date, only a few studies reported the application of nanoparticles as sophisticated additives which can reinforce oil well cements. This paper provides a review on the possible application of nanomaterials in the cement industry where physical and mechanical characteristics of the cement can be modified to have a better resistance against corrosive environments such as C O storage sites. The results obtained indicated that adding 0.5 wt% of Carbon NanoTubes (CNTs) and NanoGlass Flakes (NGFs) can reinforce the thermal stability and coating characteristics of the cement which are required to increase the chance of survival in a CO sequestrated site. Nanosilica can also be a good choice and added to the cement by as much as 3.0 wt% to improve pozzolanic reactivity and thermal stability as per the reports of recent studies. Keywords CO storage sites · Cement design · Carbonation · Nano materials · Degradation Introduction Algeria followed the footsteps and sequestrated over 20 mil- lion tons (Mt) of CO in their deep geological sites ever Carbon dioxide (C O ) sequestration is the technology devel- since (Benson and Cole 2008; Takase et al. 2010). Accord- oped in the past decades to reduce the amount of greenhouse ing to the International Energy Agency (IEA), the CCS can gases increasingly released into the atmosphere. In this tech- help to reduce more than 13% of cumulative greenhouse gas nique, which is also known as Carbon Capture and Storage emission by 2050 and restrict the global increase of tempera- (CCS), CO as a dominant greenhouse gas is captured in ture. By 2015, there were 15 large-scale facilities around the industrial sites and injected into deep geological formations world capturing 27 million tones (Mt) of CO every year for thousands of years (Gaurina-Međimurec et al. 2010). The (International Energy Agency 2015). This would be a sig- CCS technology has been initiated 20 years ago when a mil- nificant contribution into the reduction of global greenhouse lion metric tons per year of C O was injected into an aquifer gas emissions needed to restraint climate change. beneath the North Sea (Benson and Cole 2008). Canada and Coal beds, saline aquifers, and depleted oil reservoirs are often chosen for C O storage purposes, among which depleted reservoirs are the best options due to their geo- * Raoof Gholami logical history, integrity and infrastructures. Abundant and firstname.lastname@example.org closed wells of these reservoirs are the best conduits to Department of Petroleum Engineering, Curtin University, inject CO , where the injection interval is cemented to avoid Sarawak, Malaysia leakages. However, chemical degradations and mechanical Department of Civil Engineering, Curtin University, failures induced due to the reaction with supercritical (Sc) Sarawak, Malaysia Vol.:(0123456789) 1 3 Journal of Petroleum Exploration and Production Technology CO and carbonic acid under reservoir conditions may cre- 2 10000 ate leakage paths in the cement, causing seepage of C O CO Solid to the surface and other valuable subsurface resources (Xu 2 Supercric et al. 2007; Bachu and Bennion 2009; Zhang et al. 2013; al Fluid CO liquid Ansarizadeh et al. 2015). In fact, the class G cement, which is commonly used in the primary or secondary cementing Sublimaon point stages, is very vulnerable and may lose its durability once -78.5 C at 1 atm exposed to supercritical (sc) C O . As a result, its mechanical Crical point 32 C at 69 atm and physical properties such as compressive strength, per- meability, and porosity might change unfavorably, resulting in leakage of C O from the storage sites (Zhang et al. 2013; 0.1 Triple point Ansarizadeh et al. 2015). -56.6 C at 5.11 atm There have been several methods proposed in recent years 0.01 to improve the mechanical and transfer characteristics of the CO gas cement used for sequestration practices. Changing the water- 0.001 to-cement ratio, applying pozzolanic materials and employ- -140 -100 -60-20 20 60 100 ing non-Portland cement are the most important approaches Temperature, C proposed so far with limited success once tested under reser- voirs conditions (Abid et al. 2015). Employing nanoparticles Fig. 1 CO phase diagram [modified after (Oldenburg 2007; Waseem might be another approach that worth consideration as a Arshad et al. 2017)] solution for reinforcing the cement. This is mainly because chemical and mechanical properties of materials are changed when their particle size is reduced. It is also known that CO sequestration in deep geological formations Calcium–Silicate–Hydrate (C–S–H), which is one of the main components required to resist against the CO attack, CO storage sites are often referred to as deep geological is widely available in a high order structure at the nanoscale formations with a storage capacity of 675–900 billion tons (Abid et al. 2015; Arina and Irawan 2010). The benefits of (Ansarizadeh et al. 2015; Benson and Cole 2008). It is a using nanoparticles, such as nanosilica (SiO ), nanoalumina common practice for the oil and gas industry to inject C O (Al O ), clay nanocomposites, nanotitanium oxide (T iO ), into particular deep (more than 800 m) geological forma- 2 3 2 carbon nanotubes (CNTs), and nanoglass flake (NGFs) have tions (reservoirs) to increase the petroleum production, been widely presented in the building and polymer industries which is also known as Enhanced Oil Recovery (EOR). (Abid et al. 2015; Jahangir and Kazemi 2014; Lee 2012; When these reservoirs are completely depleted and verified Ghadami et al. 2014). However, there have been a very lim- as a safe geological storage sites, CO sequestration is con- ited discussion on their potential applications in the oil and sidered as part of the CCS technology in the field (Gaurina- gas industries, especially for C O sequestration sites. The Međimurec et al. 2010). aim of this paper is to provide a review of the characteris- Once injected into the storage sites, CO must be moni- tics of different nanoparticles and evaluate their potential tored carefully as it appears in different phases under applications in the cement used for the storage sites. This diverse temperature and pressure conditions (see Fig. 1). may shed some lights as to how the physical and mechani- For instance, at the ambient temperature, CO appears as a cal characteristics of the cement can be improved for a safer gas, but it becomes a supercritical fluid under the tempera- storage of CO . ture of 32 °C and the pressure of 7 MPa (IPCC 2005; Old- enburg 2007), which often happens at the depth of greater than 800 m. Background Cement systems for CO sequestration In this section, attempts are made to provide a better insight into the interactions taking place in storage sites between Secondary cementing is done to seal off the wells used to the cement and CO . The importance of CO sequestration inject CO in the reservoir. A good well cement should have 2 2 as well as physical and chemical phenomena involved are an appropriate thickening time, a good rheology, a low water discussed and approaches developed so far to resist the C O attack are presented. 1 3 Pressure, atm Journal of Petroleum Exploration and Production Technology Table 1 Major components of Portland cement (modified from Adams and Charrier 1985) Compound Chemical composition Cement Concentra- Purpose chemist tion (wt %) notation Tricalcium silicate (CaO) ∙ SiO C S 55–65 Enhances the strength and develops early strength 3 2 3 Dicalcium silicate (CaO) ∙ SiO C S 15–25 Hydrates slowly, strength generated over extended period 2 2 2 of time Tricalcium aluminate (CaO) ∙ Al O C A 8–14 Promotes rapid hydration, affects thickening time and initial 3 2 3 3 setting of the cement, and makes the cement vulnerable to sulfate attack Tetracalcium aluminoferrite (CaO) ∙ Al O ∙ Fe O C AF 8–12 Responsible for slow hydration 4 2 3 2 3 3 loss efficiency, and no free water bleeding (Lesti et al. 2013). Portland cement degradation: carbonation There are eight classes of cements listed in the American and bicarbonation Petroleum Institute (API) standard, categorized based on their specifications and functionality. Among all classes, To understand the chemical reactions taking place between Class G (Portland Cement) is the most common one. In fact, supercritical carbon dioxide (scCO ) and Portland cement, Portland cement is commonly used on many occasions due Kutchko et al. (2007) carried out an experimental study to to its accessibility and adaptability to different subsurface simulate a real reservoir condition (i.e., the temperature of conditions. This type of cement consists of four main com- 50 °C and the pressure of 30.3 MPa with a pH of 12.3). They ponents, including Tricalcium Silicate (C S), Dicalcium Sil- indicated that the cement degradation is linked to the struc- icate (C S), Tricalcium Aluminate (C A), and Tetracalcium tural transformation of C–S–H, carbonation of portlandite 2 3 Aluminoferrite (C AF), which give certain functionally to (Ca(OH) ) and the leaching of calcium carbonate (CaCO ). 2 3 the cement such as enhancing the strength or changing the In fact, when CO is injected into a storage site, it dis- hydration rate. Table 1 gives a summary of the functionality solves into the brine, which is often left in the reservoir after provided by the cement components. production, and forms carbonic acid (H CO ) as expressed in 2 3 Tricalcium silicate (C S) is the most abundant component Eq. (3). This leads to a significant reduction of pH: of the cement, hydrating faster than others (Nelson 1990). CO (aq) + H O → H CO (aq). (3) 2 2 2 3 When water is mixed with the cement, hydration takes place As carbonic acidic diffuses into the hydrated cement, and the compressive strength develops, which expressed as Portlandite is attacked, as expressed in Eq. (4), at a very fast (MacLaren and White 2003; Omosebi et al. 2016): rate due to its higher reactivity (Omosebi et al. 2016). This 2C S + 6H O → C S H + 3Ca(OH) 3 2 3 2 3 2 (1) interaction brings an equilibrium to the solution: 2+ − 2C S + 4 H O → C S H + Ca(OH) . (2) Ca(OH) (s) → Ca (aq) + 2OH (aq). 2 2 3 2 3 2 (4) Hydration of aluminate, tetracalcium aluminoferrite However, due to the consummation of Portlandite and 2+ (C AF), is similar to tricalcium aluminate (C A), which leaching of Ca out of the cement matrix, the porosity of 3 3 forms ettringite when it reacts with gypsum. As a result, the cement increases and calcium carbonate (C aCO ) is the production of calcium–silicate–hydrate (C–S–H) is precipitated, as addressed by Eq. (5). Under these circum- more than Ca(OH) due to the abundance of C S. This cal- stances, CaCO acts like a filler and occupies the pore space 2 3 cium–silicate–hydrate is a very important component acting of the cement, causing a significant reduction in porosity. In as the binder of the cement. fact, formation of CaCO not only decreases the porosity and permeability by densification of the cementitious matrix, but also increases the compressive strength. This process, which is known as carbonation, is thermodynamically favored and cannot be avoided (Santra and Sweatman 2011): 3− − 2+ Ca aq + HCO aq + OH aq → CaCO s + H O. ( ) ( ) ( ) ( ) 3 2 (5) Although carbonation improves the cement resistance to CO attack, the crystallization of Ca CO would lead to 2 3 API standard is a practice that is an accepted worldwide standard cracking and volume expansion (Abid et al. 2015). This which is followed by most of the oil and natural gas companies. 