Self-assembled mesoporous silica nanotubes as low-dose reinforcing units for balanced mechanical, thermal and tribological performance of epoxy composites

Abstract

Epoxy resin (EP) has been widely utilized as a protective coating and structural composite; however, its high brittleness and low wear resistance limit its broader application. In this study, mesoporous silica nanotubes (MSNTs) were synthesized via a facile self-assembly route and incorporated into EP via solution mixing. The as-synthesized MSNTs exhibit a uniform tubular morphology and ordered mesoporous channels, disperse homogeneously within the EP matrix with strong interfacial adhesion, and effectively enhance the mechanical properties at low filler loading. By adding 1% MSNTs, the tensile strength, rupture elongation, elastic modulus, and fracture energy were remarkably improved by 26.2%, 16.8%, 5.3%, and 21.7%, respectively, relative to neat EP, whereas Shore D hardness increased monotonically with increasing filler content. MSNTs barely altered the thermal decomposition but gradually increased the char yield of EP. Dry-sliding tests demonstrated that incorporating 1% MSNTs yields a minimum wear rate of 1.56 × 10⁻⁵ mm³∙Nm^–1 for EP composites, showing an improvement of 62.4% in wear resistance. Finally, the underlying wear mechanism was systematically elucidated based on careful examination of the worn surfaces. This study provides a high-efficiency reinforcement strategy for polymer composites with low filler mass fractions by rationally designing the one-dimensional silica-based nanofillers.

Graphical abstract

Keywords

self-assembly / mesoporous silica nanotubes / epoxy resin, mechanical property / wear mechanism

References

[1] Luo T T , Ma Y T , Cui X Y . Review on frontal polymerization behavior for thermosetting resins: materials, modeling, and application. Polymers, 2024, 16(2): 185

[2] Rostami Aghouy S , Sabzi J , Esfahani M R . The effect of long-term and short-term loading on the flexural behavior of RC beams strengthened with the NSM method. Case Studies in Construction Materials, 2025, 22: e04191

[3] Xia H Y , Li J J , Wang K , Hou X G , Yang T , Hu J J , Shi Z Q . Superior wear resistance of epoxy composite with highly dispersed graphene spheres. Advanced Composites and Hybrid Materials, 2022, 5(1): 173–183

[4] Hou Y , Wan M , Qian X , Shi C , Pan Y-T , Shen J . Structural diversity of zeolitic imidazolate frameworks in thermoplastic polyurethane: integrated fire testing and hierarchical safety assessment. Polymer Testing, 2025, 151: 108941

[5] Hou Y , Wan M , Li J , Ren F , Qian X , Shi C . Improving combustion analysis of extruded polystyrene via custom isolation methodology. Fire, 2025, 8(2): 43

[6] Shi Y , Yu B , Zheng Y , Yang J , Duan Z , Hu Y . Design of reduced graphene oxide decorated with DOPO-phosphanomidate for enhanced fire safety of epoxy resin. Journal of Colloid and Interface Science, 2018, 521: 160–171

[7] Song L , Jiang T , Yu H , Zhou Y , Cao X , Wang P , Zhang B , Yu Z , Pan K , Wei S . Research progress on the tribological properties of epoxy-based solid-lubricating composites. Polymer Composites, 2024, 45(18): 16452–16466

[8] Kitichatpayak D , Makcharoen W , Vittayakorn N , Vittayakorn W . Influence of various nanofillers on mechanical and electrical properties of epoxy resin composites. Polymer-Plastics Technology and Materials, 2022, 61(16): 1826–1832

[9] Liao Y , Cao L , Li S , Lin Z , Li W , Yu C , Zhang P , Wang Q . Enhanced mechanical and tribological properties of epoxy-based coatings by in-situ synthesized silicon dioxide nanoparticles. Journal of Applied Polymer Science, 2022, 139(36): e52852

[10] Romanes M C , D'Souza N A , Coutinho D , Balkus K J , Scharf T W . Surface and subsurface characterization of epoxy-mesoporous silica composites to clarify tribological properties. Wear, 2008, 265(1): 88–96

[11] Kang Y , Chen X , Song S , Yu L , Zhang P . Friction and wear behavior of nanosilica-filled epoxy resin composite coatings. Applied Surface Science, 2012, 258(17): 6384–6390

[12] Tagliaro I , Cobani E , Carignani E , Conzatti L , D'Arienzo M , Giannini L , Martini F , Nardelli F , Scotti R , Stagnaro P . et al. The self-assembly of sepiolite and silica fillers for advanced rubber materials: the role of collaborative filler network. Applied Clay Science, 2022, 218: 106383

