Atomic-Level Insights into Epoxy-Modified Nanofiller Adsorption and Wetting on Calcium Silicate Hydrates: Principles for Optimizing Interfacial Properties

Cheikh Makhfouss Fame; Tamon Ueda; Marc A. Ntjam Minkeng; Eskinder D. Shumuye; Yi Wang; Chao Wu

doi:10.1016/j.eng.2025.12.032

Engineering ›› :202512032 DOI: 10.1016/j.eng.2025.12.032

Research

research-article

Atomic-Level Insights into Epoxy-Modified Nanofiller Adsorption and Wetting on Calcium Silicate Hydrates: Principles for Optimizing Interfacial Properties

Author information +

History +

PDF

Abstract

Cementitious composites are ubiquitous in infrastructure, but their durability is often limited by interfacial weaknesses, particularly when bonded to epoxy polymers. These organic-inorganic interfaces are critical in applications such as fiber-reinforced polymer repair, strengthening, and additive concrete manufacturing. However, debonding and cracking at the epoxy-calcium-silicate-hydrate (CSH) interface under conditions such as elevated temperature, moisture, or fatigue-loading remain long-standing challenges. A fundamental understanding of the atomic-level interactions governing macroscopic interfacial properties is essential to optimize the performance of these composites; however, these remain largely unexplored by conventional analytical techniques owing to the buried nature of the nanoscale epoxy-CSH interface. In this study, we employed classical molecular dynamics (MD) simulations to elucidate the molecular mechanisms associated with epoxy-modifier-incorporated (nanofillers-incorporated) epoxy prepolymer (i.e., liquid epoxy) adsorption, wetting, and adhesion to CSH surfaces. We investigated three epoxy systems: epoxy prepolymer, acrylamide-modified (AM-modified) epoxy prepolymer, and nanosilica-reinforced (nano-SiO₂-reinforced) epoxy prepolymer, with their pre-curing interactions with CSH simulated for the first time. Key interfacial parameters, including interphase formation, wetting ratio, atomic-density profile, monomer-concentration profile, interfacial ionic and hydrogen bonding, interaction energy, and work of adhesion, were rigorously analyzed. Our MD simulations revealed that the diethyltoluenediamine (DETDA) epoxy hardener preferentially adsorbs over bisphenol F diglycidyl ether (DGEBF) resin on the CSH surface, leading to a hardener-rich interphase. Both resin and hardener components were found to concentrate within approximately 5 Å of the CSH surface and exhibit molar ratios significantly higher than that of the bulk, suggestive of a potentially stiffer interphase. The incorporation of AM was found to significantly enhance interfacial adhesion and improve adsorption and wetting through strong electrostatic and hydrogen bonding, resulting in a 16.43% increase in the work of adhesion compared to neat epoxy. The nanosilica filler, while improving interfacial interactions, aggregated and yielded a modest enhancement of 4.45% in the work of adhesion. These findings provide fundamental and novel molecular-level insights for the rational design of epoxy-modified cementitious composites with enhanced interfacial-bonding, durability, and mechanical properties. This study underscores the critical role played by nanofiller selection in tailoring interfacial properties and offers valuable guidelines for material formulations that optimize the interphase region in high-performance polymer-cement hybrid materials.

Keywords

Acrylamide and nanosilica fillers / Calcium silicate hydrate (CSH) / Concrete / Epoxy / Durability / Interfacial strength / Molecular dynamics simulations

Cite this article

Download citation ▾

Cheikh Makhfouss Fame, Tamon Ueda, Marc A. Ntjam Minkeng, Eskinder D. Shumuye, Yi Wang, Chao Wu. Atomic-Level Insights into Epoxy-Modified Nanofiller Adsorption and Wetting on Calcium Silicate Hydrates: Principles for Optimizing Interfacial Properties. Engineering 202512032 DOI:10.1016/j.eng.2025.12.032

登录浏览全文

4963

注册一个新账户忘记密码

References

Publishing order | Descend order by publishing year | Descend order by cited within

[1]	Ueda T, Shimomura T, Matthews SL. Conservation and intervention in MC2020. Struct Concr 2023; 24(4):4464-75.