1 3 Journal of Petroleum Exploration and Production Technology Fig. 2 Schematic view of the static reactor designed and installed at Curtin University Malaysia would provide a route for CO to migrate easily from the Neat cement degradation storage site. When portlandite is completely consumed, CaCO starts Experimental conditions to dissolve due to its continuous reaction with fresh carbonic 2+ water, which leads to further leaching of Ca and domina- Many of the laboratory experiments carried out to evalu- 3− tion of HCO , as expressed by Eq. (6). This dissolution of ate cement integrity in a C O rich environment were done CaCO is called bicarbonation: using an HPHT vessel. Half of this pressure vessel is often filled with brine (salt water) to have brine saturated CO 3− 2+ 2 H + (aq) + CaCO (s) → Ca (aq) + HCO (aq). (6) (carbonic acid), while the upper half contains only scCO Without CaCO , the remaining C–S–H, which acts as the which is known as wet CO (Barlet-Gouedard et al. 2009). binding component in the hydrated cement, is converted into This configuration allows to simulate a storage site and initi- amorphous silica gel (amSiO ), as expressed by Eq. (7). As ate carbonation of the cement in the presence of CO . Fig- 2+ a result, the amount of Ca gradually increases and more ure 2 shows a schematic view of the pressure vessel installed pores are created within the cement matrix, which leads to at Curtin University, Malaysia. the loss of zonal isolation and migration of CO to the sur- The period of the experiment may vary from a month to face and subsurface resources (Kutchko et al. 2007; Zhang a year during which the samples are constantly monitored to and Talman 2014): evaluate the carbonation rate. To achieve the best result, the 2+ − carbonation tests under these circumstances are carried out C − S − H (s) → Ca (aq) + OH (aq) + amSiO (s). under the static condition where the amount of brine/fresh (7) water initially added to the vessel is maintained (Kutchko et al. 2008). It should be noted that employing fresh water rather than brine would accelerate the degradation of the 1 3 Journal of Petroleum Exploration and Production Technology Table 2 Developed approaches to improve cement resistance in C O sequestration sites (modified after Abid et al. 2015) Approaches Result 3− Using Pozzolanic material, Reducing the permeability and quantity of the portlandite. As permeability decreases, the ingression of CO e.g. fly ash, silica fume, and carbonation slows down (Kutchko et al. 2008, Duguid and Scherer 2010) bentonite Reducing the water content in the cement and decreasing the Ca/Si ratio, causing the creation of a longer chain of C–S–H, which increases the strength of the cement An excessive amount of pozzolanic materials may result in a poor strength development (Kutchko et al. 2008, Laudet et al. 2011) Decreasing water/cement ratio Increasing the unhydrated cement clinker which eventually decreases the permeability Increasing the density which may increase the fracture possibilities May result in creating fractures in heavy weight cement (Brandl et al. 2010) Using non-portland cements It is not sufficient for a long-term wellbore integrity and not generally recommended because of its accessibility (Bai et al. 2015) The hydration products are resistant to C O (Takase et al. 2010) Using special additives Latex, for example, improves the bonding strength and controls the filtration loss. It allows a good strength development (Duguid and Scherer 2010). The resistance against C O attack will, however, not be significantly improved due to a low quantity of CaCO present Epoxy resins will chemically coat the cement but it was degraded when tested at 90 °C and 28 MPa for 31 days (Brandl et al. 2010) Using nanomaterials Nanosilica, for example, improves the microstructure and the strength of the cement by decreasing the porosity and permeability of mortar (Zhang et al. 2014) Polymer/clay nanocomposites increase the tensile strength (Barlet-Gouédard et al. 2007) Nanoiron enhances the compressive strength (Barlet-Gouedard et al. 2012) cement due to the faster rate of CO getting dissolved in the cement morphology is modified by temperature under fresh water. these circumstances. Laudet et al. (2011) carried out a car- bonation test using neat Class G cements exposed to scCO Experimental studies for about 90 days, at the pressure of 8 MPa and two different temperatures of 90 and 140 °C. A faster carbonation front Experimental studies carried out to evaluate cement deg- was found at 140 °C due to the mineralogical nature of the radation are often conducted by an HPHT chamber (ves- hydrates which reduces the cement’s transport properties and sel) to simulate reservoir conditions. These studies are ultimately