[13] Wang W , Zhou G , Yu B , Peng M . New reactive rigid-rod aminated aromatic polyamide for the simultaneous strengthening and toughening of epoxy resin and carbon fiber/epoxy composites. Composites Part B: Engineering, 2020, 197: 108044

[14] Uysal B Ö , Tepehan F Z . Determination of growth kinetics and size dependent structural, morphological, optical characteristics of sol-gel derived silica nanoparticles in silica matrix. Materials Science-Poland, 2019, 37(1): 16–24

[15] D’Angelo A , Mortalò C , Comune L , Raffaini G , Fiorentino M , Catauro M . Sol-gel synthesized silica/sodium alginate hybrids: comprehensive physico-chemical and biological characterization. Molecules, 2025, 30(17): 3481

[16] Ellerbrock R , Stein M , Schaller J . Comparing amorphous silica, short-range-ordered silicates, and silicic acid species by FTIR. Scientific Reports, 2022, 12: 11708

[17] Petreanu I , Niculescu V-C , Enache S , Iacob C , Teodorescu M . Structural characterization of silica and amino-silica nanoparticles by fourier transform infrared (FTIR) and raman spectroscopy. Analytical Letters, 2023, 56(2): 390–403

[18] Imoisili P E , Ukoba K O , Jen T-C . Green technology extraction and characterisation of silica nanoparticles from palm kernel shell ash via sol-gel. Journal of Materials Research and Technology, 2020, 9(1): 307–313

[19] Nakashima Y , Fukushima M , Hyuga H . Fiber template approach toward preparing one-dimensional silica nanostructure with rough surface. Advanced Powder Technology, 2021, 32(4): 1099–1105

[20] Cheng Y , Zhang Y , Jiang H , Dong X , Zheng J , Meng C . Synthesis of amorphous cobalt silicate nanobelts@manganese silicate core-shell structures as enhanced electrode for high-performance hybrid supercapacitors. Journal of Colloid and Interface Science, 2020, 561: 762–771

[21] Tharani D , Ananthasubramanian M . Influence of pre-treatment processes on the purity and characteristics of silica extracted from rice husk. Biomass Conversion and Biorefinery, 2024, 14(11): 12517–12529

[22] Xu J , Zhao J , Zhang N , Chen X , Ding X . Improved electrochemical performance of SBA-15 based SiO₂ anodes with N-doping porous carbon. Journal of Electroanalytical Chemistry, 2023, 928: 117019

[23] Zhang P , Kan L , Zhang X , Li R , Qiu C , Ma N , Wei H . Supramolecularly toughened and elastic epoxy resins by grafting 2-ureido-4[1H]-pyrimidone moieties on the side chain. European Polymer Journal, 2019, 116: 126–133

[24] Jiang L , Nie S , Yang J , Dong J . Synthesis and application of setaria viridis-like heterostructures using nickel phyllosilicate decorating polyaniline nanorods: toward the robust and wear-resisting epoxy-based composites. Polymer Composites, 2023, 44(12): 8541–8558

[25] Wang W , Wang Z . Facile synthesis of carbon microspheres/tin ethylenediamine tetramethylene phosphonate hybrid for improving the mechanical, flame-retardant, and thermal properties of epoxy resin. Polymers for Advanced Technologies, 2021, 32(8): 2953–2968

[26] Yamini S , Young R J . Stability of crack propagation in epoxy resins. Polymer, 1977, 18(10): 1075–1080

[27] Wang K , Wu J , Ye L , Zeng H . Mechanical properties and toughening mechanisms of polypropylene/barium sulfate composites. Composites Part A: Applied Science and Manufacturing, 2003, 34(12): 1199–1205

[28] Verma A , Negi P , Singh V K . Experimental analysis on carbon residuum transformed epoxy resin: chicken feather fiber hybrid composite. Polymer Composites, 2019, 40(7): 2690–2699

[29] Verma A , Baurai K , Sanjay M R , Siengchin S . Mechanical, microstructural, and thermal characterization insights of pyrolyzed carbon black from waste tires reinforced epoxy nanocomposites for coating application. Polymer Composites, 2020, 41(1): 338–349

[30] Chen W , Yang J , Zhang F , Liu J , Nie S , Wang Z , Liu L . Significance of structurally inherited nickel/cobalt bimetallic phyllosilicates for enhancing the mechanical, thermal, and dry-sliding properties of epoxy composites. Construction and Building Materials, 2025, 472: 140898