[2]	Scrivener KL, John VM, Gartner EM. Eco-efficient cements: potential economically viable solutions for a low-CO₂ cement-based materials industry. Cem Concr Res 2018;114:2-26.

[3]	Bazli M, Heitzmann M, Hernandez BV. Hybrid fibre reinforced polymer and seawater sea sand concrete structures: a systematic review on short-term and long-term structural performance. Constr Build Mater 2021;301:124335.

[4]	Scrivener KL, Kirkpatrick RJ. Innovation in use and research on cementitious material. Cem Concr Res 2008; 38(2):128-36.

[5]	Li K, Ueda T. Durability-based design: Asian perspectives. Sustain Resilient Infrastruct 2023; 8(2):158-68.

[6]	Ueda T. Material mechanical properties necessary for the structural intervention of concrete structures. Engineering 2019; 5(6):1131-8.

[7]	Brandtner-Hafner M. Evaluating the bonding effectiveness of CFRP patches in strengthening concrete structures. Constr Build Mater 2024;436:136966.

[8]	Lv L, Guo P, Liu G, Han N, Xing F. Light induced self-healing in concrete using novel cementitious capsules containing UV curable adhesive. Cem Concr Compos 2020;105:103445.

[9]	Wang X, Chen J, Liu Y, Sheng M, Long W, Luo Q, et al. Experimental study on bending fatigue properties of microcapsule self-healing cementitious composites. J Build Eng 2025;101:111873.

[10]	Daneshvar D, Behnood A, Robisson A. Interfacial bond in concrete-to-concrete composites: a review. Constr Build Mater 2022;359:129195.

[11]	Daneshvar D, Deix K, Robisson A. Effect of casting and curing temperature on the interfacial bond strength of epoxy bonded concretes. Constr Build Mater 2021;307:124328.

[12]	Portela GM, Pacheco F, Ehrenbring HZ, Christ R, Tutikian B, Mancio M. Effects of different coatings on concrete elements due to chloride ion penetration. Coatings 2025; 15(1):46.

[13]	Hosseini E, Zakertabrizi M, Habibnejad Korayem A, Zaker Z, Shahsavari R. Orbital overlapping through induction bonding overcomes the intrinsic delamination of 3D-printed cementitious binders. ACS Nano 2020; 14(8):9466-77.

[14]	Morsch S, Wand CR, Gibbon S, Irwin M, Siperstein F, Lyon S. The effect of cross-linker structure on interfacial interactions, polymer dynamics and network composition in an epoxy-amine resin. Appl Surf Sci 2023;609:155380.

[15]	Djouani F, Connan C, Delamar M, Chehimi MM, Benzarti K. Cement paste-epoxy adhesive interactions. Constr Build Mater 2011; 25(2):411-23.

[16]	Djouani F, Connan C, Chehimi MM, Benzarti K. Interfacial chemistry of epoxy adhesives on hydrated cement paste. Surf Interface Anal 2008; 40(3-4):146-50.

[17]	Palmese GR, McCullough RL, Sottos NR. Relationship between interphase composition, material properties, and residual thermal stresses in composite materials. J Adhes 1995; 52(1):101-13.

[18]	Starostina IA, Nguyen DA, Burdova EV, Stoyanov OV. Adhesion of polymers: new approaches to determination of surface properties of metals. Polym Sci Ser D Glues Sealing Mater 2013; 6(1):1-4.

[19]	Morsch S, Liu Y, Malanin M, Formanek P, Eichhorn KJ. Exploring whether a buried nanoscale interphase exists within epoxy-amine coatings: implications for adhesion, fracture toughness, and corrosion resistance. ACS Appl Nano Mater 2019; 2(4):2494-502.