limits the carbonation process. They emphasized categorized into two classes: (1) cements are exposed to that the wellbore temperature and pressure should be moni- scCO saturated brine and (2) cement samples are solely tored before the cement design. tested against scCO , which is also known as wet scCO To further understand the behavior of Portland cement 2 2 (Kutchko et al. 2007, 2008; Barlet-Gouedard et al. 2009; under sequestrated environments, Kutchko et al. (2007, Arina and Irawan 2010; Duguid and Scherer 2010; Laudet 2008) carried out a series of experiments in which neat et al. 2011). Having done such tests, Barlet-Gouédard et al. class H cement samples were exposed to scCO under the (Barlet-Gouedard et al. 2009) suggested that brine should be reservoir condition (i.e., the pressure of 30.3 MPa and the used for the carbonation test rather than fresh water. They temperature of 50 °C). They observed that the cement resist- used a 0.4M NaCl brine solution and observed a dramatic ance depends mainly on the curing environment. In fact, fall in the propagation rate of the cement samples after 2 the cement cured under HPHT conditions for 28 days had days of exposure to CO -saturated brine. To investigate the the least amount of CO penetration due to the formation of 2 2 effect of temperature and pressure on the cement degrada- calcite. This study was further investigated by Kutchko et al. tion, Arina and Irawan (2010) conducted an experiment by (2008) in which the period of carbonation test was extended preparing the neat Class G cement according to the API from 9 days to 1 year. The results obtained indicated that recommended practice. They cured the cement slurry for 8 h the carbonation reaction is a diffusion controlled phenom- at different temperatures (40 and 120 °C) and pressures (10.5 enon for samples exposed to the scCO environment. Duguid and 14.0 MPa) where it was found that the HPHT condition and Scherer (2010) did a series of experiments to study the reduces the compressive strength, causing densification of relationship between the cement degradation and pH vari- C–S–H, which would increase the rate of CO penetration. ation. There was no degradation in the samples exposed to Barlet-Gouedard et al. (2009) found out that the degradation scCO having a leaching solution of pH 5. Hence, they con- of the cement is faster under high-temperature (90 °C) and cluded that if CaCO can be dissolved into the formation high-pressure (20.68 MPa) conditions. They indicated that water, the degradation would stop. This could be the reason 1 3 Journal of Petroleum Exploration and Production Technology why sandstone reservoirs have a greater carbonation front of the cement, which is one of the key components govern- compared to carbonates. However, this experiment was con- ing the cement’s durability. Hence, the nanosized C–S–H ducted under dynamic conditions and it may not be a true particles with an average size of 5–10 nm can significantly representative of reservoir conditions. reduce the porosity and permeability of the cement (Sobolev Knowing that cement degradation taking place under 2015). Sanchez and Sobolev (2010) highlighted the follow- CO -rich environments, a number of attempts were made in ing advantageous of adding nanoparticles to the cement: the past decade to resolve this issue by providing different approaches, which are discussed in the next section. Well-dispersed nanoparticles can help to suspend the cement grains and aggregate by increasing the viscosity of the liquid phase. At the same time, they can improve Developed approaches to improve cement the segregation resistance and workability of the system; resistance Nanoparticles fill the voids between the cement grains, ceasing the movement of “free” water; As per the discussion provided, the carbonation of Port- Well-dispersed nanoparticles can accelerate the hydration land cement is unavoidable and, hence, a few method- by acting as the centers of the crystallization of cement ologies were proposed to enhance the cement resistance hydrates; as reported in Table 2. Looking at Table 2, it seems that Nanoparticles favor the formation of small-sized crystals nanomaterials have gained the attention of many research- and small-sized uniform clusters of C–S–H; ers in the past few years considering their remarkable Nanoparticles enhance the structure of the aggregates’ functionality and proven applications in the construction contact zone, resulting in a better bond between aggre- and building-related applications. It is undeniable that gates and the cement paste; other supplementary materials can improve the overall Nanoparticles can provide crack arrest and interlock- performance of the cement if properly selected/used. How- ing effects between the slip planes, which improves the ever, the improvement achieved by nanomaterials used so toughness, shear, tensile, and flexural strength of the far is significantly higher than the other materials, mainly cement-based materials; because of their large surface areas, fast interactions, and The tremendous surface area/volume ratio of nanomateri- favorable pozzolanic components. In the next section, als alters the chemical reactions of hydrating cements and different nanomaterials which were already used or may enhances their mechanical strength. have applications to improve the efficiency of cements and concretes are presented together with