[31] Chen W , Yang J , Li B , Yang H , Zhang Y , Xu X , Wang Z , Nie S . Interfacial-engineered construction of heterostructured PZM@P-NiCoPS architectures: towards robust, wear-resistant, and non-flammable epoxy composites. Journal of the Taiwan Institute of Chemical Engineers, 2026, 185: 106663

[32] Wang T T , Huang P , Li Y Q , Hu N , Fu S Y . Epoxy nanocomposites significantly toughened by both poly(sulfone) and graphene oxide. Composites Communications, 2019, 14: 55–60

[33] Che Y , Sun Z , Zhan R , Wang S , Zhou S , Huang J . Effects of graphene oxide sheets-zirconia spheres nanohybrids on mechanical, thermal, and tribological performances of epoxy composites. Ceramics International, 2018, 44(15): 18067–18077

[34] Lei F , Zhang C , Cai Z , Yang J , Sun H , Sun D . Epoxy toughening with graphite fluoride: toward high toughness and strength. Polymer, 2018, 150: 44–51

[35] Wan R , Chen S , Tang X , Feng Z , Liu J , Li Y . Effect mechanism of the Fe₃O₄ nanoparticles on mechanical properties and anticorrosion performances of epoxy coatings. Progress in Organic Coatings, 2022, 173: 107181

[36] Purohit A , Tripathy V , Mishra S K , Swain P T R , Patnaik P K . Mechanical and tribo-performance analysis of linz donawitz sludge-filled glass–epoxy composites using taguchi experimental design. Journal of The Institution of Engineers (India): Series E, 2022, 103(2): 245–251

[37] Qi Y , Ye X , Huan X , Xu Q , Ma S , Bao D , Zhou G , Zhang D , Zhang Y , Du H . P/N/S flame retardant based on DOPS-triazine groups for improving the flame retardancy, char formation properties, and mechanical properties of epoxy resin. European Polymer Journal, 2024, 202: 112634

[38] Jin P , Yang J , Chen W , Nie S . Synthesis of rice-granular bimetallic nickel/iron phyllosilicates to simultaneously lubricate and strengthen the epoxy-based composites. Polymer Composites, 2025, 46(1): 486–505

[39] Zhou K , Liu J , Shi Y , Jiang S , Wang D , Hu Y , Gui Z . MoS₂ nanolayers grown on carbon nanotubes: an advanced reinforcement for epoxy composites. ACS Applied Materials & Interfaces, 2015, 7(11): 6070–6081

[40] Hou Y , Hu W , Liu L , Gui Z , Hu Y . In-situ synthesized CNTs/Bi₂Se₃ nanocomposites by a facile wet chemical method and its application for enhancing fire safety of epoxy resin. Composites Science and Technology, 2018, 157: 185–194

[41] Kim S H , Heo Y J , Park M , Min B G , Rhee K Y , Park S J . Effect of hydrophilic graphite flake on thermal conductivity and fracture toughness of basalt fibers/epoxy composites. Composites Part B: Engineering, 2018, 153: 9–16

[42] Kim H , Abdala A A , Macosko C W . Graphene/polymer nanocomposites. Macromolecules, 2010, 43(16): 6515–6530

[43] Khawam A , Flanagan D R . Solid state kinetic models basics and mathematical fundamentals. The Journal of Physical Chemistry B, 2006, 110(35): 17315–17328

[44] Sakka M M , Antar Z , Elleuch K , Feller J F . Tribological response of an epoxy matrix filled with graphite and/or carbon nanotubes. Friction, 2017, 5(2): 171–182

[45] Bassani R , Levita G , Meozzi M , Palla G . Friction and wear of epoxy resin on inox steel: remarks on the influence of velocity, load, and induced thermal state. Wear, 2001, 247(2): 125–132

[46] Tian J , Qi X , Li C , Xian G . Friction behaviors and wear mechanisms of multi-filler reinforced epoxy composites under dry and wet conditions: effects of loads, sliding speeds, temperatures, water lubrication. Tribology International, 2023, 179: 108148

[47] Wang Y , Zhang Z , Yang M , Yuan J , Li P , Liu M . Modified montmorillonite synergizes with Co-MOF@PBO fabric to improve the wear resistance of PBO/phenolic resin composites. Journal of Colloid and Interface Science, 2022, 611: 480–490

[48] Yang K , Niu Y , Li Y , Wang X , Du S , