Exploratory Analysis of a Green Resin with Carbon Nanotubes for Chemical Sand Consolidation

Abstract:

This study investigates the feasibility of a nano-reinforced green resin derived from Almaciga tree (Agathis philippinensis) exudates as an adhesive for sand consolidation in petroleum applications. While green resins often lack mechanical strength, nanoparticle reinforcement with carbon nanotubes has shown promise in enhancing binding properties. This research seeks to investigate how curing time, temperature, dosage, and nanoparticle concentration influence the performance of Almaciga resin as a binder. By investigating these factors, the study aims to provide a foundation for advancing the understanding and application of this sustainable adhesive. The chemical composition of the resin was analyzed using Gas chromatography to confirm the presence of compounds with adhesive properties with solubility tested through insoluble solids mass-ratio method. The green resin was then formulated using multi-walled Carbon Nanotubes (CNT) as fillers dispersed within a matrix of Almaciga resin dissolved in 95% ethanol using solution processing with zeta potential measured using a Malvern Zetasizer to test whether the nanoparticle reinforced formulations can hold a stable dispersion. Sand consolidation tests were done by mixing the formulations with loose sand and placed in 1” x 2" PVC molds using different dosage, curing times, and temperatures. Results show that the resin contains adhesive compounds such as limonene, beta-pinene, pimaric acid, and palustric acid, and resin solubility in 95% ethanol was 93.5%. The zeta potential ranged from -1.66 to 3.56 mV, showing the tendency of the CNT to agglomerate and settle out of the suspension. The results demonstrate that the resin can effectively consolidate samples using a minimum of 14 mL with a curing duration of 48 hours at 30 °C or 7 hours at 90 °C. Logistic regression revealed curing time, dosage, and temperature as key predictors of consolidation success, while CNT concentration demonstrated no statistical significance within the tested range, highlighting the need for further investigation. It is recommended that future research focus on optimizing curing parameters and leveraging uniaxial compressive strength testing to refine the role of CNT concentration. With these findings, this study established a foundation for advancing Almaciga resin as a sustainable adhesive for enhanced sand consolidation outcomes.

• Periodical: Advanced Materials Research (Volume 1184)
• Pages: 101-114
• DOI: https://doi.org/10.4028/p-RiMqh0
• Online since: November 2025
• Authors: Jayson D. Santos*, Ismail Mohd Saaid, Manuel Jr. L. Cabiguen, Lexyber C. Manalo
• Keywords: Green Adhesives, Nanocomposites, Nanotubes, Natural Resins, Sand Consolidation

References

[1] Nejati, H., et al., (2023) Synthesis and optimization of a Novel epoxy-based nanofluid for sand consolidation in oil wells. Geoenergy Science and Engineering, 230: p.212217.

DOI: 10.1016/j.geoen.2023.212217

[2] Kravchenko, O., D. Veligotskyi, and U. Agaev. (2023) Improving the Technology of Complex Hydrogen Thermobarochemical Treatment CHTBCE for Effective Use in Oil Wells With Weakly Consolidated Sandy Reservoirs. in SPE Caspian Technical Conference and Exhibition.

DOI: 10.2118/217608-ms

[3] Saghandali, F., M. Baghban Salehi, and V. Taghikhani, (2023) Design and fabrication of a Preformed Thixotropic-Viscoelastic Nanocomposite hydrogel system (PNCH) for controlling sand production in reservoirs. Results in Engineering. 18: p.101089.

DOI: 10.1016/j.rineng.2023.101089

[4] Tabar, M.A., et al., (2021) A comprehensive research in chemical consolidator/stabilizer agents on sand production control. Journal of Petroleum Exploration and Production Technology. 11(12): pp.4305-4324.

DOI: 10.1007/s13202-021-01303-1

[5] Tabbakhzadeh, M.N., et al., (2020) Experimental study of chemical sand consolidation using epoxy and furan resins for oil wells: Experimental design models. International Journal of Rock Mechanics and Mining Sciences. 135: p.104486.

DOI: 10.1016/j.ijrmms.2020.104486

[6] Alakbari, F.S., et al., (2020) Chemical Sand Consolidation: From Polymers to Nanoparticles. Polymers. 12(5): p.30.

[7] Fink, J.K., 3 - Epoxy Resins, in Reactive Polymers: Fundamentals and Applications (Third Edition), J.K. Fink, Editor. 2018, William Andrew Publishing. pp.139-223.

DOI: 10.1016/b978-0-12-814509-8.00003-8

[8] Fink, J.K., 4 - Phenol/Formaldehyde Resins, in Reactive Polymers: Fundamentals and Applications (Third Edition), J.K. Fink, Editor. 2018, William Andrew Publishing. pp.225-253.

DOI: 10.1016/b978-0-12-814509-8.00004-x

[9] Fink, J.K., 7 - Furan Resins, in Reactive Polymers: Fundamentals and Applications (Third Edition), J.K. Fink, Editor. 2018, William Andrew Publishing. pp.287-301.