their advantageous However, it should be noted that the nature of nanopar- and shortcomings. This may provide a deeper insight into ticles, their composition, and dosage may cause some unfa- the potential applications of these nanomaterials in the oil vorable changes in the matrix of the cement. As such, cau- well cementing. tions must be taken to ensure that the nanoparticles chosen for oil well cementing does not pose any negative impact on the physical and mechanical characteristics of the cement once used. In the next section, some of the most common Nanomaterials nanoparticles used in the cement and concrete industry are presented and their potential application for oil well cement- Modification of cement-based materials using nanoparticles ing is discussed. is currently recognized as an active research area for the construction and civil industry. In this technique, nanosize Current state of the art −9 (< 10 ) additives are included in the mixing procedure to improve the desired properties of the cement and concrete In this section, recent studies carried out to improve the (Lee 2012). This is mainly because nanoatoms can much physical and mechanical characteristics of Portland cement easily attached to the surface of each particle and increase are presented. It should be noted that many of these stud- the surface area-to-volume ratio, which potentially increases ies were done in the civil industry and there are a limited the mechanical strength and reduces the porosity of con- number of research works conducted to modify of oil well cretes. Moreover, adding nanoparticles promotes the hydra- cements using nanomaterials. However, since a very same tion process at the early stages due to the large surface area type of the cement is used in the civil and construction of particles (Zhang and Li 2011; Choolaei et al. 2012; Meng industry, the potential benefits and disadvantageous of these et al. 2012). Besides, cement is composed mainly of nano/ nanomaterials in the primary/secondary cementing of wells microsize crystals and amorphous calcium-silicate-hydrate can be understood. (C–S–H). As mentioned earlier, C–S–H acts as the binder 1 3 Journal of Petroleum Exploration and Production Technology Nanosilica (nanoSiO ) for densifying the cement paste. Li et al. (2006) found that water could be trapped between the agglomerated structure Nanosilica has been used in many studies for cement-based of nanoparticles during mixing which later became a porous materials as it is the cheapest oxide nanoparticles (Ershadi zone. This indicated the fact that agglomerated nanosilica et al. 2011; Choolaei et al. 2012). Qing et al. (2007) found had weakened the cement paste matrix. Hence, a proper dis- that 3% wt nanosilica can reduce the amount of calcium persion would be needed to fully harness the nanoparticles hydrate (portlandite), and improves the compressive and in the cement slurry. bonding strength at the early stage of hardening. Ershadi et al. (2011) conducted an oil well cementing experiment Nanoalumina (nanoAl O ) 2 3 by adding nanosilica into the class G cement. The water- to-cement ratio of 0.6 was used to produce a cement slurry Several studies have been conducted to investigate the appli- with a large thickening time, high porosity, and permeability cation of nanoalumina in the cement and concrete industry. and a low compressive strength. They indicated that add- Oltulu and Şahin (2011) studied the single and combined ing nanosilica improves the rheological and mechanical effects of nanopowders (i.e., nanoalumina and nanosilica) on properties of the cement, while the porosity and perme- the cement strength and capillary permeability. They added ability decreases by 33 and 99%, respectively. This could 0.5, 1.25, and 2.5 wt% binder amount of nanoparticles to the be due to the filler characteristics of nanosilica, which can cement and tested the compressive strength at the early (i.e., enhance the microstructure and promote further pozzolanic 3 and 7 days), standard (i.e., 28 days), and late stages (i.e., 56 reactions (Ershadi et al. 2011; Choolaei et al. 2012). The and 180 days), whereas the capillary permeability was only results obtained from the study of Choolaei et al. (2012) determined after 180 days. The best result for the compres- also emphasized on the great increase of the compressive sive strength and the capillary permeability were observed strength after adding different portions of nanosilica into when 1.25 wt% nanoalumina was used. They concluded that an ordinary Portland cement. They also indicated that the nanoalumina is a better option compared to nanosilica when porosity and permeability of the cement decreases which it comes to the improvements of the physical and mechanical was subjected to the quantity of nanosilica used. They con- properties of the cement. They also indicated that a com- cluded that a certain quantity of nanosilica must be added bination of these two nanoparticles would lead to agglom- to the cement to achieve the desired functionality. A very eration and reduces the overall performance of the cement similar conclusion was made by Mendes et al. (Mendes mortar. Later, in a similar study, Oltulu and Şahin (2013) and Hotza, Repette 2014) as they highlighted that a large highlighted that 1.25 wt% single nanopowder would be good amount of nanosilica would reduce the performance of the enough to maximize the compressive