[20]	Salgin B, Özkanat Ö, Mol JMC, Terryn H, Rohwerder M. Role of surface oxide properties on the aluminum/epoxy interfacial bonding. J Phys Chem C Nanomater Interfaces 2013; 117(9):4480-7.

[21]	Taheri P, Terryn H, Mol JMC. An in situ study of amine and amide molecular interaction on Fe surfaces. Appl Surf Sci 2015;354:242-9.

[22]	Büyüköztürk O, Buehler MJ, Lau D, Tuakta C. Structural solution using molecular dynamics: fundamentals and a case study of epoxy-silica interface. Int J Solids Struct 2011; 48(14-15):2131-40.

[23]	Lau D, Jian W, Yu Z, Hui D. Nano-engineering of construction materials using molecular dynamics simulations: prospects and challenges. Compos Part B Eng 2018;143:282-91.

[24]	Hou D, Yang Q, Wang P, Jin Z, Wang M, Zhang Y, et al. Unraveling disadhesion mechanism of epoxy/CSH interface under aggressive conditions. Cem Concr Res 2021;146:106489.

[25]	Hue KY, Lew JH, Matar OK, Luckham PF, Müller EA. Parametric studies of polyacrylamide adsorption on calcite using molecular dynamics simulation. Molecules 2025; 30(2):285.

[26]	Jang C, Lacy TE, Gwaltney SR, Toghiani H, Pittman Jr CU. Interfacial shear strength of cured vinyl ester resin-graphite nanoplatelet from molecular dynamics simulations. Polymer 2013; 54(13):3282-9.

[27]	Nouranian S, Jang C, Lacy TE, Gwaltney SR, Toghiani H, Pittman Jr CU. Molecular dynamics simulations of vinyl ester resin monomer interactions with a pristine vapor-grown carbon nanofiber and their implications for composite interphase formation. Carbon 2011; 49(10):3219-32.

[28]	Jiao W, Liu W, Yang F, Jiang L, Jiao W, Wang R. Improving the interfacial strength of carbon fiber/vinyl ester resin composite by self-migration of acrylamide: a molecular dynamics simulation. Appl Surf Sci 2018;454:74-81.

[29]	Morsch S, Liu Y, Harris K, Siperstein FR, Di Lullo C, Visser P, et al. Probing the nanostructure and reactivity of epoxy-amine interphases. ACS Appl Mater Interfaces 2024; 16(50):70097-107.

[30]	Hou D, Yu J, Liu Q, Dong B, Wang X, Wang P, et al. Nanoscale insight on the epoxy-cement interface in salt solution: a molecular dynamics study. Appl Surf Sci 2020;509:145322.

[31]	Luo Q, Xie Y, Nie Q, Yang Q, Zhang X. Impact of pore sizes and defects on C-S-H/epoxy bonding in wet conditions: a molecular dynamics analysis. Next Mater 2024;5:100253.

[32]	Bahraq AA, Al-Osta MA, Al-Amoudi OSB, Saleh TA, Obot IB. Atomistic simulation of polymer-cement interactions: progress and research challenges. Constr Build Mater 2022;327:126881.

[33]	Thompson AP, Aktulga HM, Berger R, Bolintineanu DS, Brown WM, Crozier PS, et al. LAMMPS—a flexible simulation tool for particle-based materials modeling at the atomic, meso, and continuum scales. Comput Phys Commun 2022;271:108171.

[34]	Humphrey W, Dalke A, Schulten K. VMD: visual molecular dynamics. J Mol Graph 1996; 14(1):33-8.

[35]	Stukowski A. Visualization and analysis of atomistic simulation data with OVITO—the open visualization tool. Model Simul Mater Sci Eng 2010; 18(1):015012.

[36]	Pellenq RJM, Kushima A, Shahsavari R, van Vliet KJ, Buehler MJ, Yip S, et al. A realistic molecular model of cement hydrates. Proc Natl Acad Sci USA 2009; 106(38):16102-7.