DOI: 10.1016/b978-0-12-814509-8.00007-5

[10] Andersen, M.E., et al., Considerations for refining the risk assessment process for formaldehyde: Results from an interdisciplinary workshop. Regulatory Toxicology and Pharmacology, 2019. 106: pp.210-223.

DOI: 10.1016/j.yrtph.2019.04.015

[11] Schroeter, J.D., et al., Effects of Endogenous Formaldehyde in Nasal Tissues on Inhaled Formaldehyde Dosimetry Predictions in the Rat, Monkey, and Human Nasal Passages. Toxicological Sciences, 2014. 138(2): pp.412-424.

DOI: 10.1093/toxsci/kft333

[12] Swenberg, J.A., et al., Formaldehyde Carcinogenicity Research:30 Years and Counting for Mode of Action, Epidemiology, and Cancer Risk Assessment. Toxicologic Pathology, 2013. 41(2): pp.181-189.

DOI: 10.1177/0192623312466459

[13] Baroncini, E.A., et al., Recent advances in bio-based epoxy resins and bio-based epoxy curing agents. Journal of Applied Polymer Science, 2016. 133(45).

DOI: 10.1002/app.44103

[14] Taylor, T.J., et al., Emulsified furan resin-based glass fiber binding compositions, process of binding glass fibers, and glass fiber compositions. 2000, Johns Manville International

[15] Inc., Denver, CO; QO Chemicals, Inc. West Lafayette, IN: USA.

[16] Smith, R.M., R.A. Marty, and C.F. Peters, The diterpene acids in the bled resins of three pacific kauri, Agathis vitiensis, A. Lanceolata and A. Macrophylla. Phytochemistry, 1981. 20(9): pp.2205-2207.

DOI: 10.1016/0031-9422(81)80113-6

[17] Ametek, Haveg 4800 Phenolic Resin Material Safety Data Sheet. 2001: Chemical Products Division, Haveg Site, 900 Greenbank Road, Wilmington, Delaware 19808.

[18] Ehtemam, J.C., Material Safety Data Sheet, in Urea-Formaldehyde Concentrate, UFC 85. 2012: Tehran, Iran.

[19] Hexion, Urea Formaldehyde Resin - Casco-Resin(TM) CR-596 Safety Data Sheet, in Urea Formaldehyde Resin - Casco-Resin(TM) CR-596. 2015: Ohio, USA. p.15.

DOI: 10.1520/d4690-99

[20] Plenco, P.E.C., Phenol-formaldehyde resol molding compound Safety Data Sheet. 2017: 3518 Lakeshore Road, Sheboygan, WI 53083 USA.

[21] Halliburton, E.S., Furan Resin Mixture Material Safety Data Sheet. 2011: February 17, 2016. p.6.

[22] Razal, R.A., et al., Geographical variations and correlation among some chemical and thermal properties of Almaciga (Agathis philippinensis Warb.) resins from selected commercial sites in the Philippines. Heliyon, 2021. 7(3): p. e06413.

DOI: 10.1016/j.heliyon.2021.e06413

[23] Gonzales, E. and F. Abejo, Properties of Manila copal (almaciga) resin from 15 different localities in the Philippines. 1. Progress report. 1976.

[24] Ella, A. and A. Tongacan, Techniques in tapping almaciga [Agathis philippinensis Warb.] for sustained productivity of the tree: the Philippine experience. FPRDI Journal (Philippines), 1992.

[25] Lassak, E. and J. Brophy, The Steam-Volatile Oil of Commercial "Almaciga" Resin (Agathis philippinensis Warb.) from the Philippines. Journal of Essential Oil Bearing Plants, 2013. 11: pp.634-637.

DOI: 10.1080/0972060x.2008.10643679

[26] Schadler, L., S.a. Giannaris, and P. Ajayan, Load transfer in carbon nanotube epoxy composites. Applied physics letters, 1998. 73(26): pp.3842-3844.

DOI: 10.1063/1.122911

[27] Ella, A. and E. Domingo, Almaciga (Agathis philippinensis Warb.): Valuable but diminishing tree species in the Philippines pp.75-78. In: Heok-Choh, S., Hamid, S.A. and L. Mei (eds.), in Multinational and Transboundary Conservation of Valuable and Endangered Forest Tree Species, Asia and the Pacific Workshop International Union of Forest Research Organization, 30: 136pp. 2011.

[28] Ella, A., M. Santander, and C. Garcia, Almaciga [Agathis philippinensis Warb.] resin production in New Bataan, Compostella Valley Province [Philippines]. Journal on Tropical Forests and Natural Resources, 2009.

[29] Fernandez, E. and A. Duldulao. Physico-chemical properties of resin and essential oils of Almaciga (Agathis philippinensis). in 6. Asian Chemical Congress/11. Philippine Chemistry Congress/and 3. Asia-Pacific Food Analysis Network Conference. Manila (Philippines). 22-25 May 1995. 1995.

[30] Gonzales, E., C.C. Moredo Jr, and F.C. Moredo, Modified almaciga (Agathis philippinensis) resin for paint manufacture. FPRDI Journal (Philippines), 1991.

[31] Gonzales, L.L. and V.C.d.l. Cruz, Almaciga resin: sticky dollars. Canopy Forest Research Institute, 1980. 6(4): p.1, 14.

[32] Guerrero, M., R. Razal, and M. Ramnath, Non-Timber Forest Products for Food Security, Income Generation and Conservation in Asia. 2015.

[33] De Leon, L. and A. Sagcal, Processing and utilization of almaciga (Agathis philippinensis) resin as a plywood adhesive. 1994.

[34] Patricio, J., Formulation and evaluation of almaciga (Agathis philippinensis Warb.) resin as component in phenol formaldehyde adhesive for plywood. 1996.

[35] Gojny, F.H., et al., Carbon nanotube-reinforced epoxy-composites: enhanced stiffness and fracture toughness at low nanotube content. Composites Science and Technology, 2004. 64(15): pp.2363-2371.

DOI: 10.1016/j.compscitech.2004.04.002

[36] Zhu, J., et al., Improving the Dispersion and Integration of Single-Walled Carbon Nanotubes in Epoxy Composites through Functionalization. Nano Letters - NANO LETT, 2003. 3.

DOI: 10.1021/nl0342489

[37] Song, Y.S. and J.R. Youn, Influence of dispersion states of carbon nanotubes on physical properties of epoxy nanocomposites. Carbon, 2005. 43(7): pp.1378-1385.

DOI: 10.1016/j.carbon.2005.01.007

[38] Thostenson, E.T., Z. Ren, and T.-W. Chou, Advances in the science and technology of carbon nanotubes and their composites: a review. Composites Science and Technology, 2001. 61(13): pp.1899-1912.

DOI: 10.1016/s0266-3538(01)00094-x

[39] Coleman, J.N., et al., Small but strong: A review of the mechanical properties of carbon nanotube–polymer composites. Carbon, 2006. 44(9): pp.1624-1652.

DOI: 10.1016/j.carbon.2006.02.038

[40] Spitalsky, Z., et al., Carbon nanotube–polymer composites: Chemistry, processing, mechanical and electrical properties. Progress in Polymer Science, 2010. 35(3): pp.357-401.

DOI: 10.1016/j.progpolymsci.2009.09.003

[41] Qian, D., et al. (2000). "Load transfer and deformation mechanisms in carbon nanotube-polystyrene composites." Applied physics letters 76(20): 2868-2870.

DOI: 10.1063/1.126500

[42] Mishra, S. and K. Ojha, Chemical Sand Consolidation: An Overview. Journal of Petroleum Engineering and Technology, 2015. 5: pp.21-34.

[43] Nguyen, P.D., et al., Stabilizing Wellbores in Unconsolidated, Clay-Laden Formations, in SPE International Symposium and Exhibition on Formation Damage Control. 2004, Society of Petroleum Engineers: Lafayette, Louisiana. p.16.

DOI: 10.2523/86559-ms

[44] Shang, X., et al., A novel chemical-consolidation sand control composition: Foam amino resin system. e-Polymers, 2019. 19: pp.1-8.

DOI: 10.1515/epoly-2019-0001

[45] Carbas, R. J. C., et al. (2019). "The Mechanical Response of a Structural Epoxy Adhesive Reinforced with Carbon Black Nanoparticles." Microscopy and Microanalysis 25(1): 187-191.

DOI: 10.1017/s1431927618015106

[46] Abbasi, Z., et al. (2021). "Designing of high-performance epoxy adhesive with recycled polymers and silica nano particles (SNPs) in epoxy/carbon fiber composite-steel bonded joints: Mechanical properties, thermal stability and toughening mechanisms." Journal of the Taiwan Institute of Chemical Engineers 123: 310-327.

DOI: 10.1016/j.jtice.2021.05.016

[47] Khoramishad, H., et al. (2018). "Effect of multi-walled carbon nanotubes and silicon carbide nanoparticles on the deleterious influence of water absorption in adhesively bonded joints." Journal of Adhesion Science and Technology 32(16): 1795-1808.

DOI: 10.1080/01694243.2018.1447295

[48] Cakir, M. V., et al. (2021). "Graphene nanoparticle effect on flexural and shear behaviors of adhesively bonded single lap joints of GFRP composites." Journal of the Brazilian Society of Mechanical Sciences and Engineering 43(4): 11.

DOI: 10.1007/s40430-021-02920-x

[49] De Luca, P., et al., Preparation and Optimization of Natural Glues Based on Laricio Pine Resin. IOP Conference Series: Materials Science and Engineering, 2018. 374: p.012071.

DOI: 10.1088/1757-899x/374/1/012071

[50] Mishra, S. and K. Ojha, Application of an improvised inorganic–organic chemical mixture to consolidate loose sand formations in oil fields. Journal of Petroleum Science and Engineering, 2016. 137: pp.1-9.

DOI: 10.1016/j.petrol.2015.11.008

[51] Talaghat, M.r. and A.R. Bahmani. Sand Production Control in Sandstone Reservoirs Using a Modified Urea-formaldehyde Re. 2017.