Zeolite-Enhanced Portland Cement: Solution for Durable Wellbore-Sealing Materials
<p>The various possible leakage pathways that could be observed in a wellbore cement plug due to the challenging P&A conditions [<a href="#B9-materials-16-00030" class="html-bibr">9</a>].</p> "> Figure 2
<p>Challenges in usage of cement for subsurface conditions, additives and the aims of P&A.</p> "> Figure 3
<p>Raman results for polished cores of neat Class-H cement: (<b>a</b>) optical micrograph of polished cement core; (<b>b</b>) large-area profilometry scan of the cement; (<b>c</b>) phase peaks at 600–630 nm (C-S-H), 740 nm (C<sub>3</sub>A), 842 nm and 972 nm (C<sub>2</sub>S) were observed.</p> "> Figure 4
<p>Raman results for polished cores of 5% ferrierite-added Class-H cement: (<b>a</b>) optical micrograph of polished cement core; (<b>b</b>) large-area profilometry scan of the cement; (<b>c</b>) phase peak at 416 nm (ferrierite (Fer)). C-S-H, C<sub>3</sub>A and C<sub>2</sub>S are the same as those mentioned in the plot for neat Class-H cement.</p> "> Figure 5
<p>Raman results for polished cores of 15% ferrierite-added Class-H cement: (<b>a</b>) optical micrograph of polished cement core; (<b>b</b>) large-area profilometry scan of the cement; (<b>c</b>) phase peaks identical to those observed in <a href="#materials-16-00030-f003" class="html-fig">Figure 3</a> for ferrierite, C-S-H, C<sub>3</sub>A and C<sub>2</sub>S.</p> "> Figure 6
<p>Raman results for polished cores of 30% ferrierite-added Class-H cement: (<b>a</b>) optical micrograph of polished cement core; (<b>b</b>) large-area profilometry scan of the cement; (<b>c</b>) phase peaks for ferrierite, C-S-H and C<sub>2</sub>S are observed in this plot. However, C<sub>3</sub>A was not resolved well in these scans.</p> "> Figure 7
<p>XRF results showing the percentage distribution of various oxides present in unhydrated (<b>a</b>) commercial zeolite cement and (<b>b</b>) plain Class-H cement; (<b>c</b>) XRF data plot for ferrierite, which is a zeolite. The similarity in phases and or oxide compositions indicates that there are no new/intermediary phases that are formed. However, the addition of zeolite reduces the CaO content, which would eventually result in the more brittle phases of cement with hydration.</p> "> Figure 8
<p>CT scans of cement cores after failure under triaxial testing at a confining pressure of 13.7 MPa and 90 °C: (<b>a</b>) neat Class-H cement showing the failure in comparison to the others; (<b>b</b>) 5% ferrierite-added cement; (<b>c</b>) 15% ferrierite-added cement; (<b>d</b>) 30% ferrierite-added cement.</p> "> Figure 9
<p>Indentation results for polished cores of neat cement with 25 indents, represented as maps of hardness (avg. of 0.506 GPa) and elastic modulus (avg. of 15.72 GPa).</p> "> Figure 10
<p>Indentation results for polished cores of 5% ferrierite-added Class-H cement with 25 indents, represented as maps of hardness (avg. of 0.394 GPa) and elastic modulus (avg. of 14.03 GPa).</p> "> Figure 11
<p>Indentation results for polished cores of 15% ferrierite-added Class-H cement with 25 indents, represented as maps of hardness (avg. of 0.319 GPa) and elastic modulus (avg. of 11.01 GPa).</p> "> Figure 12
<p>Indentation results for polished cores of 30% FER-added Class-H cement with 25 indents, represented as maps of hardness (avg. of 0.256 GPa) and elastic modulus (avg. of 7.88 GPa).</p> "> Figure 13