[37]	Hou D, Ma H, Zhu Y, Li Z. Calcium silicate hydrate from dry to saturated state: structure, dynamics and mechanical properties. Acta Mater 2014;67:81-94.

[38]	Abdolhosseini Qomi MJ, Krakowiak KJ, Bauchy M, Stewart KL, Shahsavari R, Jagannathan D, et al. Combinatorial molecular optimization of cement hydrates. Nat Commun 2014; 5(1):4960.

[39]	Murray SJ, Subramani VJ, Selvam RP, Hall KD. Molecular dynamics to understand the mechanical behavior of cement paste. Transp Res Rec 2010; 2142(1):75-82.

[40]	Selvam RP, Subramani VJ, Murray S, Hall K. Potential application of nanotechnology on cement based materials. Report. Fayetteville: Mack Blackwell Rural Transportation Center (MBTC); 2009.

[41]	Chen JJ, Thomas JJ, Taylor HFW, Jennings HM. Solubility and structure of calcium silicate hydrate. Cem Concr Res 2004; 34(9):1499-519.

[42]	Bahraq AA, Al-Osta MA, Baghabra Al-Amoudi OS, Obot IB, Adesina AY, Maslehuddin M. A nanoscale adhesion mechanism of cement-epoxy interface under varying moisture conditions: a molecular dynamics study. Surf Interfaces 2022;35:102446.

[43]	Hou D, Lu Z, Li X, Ma H, Li Z. Reactive molecular dynamics and experimental study of graphene-cement composites: structure, dynamics and reinforcement mechanisms. Carbon 2017;115:188-208.

[44]	Amornsakchai T, Doaddara O. Grafting of acrylamide and acrylic acid onto polyethylene fiber for improved adhesion to epoxy resin. J Reinf Plast Compos 2008; 27(7):671-82.

[45]	Sprenger S. Nanosilica-toughened epoxy resins. Polymers 2020; 12(8):1777.

[46]	Sprenger S. Improving mechanical properties of fiber-reinforced composites based on epoxy resins containing industrial surface-modified silica nanoparticles: review and outlook. J Compos Mater 2015; 49(1):53-63.

[47]	Karnati SR, Agbo P, Zhang L. Applications of silica nanoparticles in glass/carbon fiber-reinforced epoxy nanocomposite. Compos Commun 2020;17:32-41.

[48]	Odegard GM, Patil SU, Deshpande PP, Kanhaiya K, Winetrout JJ, Heinz H, et al. Molecular dynamics modeling of epoxy resins using the reactive interface force field. Macromolecules 2021; 54(21):9815-24.

[49]	Saraç I, Adin H, Temiz Sş. Investigation of the effect of use of nano-Al₂O₃, nano-TiO₂ and nano-SiO₂ powders on strength of single lap joints bonded with epoxy adhesive. Compos Part B Eng 2019;166:472-82.

[50]	Alhabill FN, Ayoob R, Andritsch T, Vaughan AS. Influence of filler/matrix interactions on resin/hardener stoichiometry, molecular dynamics, and particle dispersion of silicon nitride/epoxy nanocomposites. J Mater Sci 2018; 53(6):4144-58.

[51]	Fame CM, Ueda T, Ntjam Minkeng MA, Wu C. Durability of epoxy and vinyl ester polymers in wet, seawater, and seawater sea sand concrete environments: molecular dynamics simulations. Constr Build Mater 2024;451:138645.

[52]	Heinz H, Lin TJ, Kishore Mishra R, Emami FS. Thermodynamically consistent force fields for the assembly of inorganic, organic, and biological nanostructures: the INTERFACE force field. Langmuir 2013; 29(6):1754-65.

[53]	Heinz O, Heinz H. Cement interfaces: current understanding, challenges, and opportunities. Langmuir 2021; 37(21):6347-56.