strength and minimize cement, while a small amount would not make any signifi- the permeability of the cement. Mendes et al. (Mendes and cant changes. Choolaei et al. (2012) proposed to use 1 wt% Hotza, Repette 2014) also pointed out that nanoalumina and Oltulu and Şahin (2011) suggested 2 wt %, whereas improves the abrasion resistance and thermal shock as well Mendes et al. (Mendes and Hotza, Repette 2014) recom- as resistance against any drastic changes in temperature. mended 3 wt% nanosilica for being mixed with the cement Heikal et al. (2015) partially replaced cement with 1, 2, to have the best performance. Nevertheless, these portions 4, and 6 wt% nanoalumina to study their influences on the significantly increased the viscosity of the cement slurry by cement strength. Polycarboxylate-based superplasticizer was preventing the separation of cement particles. also used as part of this study to maintain the rheology of However, the observation made by Ghafoori et al. (2016) the cement slurry. The samples were cured for 28 days in a was not aligned with the previous findings. They replaced water bath and the results revealed that adding nanoalumina their Portland cements (Class I) with 6 wt% nanosilica/ enhances the hydration of the cement by accelerating the microsilica and fully submerged the cement samples in a initial and final setting times. The compressive strength was 5 wt% chemical sodium sulfate (N a SO ) solution for 1 year. also increased for the slurry having superplasticizer. They 2 4 The results obtained indicated that the microsilica-based concluded that 1 wt% nanoalumina is the optimum amount cement expands by 0.043%, whereas the nanosilica-based to achieve the desired properties. cement could swell by 0.054%. It was also observed that To study the effect of sulfate attack on the cement, Jahan- the compressive strength of 6 wt% nanosilica-based cement gir and Kazemi (2014) added 0.1 kg nanosilica and 0.05 kg (~ 44 MPa) is lower than that of the microsilica-based nanoalumina to the cement, cured the samples at the room cement (~ 52 MPa). Their mercury intrusion porosimetry temperature for 24 h, and exposed them to 10 wt% sulfuric (MIP) testing showed a higher volume of pores in the nano- acids for 3 to 28 days. Their study indicated that the com- silica mixture. These could be linked to the agglomeration pressive strength increases by 50% when nanoparticles are effect of the dry nanosilica during mixing. They indicated used. It was also found that a combination of nanoalumina that agglomerated nanosilica failed to be a nucleation site 1 3 Journal of Petroleum Exploration and Production Technology and nanosilica may result in a lesser expansion, since nanoa- cement-based materials. Hakamy and Shaikh (Hakamy et al. lumina is a great gelatinous preserver. 2014) carried out an experiment on hemp-fabric-reinforced nanocomposites by partially substituting ordinary Portland Nanotitanium dioxide (nanoTiO ) cement (OPC) with 1, 2, and 3 wt% nanoclay. The water-to- cement ratio was considered as 0.48, and it was found that Nanotitanium dioxide has been used in several studies with 1 wt% nanoclay would be the optimum quantity required to cement-based materials due to its functionalities, such as improve the hemp-fabric, nanomatrix adhesion, and thermal removal of volatile organic compounds and self-cleaning, stability. It would also reduce the porosity and water absorp- which are commonly known as photocatalytic properties tion, and increase the flexural strength, fracture toughness, (Lee and Kurtis 2010; Chen et al. 2012). Unlike nanosil- and impact strength. The reduction of transport properties ica, it is a non-reactive filler and has no pozzolanic activity was highlighted by Surendra et al. (Surendra et al. 2015), (Chen et al. 2012). Zhang and Li (2011) conducted a test as well. According to them, nanoclay has a two-layer struc- on the concrete and demonstrated that a small quantity of ture which helps to block the water molecules transport nanoTiO may have a better performance than adding a large and reduce the permeability of the cement mortar, which volume. According to them, adding 1 wt% nanotitanium increases the compressive strength by 12% when 1 wt% kao- dioxide would increase the compressive strength by 118%. linite is added. The flexural strength of the cement paste was This quantity could also reduce the porosity from 11 to 9%. increased when 1 wt% kaolinite was added to the cement. They concluded that the finer the pore structure of the con- Baueregger (2015) studied the use of nanoclay on the early crete is, the higher the resistance of the concrete would be cement strength. The kaolinite was used by different portion against the chloride penetration. Senff et al. (2012) prepared as the nanoclay. Their results showed that nanokaolin clay cement samples with 12 wt% nanotitanium dioxide based on could boost the early compressive and tensile strength of the a water/binder weight ratio of 0.5 and did rheological and cement without negatively impacting the final strength after flow table measurements. They found that the torque, yield 28 days. They also pointed out that a proper dispersion tech- stress, and plastic viscosity of mortars increase significantly nique and an optimum size selection would be critical factors by this modification. However, changes in the mechani - to improve the overall performance of the cement. Hakamy