<p>An EDS map corresponding to an SEM image showing a single indent on neat cement. Indentation was conducted for the other formulations (for 5%, 15% and 30% ferrierite-added Class-H cement) as well, and SEM and EDS studies were undertaken to see if there is any noticeable surface chemical change upon failure.</p> "> Figure 14
<p>UCS versus indentation-derived hardness and elastic modulus for 5%, 15% and 30% ferrierite-added Class-H and neat Class-H cement, showing slightly similar trends. UCS is the highest for 5% ferrierite-added cement at 9934.3 psi compared to neat UCS at 7041.5 psi. Elastic modulus and hardness, on the other hand, are highest for neat Class-H with averages of 15.72 GPa (EM) and 47.82 (hardness) followed by the 5% ferrierite addition at 14.03 GPa (EM) and 37.3 (hardness). The hardness and elastic modulus decrease gradually with the increase in the percentage addition of ferrierite, which is a similar trend as that of UCS.</p> "> Figure 15
<p>Triaxial test results for 5%, 15% and 30% FER-added and neat Class-H cement at 13.7 MPa confining pressure and 90 °C; 5% FER-added cement has the highest axial stress at 68.8 MPa, followed by 62.9 MPa and 54.5 MPa for the 15% and 30% additions, respectively, whereas the neat Class-H cement sample has a maximum of 53.3 MPa. These results coincide with the UCS results showing a similar trend, with 5% having the best performance. The initial linear regime is shown in a magnified scale in the inset, and the slope of this initial linear regime is used to calculate Young’s modulus.</p> "> Figure 16
<p>Average porosity and permeability values of 5%, 15% and 30% FER-added and neat Class-H cement measured using Core Lab UltraPore 300 Porosimeter and Nan-Perm Permeameter. Although 30% ferrierite has the least porosity due to better hydration, the 5% ferrierite addition shows the best zonal isolation as it has the least permeability of 13.54 μD in comparison to neat Class-H cement (49.53 μD).</p> "> Figure 17
<p>Pore-throat radius as measured via mercury intrusion porosimetry, where the greatest pore-throat radius distribution is in the nano-range (0.025 μm), supporting the hypothesis that an increase in porosity is attributed to the nano-porosity introduced by the addition of ferrierite. Ferrierite is a zeolite mineral that is characterized by its crystalline structure with a porosity in the nano-range, and hence, it could also support the fact that the porous crystalline structure of the zeolite is preserved in the cement matrix even after hydration.</p> ">
Abstract
:1. Introduction
- Ferrierite-Mg ([Mg2(K,Na)2Ca0.5](Si29Al7)O72.18H2O);
- Ferrierite-Na ((Na,K)5(Si31Al5)O72.18H2O);
- Ferrierite-K ((K,Na)5(Si31Al5)O72.18H2O).
2. Experimental Methods and Material Characterizations
2.1. Materials and Methods
2.2. Cement Slurry Preparation
2.3. Raman Spectroscopy
2.4. X-ray Fluorescence (XRF)
2.5. X-ray Computed Tomography (CT)
2.6. Microindentation
2.7. Unconfined Compressive Strength (UCS)
- (1)
- The piston was loaded to be actuated under stress control until 50 psi was reached.
- (2)
- The piston was then switched to be under strain (position) control.
- (3)
- The sample was loaded at a constant rate until failure, and then unloaded.