[54]	Javadi A, Jamil T, Abouzari-Lotf E, Soucek MD, Heinz H. Working mechanisms and design principles of comb-like polycarboxylate ether superplasticizers in cement hydration: quantitative insights for a series of well-defined copolymers. ACS Sustain Chem & Eng 2021; 9(25):8354-71.

[55]	Mishra RK, Mohamed AK, Geissbühler D, Manzano H, Jamil T, Shahsavari R, et al.A force field database for cementitious materials including validations, applications and opportunities. Cem Concr Res2017;102:68-89.

[56]	Computer VL. “experiments” on classical fluids. I. Thermodynamical properties of Lennard-Jones molecules. Phys Rev 1967; 159(1):98-103.

[57]	Nosé S. A molecular dynamics method for simulations in the canonical ensemble. Mol Phys 1984; 52(2):255-68.

[58]	Mishra RK, Darouich S, in’t Veld PJ, Flatt RJ, Heinz H.. Understanding hydration reactions, mechanical properties, thermal expansion, and organic interfacial interactions of calcium sulfate hydrates from the atomic scale. Cem Concr Res 2025;189:107740.

[59]	Israelachvili JN. Intermolecular and surface forces. 3rd ed. San Diego: Academic Press; 2011.

[60]	Jamil T, Javadi A, Heinz H. Mechanism of molecular interaction of acrylate-polyethylene glycol acrylate copolymers with calcium silicate hydrate surfaces. Green Chem 2020; 22(5):1577-93.

[61]	Wang S, Yan X, Chang B, Liu S, Shao L, Zhang W, et al. Atomistic modeling of the effect of temperature on interfacial properties of 3D-printed continuous carbon fiber-reinforced polyamide 6 composite: from processing to loading. ACS Appl Mater Interfaces 2023; 15(48):56454-63.

[62]	Giorgino T. Computing 1-D atomic densities in macromolecular simulations: the density profile tool for VMD. Comput Phys Commun 2014; 185(1):317-322.

[63]	Wei T, Xiao J, Cheng X, Gong P, Mei K, Hou Z, et al. Improving the mechanical properties of cement-based materials under high temperature: reducing the C₃S/C₂S ratio. Constr Build Mater 2024;421:135741.

[64]	Harris K, Wand CR, Visser P, Siperstein FR. Segregation in epoxy/amine systems on iron oxide surfaces. RSC Appl Interfaces 2024; 1(4):812-20.

[65]	Benzarti K, Perruchot C, Chehimi MM. Surface energetics of cementitious materials and their wettability by an epoxy adhesive. Colloids Surf A Physicochem Eng Asp 2006; 286(1-3):78-91.

[66]	Kai MF, Ji WM, Dai JG. Atomistic insights into the debonding of epoxy-concrete interface with water presence. Eng Fract Mech 2022;271:108668.

[67]	Hue KY, Lew JH, Myo Thant MM, Matar OK, Luckham PF, Müller EA. Molecular dynamics simulation of polyacrylamide adsorption on calcite. Molecules 2023; 28(17):6367.

[68]	Yoshizawa K, Semoto T, Hitaoka S, Higuchi C, Shiota Y, Tanaka H. Synergy of electrostatic and van der Waals interactions in the adhesion of epoxy resin with carbon-fiber and glass surfaces. Bull Chem Soc Jpn 2017; 90(5):500-5.

[69]	Kisin S, Bozˇovic´ Vukic´ J, van der Varst PGT, de With G, Koning CE. Estimating the polymer-metal work of adhesion from molecular dynamics simulations. Chem Mater 2007; 19(4):903-7.

[70]	Zhou S, Vu-Bac N, Arash B, Zhu H, Zhuang X. Interface characterization between polyethylene/ silica in engineered cementitious composites by molecular dynamics simulation. Molecules 2019; 24(8):1497.