cal properties, such as the compressive strength, were not et al. (2015) studied cement nanocomposites reinforced with obvious. According to the study carried out by Meng et al. hemp-fabric and calcined nanoclay (CNC) under the NaOH (2012), where 0, 5, and 10 wt% nano TiO were mixed by the treatment. They reported that 1 wt% CNC reduces the poros- cement, the compressive strength decreases once 10 wt% ity and water absorption and increases the flexural strength, nanotitanium dioxide were added to the cement. Similar fracture toughness, impact strength, and thermal stability. results were shown by Perez-Nicolas et al. (Pérez-Nicolás They also stated that a significant amount of CNC being et al. 2017) where they found that after 28 days of curing, used in the cement would cause agglomeration. As such, a increasing the amount of nanometrically structured TiO in proper dispersion method must be considered to ensure that the cement decreased the compressive strength due to the clay nanoparticles can reinforce the cement structure. increase of mixing water. Chen et al. (2012) used a similar percentage as Meng et al. (2014) and showed that the com- Carbon nanotubes (CNTs) pressive strength increases at all ages. Besides, cement sam- ples could withstand the corrosion and flame abrasion (Lee Carbon nanotubes (CNTs) are hollow tubular channels, and Kurtis 2010). Mohseni et al. (2016) studied the applica- which are a rolled up version of the single or multiple layer tion of nanoTiO on rice hush ash-based cement compos- graphene (Ferro et al. 2011). Their length is not restricted ites. The percentage of nanoparticles used varies from 1 to but often in micrometer size, while their diameters are 5 wt% of the binder, and the water-to-binder ratio of 0.4 was something between 0.4 and 10 nm for a single-walled CNT used to prepare the slurry. Improvements of the compres- (SWCNT) or from 4 to 100 nm for a multi-walled CNT sive strength and durability were recorded, especially for the (MWCNT). Figure 3 shows a schematic view of SWCNT mixture having 10 wt% rice hush ash and 5 wt% nano TiO . and MWCNT. They also observed reductions in the transfer properties with CNTs were discovered by Iijima (1991) as the materials the increase of nanoadditives in the chloride permeability exhibit outstanding mechanical, thermal, and conductive test. properties. This ultralight weight material has been involved in different studied ranging from medicinal and construc- Polymer/clay nanocomposites tions to buildings of structures ever since. There have also been a few studies on the application of CNTs in the oil well Nanoclay is another nanomaterial which can be con- cementing where improvements in the compressive strength sidered as a potential alternative for the modification of (Nasibulina et al. 2010), ductility (Abu Al-Rub et al. 2012), 1 3 Journal of Petroleum Exploration and Production Technology Fig. 3 a SWCNT and b MWCNT structures (http:// www.nanoc arbon .cz) resilience (Yazdanbakhsh et al. 2009), and Young’s modulus of the dispersion technique applied. Mendoza et al. (Men- (Sáez de Ibarra et al. 2006) were reported. doza Reales et al. 2016) indicated that addition of MWCNTs For instance, Tyson (Tyson et al. 2011) indicated that by the mass of cement up to 0.5% in an anionic surfactant CNT can increase the fracture toughness and prevent the can help to have a good dispersion. There was no negative creation of crack induced due to the expansion. It was also impact or chemical affinity reported to the cement in that found that the rheology and stability of the cement slurry study, even at the temperature of 65 °C. will not be altered if a sophisticated dispersion technique On the contrary, the study of Camacho et al. (2014) con- is employed (de Paula et al. 2014). Moreover, CNTs can cluded that the incorporation of MWCNTs in the cement increase the stiffness of C–S–H and decrease the porosity would lead to a higher corrosion rate. In their study, they of the cement matrix, which ultimately reinforce the cement considered a water-to-cement ratio of 0.5 with 0.05, 0.1, (Ferro et al. 2011). Rahimirad and Baghbadorani (2012) 0.25, and 0.5 wt% MWCNTs dosage to the cement. Distilled studied the use of CNT-reinforced cements in preventing water was used for the sample preparation and the cement gas migration, which is one of the cementing problems in pastes were fabricated in 20 °C and 65% relative humidity gas wells. They concluded that the probability of having (RH) for 28 days. Prismatic specimens were prepared for two casing failure in oil and gas wells can be reduced, because corrosion tests: (1) chloride attack tests conducted by par- CNTs have a high aspect ratio and, hence, would require tially immersion of the specimens in a brine solution and (2) significant energies to allow the crack propagation around a accelerated carbonation tests where samples were exposed to tube. However, to have an efficient CNT synthesized cement, dry and wet CO . The results obtained from both tests were a proper dispersion technique must be used and an optimum similar and revealed that the increasing MWCNT dosage quantity of CNTs must be found. de Paula et al. (2014) dis- increases the corrosion rate. These could be explained with persed the single-layered carbon nanotube (SWCNT) into the depassivation of the steel surface which was due to a the ground cement clinker using lignosulfonate. Although pH decrease induced by the cement carbonation. However, the results were promising, the scanning electron micro- this corrosion study was based on the electrode interactions scopic images did not show the perfect bonds between the which could not be considered as an approach to directly cement matrix and SWCNT, which indicate the inefficiency observe the behavior of MWCNT-based cements. 