2.8. Triaxial Tests at Elevated Temperature
2.9. Petrophysical Properties (Porosity and Permeability)
3. Results
3.1. Microstructural Characterisation
3.1.1. Chemical Characterization I (Raman Spectroscopy)
3.1.2. Chemical Characterization II (X-ray Fluorescence (XRF))
3.2. Three-Dimensional Internal Morphology Characterization (CT)
3.3. Micromechanical Characterization (Microindentation)
3.4. Mechanical Strength Characterisation
3.4.1. Mechanical Property Characterization I (Unconfined Compressive Strength (UCS))
3.4.2. Strength Property Characterization II (Triaxial Strength Testing)
3.5. Petrophysical Property Testing
4. Discussion
5. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
Abbreviations
API | American Petroleum Institute |
ASTM | American Society for Testing and Materials |
bwoc | By weight of cement |
CCS | Confined compressive strength |
C3A | Tricalcium aluminate |
C2S | Dicalcium silicate |
C3S | Tricalcium silicate |
C-S-H | Calcium silicate hydrate |
CT | Computed tomography |
EDS | Energy dispersive spectroscopy |
FER | Ferrierite cement |
HPHT | High-pressure and high-temperature |
MIP | Mercury intrusion porosimetry |
P&A | Plugging and abandonment |
SEM | Scanning electron microscopy |
UCS | Unconfined compressive strength |
XRD | X-ray diffraction |
XRF | X-ray fluorescence |
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Oxide Formula | Class-H Cement (%) | Commercial Geothermal Zeolite Cement (%) | Ferrierite (%) |
---|---|---|---|
Al2O3 | 1.47 | 6.47 | 8.16 |
SiO2 | 16.28 | 29.65 | 82.43 |
SO3 | 6.97 | 9.48 | n/a |
K2O | 0.53 | 1.81 | 6.05 |
CaO | 68.08 | 46.27 | 1.12 |
TiO2 | 0.23 | 0.52 | 0.13 |
MnO | 0.1 | 0.26 | 0.01 |
FeXOY | 5.93 | 5.31 | 1.81 |
ZnO | 0.14 | 0.06 | n/a |
SrO | 0.28 | 0.17 | 0.04 |
Materials Used | Neat Cement (Grams) | 5% FER (Grams) | 15% FER (Grams) | 30% FER (Grams) |
---|---|---|---|---|
Class-H cement | 557.80 | 537.17 | 500.17 | 453.34 |
Water | 214.03 | 208.33 | 198.11 | 185.17 |
Ferrierite | 0.00 | 26.86 | 75.03 | 136.00 |
D-Air 5000 | 1.40 | 1.34 | 1.25 | 1.13 |
CFR-3 | 1.67 | 1.61 | 1.50 | 1.36 |
Bentonite | 11.16 | 10.74 | 10.00 | 9.07 |
Sample | Indentation | Triaxial | UCS | ||
---|---|---|---|---|---|
Hardness (GPa) | Elastic (Young’s) Modulus (GPa) | Peak Axial Stress (MPa) | Elastic (Young’s) Modulus (GPa) | Compressive Strength (MPa) | |
Neat (0% Fer) | 0.506 | 15.72 | 53.30 | 9.65 | 48.55 |
5% Fer | 0.394 | 14.03 | 61.13 | 8.82 | 68.49 |
15% Fer | 0.319 | 11.01 | 62.97 | 7.72 | 45.86 |
30% Fer | 0.256 | 7.88 | 54.77 | 11.29 | 43.57 |
Sample Design | UCS | Porosity | Permeability |
---|---|---|---|
Compressive Strength (MPa) | Percentage (%) | Micro-Darcy (μD) | |
Neat (0% Fer) | 48.55 | 28.82 | 49.53 |
5% Fer | 68.49 | 29.75 | 13.54 |
15% Fer | 45.86 | 30.29 | 57.25 |
30% Fer | 43.57 | 24.62 | 22.58 |
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Vissa, S.V.K.; Massion, C.; Lu, Y.; Bunger, A.; Radonjic, M. Zeolite-Enhanced Portland Cement: Solution for Durable Wellbore-Sealing Materials. Materials 2023, 16, 30. https://doi.org/10.3390/ma16010030
Vissa SVK, Massion C, Lu Y, Bunger A, Radonjic M. Zeolite-Enhanced Portland Cement: Solution for Durable Wellbore-Sealing Materials. Materials. 2023; 16(1):30. https://doi.org/10.3390/ma16010030
Chicago/Turabian StyleVissa, Sai Vamsi Krishna, Cody Massion, Yunxing Lu, Andrew Bunger, and Mileva Radonjic. 2023. "Zeolite-Enhanced Portland Cement: Solution for Durable Wellbore-Sealing Materials" Materials 16, no. 1: 30. https://doi.org/10.3390/ma16010030