[71]	Nikkhah SJ, Moghbeli MR, Hashemianzadeh SM. Dynamic study of deformation and adhesion of an amorphous polyethylene/graphene interface: a simulation study. Macromol Theory Simul 2016; 25(6):533-49.

[72]	Odagiri N, Shirasu K, Kawagoe Y, Kikugawa G, Oya Y, Kishimoto N, et al. Amine/epoxy stoichiometric ratio dependence of crosslinked structure and ductility in amine-cured epoxy thermosetting resins. J Appl Polym Sci 2021; 138(23):50542.

[73]	Jeyranpour F, Alahyarizadeh G, Arab B. Comparative investigation of thermal and mechanical properties of cross-linked epoxy polymers with different curing agents by molecular dynamics simulation. J Mol Graph Model 2015;62:157-64.

[74]	Guha RD, Idolor O, Grace L. An atomistic simulation study investigating the effect of varying network structure and polarity in a moisture contaminated epoxy network. Comput Mater Sci 2020;179:109683.

[75]	Li C, Strachan A. Molecular dynamics predictions of thermal and mechanical properties of thermoset polymer EPON862/DETDA. Polymer 2011; 52(13):2920-8.

[76]	Wu F, Zou H, Zhang Q, Zhang T, Yu J. Combining machine learning and molecular dynamics to predict strength-toughness and energy dissipation mechanisms of hybrid double-crosslinked CNT networks. Comput Mater Sci 2025;246:113403.

[77]	Fame CM, Ramôa Correia J, Ghafoori E, Wu C. Damage tolerance of adhesively bonded pultruded GFRP double-strap joints. Compos Struct 2021;263:113625.

[78]	Fame CM, Wu C, Feng P, Tam L. Numerical investigations on the damage tolerance of adhesively bonded pultruded GFRP joints with adhesion defects. Compos Struct 2022;301:116223.

[79]	Wu C, Zhao XL, Chiu WK, Al-Mahaidi R, Duan WH. Effect of fatigue loading on the bond behaviour between UHM CFRP plates and steel plates. Compos Part B Eng 2013;50:344-53.

[80]	Fame CM, He L, Tam L, Wu C. Fatigue damage tolerance of adhesively bonded pultruded GFRP double-strap joints with adhesion defects. J Compos Constr 2023; 27(1):04022100.

[81]	Li Q, Siddaramaiah KNH, Hui D, Lee JH. Effects of dual component microcapsules of resin and curing agent on the self-healing efficiency of epoxy. Compos Part B Eng 2013;55:79-85.

[82]	Dittanet P, Pearson RA. Effect of silica nanoparticle size on toughening mechanisms of filled epoxy. Polymer 2012; 53(9):1890-905.

[83]	Baller J, Becker N, Ziehmer M, Thomassey M, Zielinski B, Müller U, et al. Interactions between silica nanoparticles and an epoxy resin before and during network formation. Polymer 2009; 50(14):3211-9.

[84]	Zhou Y, Hou D, Manzano H, Orozco CA, Geng G, Monteiro PJM, et al. Interfacial connection mechanisms in calcium-silicate-hydrates/polymer nanocomposites: a molecular dynamics study. ACS Appl Mater Interfaces 2017; 9(46):41014-25.

[85]	Bahraq AA, Obot IB, Al-Osta MA, Baghabra Al-Amoudi OS, Maslehuddin M. Molecular-level investigation on the effect of surface moisture on the bonding behavior of cement-epoxy interface. J Build Eng 2022;61:105299.

[86]	Kim T, Kwon SH, Kim HJ, Lim CS, Chung I, Lee WK, et al. Effect of the surface modification of silica nanoparticles on the viscosity and mechanical properties of silica/epoxy nanocomposites. Compos Interfaces 2022; 29(13):1573-90.

[87]	Nakamura S, Tsuji Y, Yoshizawa K. Molecular dynamics study on the thermal aspects of the effect of water molecules at the adhesive interface on an adhesive structure. Langmuir 2021; 37(50):14724-32.