1 3 Journal of Petroleum Exploration and Production Technology their behaviors under the HPHT condition of C O sequestra- tion conditions have not been fully understood. Conclusion There have been many studies proposing solutions to improve the overall performance of the cements used in CO sequestration sites, but none of these approaches were totally successful in resolving these issues, due, perhaps, to the severity of interactions between the cement and supercritical CO . Nanoparticles have revealed promis- ing results once added to the cement in various condi- tions, which might be due to their large surface area and reactivity. It seems that almost all types of nanomaterials Fig. 4 Appearance of GFs in a coated substrate can act like a filler to densify the microstructure, reduce the porosity, improve the transfer properties, and, eventu- Nanoglass flake (NGFs) ally, enhance the mechanical strength. However, it appears that combination of two or more nanoparticles can lead Glass flake (GF) substrates are defined as highly planar to agglomeration and creates unfavorable changes in platelets with a very smooth surface. They are transparent the cement properties. Superplasticizer, as a dispersant with a transparent color tone. Nanoglass flakes (NGFs) were agent, may help to have a better and uniform dispersion introduced early in 2010, having a thickness of 100–750 nm. of nanoparticles in the cement structure, but there is no Because of the layered structure, GFs have many advantages established approach to determine the amount of nanopar- over other nanomaterials, such as providing a better interac- ticles required to have an efficient cement under different tion between filler and matrix, which improves the overall conditions. properties of the final cement product (see Fig. 4) (Nematol- Nanosilica might be one of the best nanoparticles for the lahi et al. 2010; Salehi et al. 2017). cement probably due to its lower cost and pozzolanic activ- As it is seen in Fig. 4, the laminar structure of NGFs ity. Nanoclay is also cheap, but it is not as much good as creates a tortuous path, preventing any particles to intrude nanosilica due to its lesser pozzolanic activity. NanoAl O 2 3 into the substrate easily. Since their introduction in the coat- has a better performance compared to nanoSiO , but it is not ing industry in the 1960s, GFs have been widely used in a commonly used, perhaps, because of cost-saving purposes. variety of different applications due to their excellent mate- NanoTiO has no pozzolanic activity, but it has photocata- rial improvements. GFs can also improve the chemical and lytic properties, which can help to decrease the migration corrosion resistance properties of materials (Nematollahi of CO . However, Nanotitanium dioxide may not be suit- et al. 2010; Ghadami et al. 2014). Moreover, they have been able for CO sequestrated sites due to its instability under extensively used as an in-situ barrier for many industrial high-temperature and high-pressure conditions. CNTs and applications, such as external coating of high-temperature NGFs can withstand harsh environments, but there are a oil flow lines in Duri Oil Field, Indonesia (Watkinson 2009). limited number of studies reporting their applications in the Watkinson (2009) in his study on the concrete indicated that oil well cementing. Thus, further studies are recommended NGFs are capable of enhancing the chemical resistance and to evaluate the application of these nanoparticles when they the compressive and tensile strength of materials. Consider- are mixed in the cement and exposed to CO . ing the fact that NGFs can provide a tough impermeable bar- Acknowledgements The authors would like to acknowledge the Min- rier for steel and concrete surfaces by generating the tortuous istry of Higher Education (MoHE) in Malaysia to fund this research paths, they might be a good option to improve the cement through the Fundamental Research Grant Scheme (FRGS) under the properties under the severe and abrasive conditions of C O 2 grant number FRGS/1/2015/TK05/CURTIN/03/4. storage sites. According to Salehi et al. (2017), by adding 0.5 Open Access This article is distributed under the terms of the Crea- wt% GFs, a lesser amount of fillers would be required for the tive Commons Attribution 4.0 International License (http://creat iveco cement preparation, which reduces the manufacturing costs mmons.or g/licenses/b y/4.0/), which permits unrestricted use, distribu- and fabricating substances in many industrial applications. tion, and reproduction in any medium, provided you give appropriate However, there have not been any studies so far reporting the credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. application of NGFs in the oil well cementing and, hence, 1 3 Journal of Petroleum Exploration and Production Technology decrease the pollution of receptive environment. 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Published: May 31, 2018
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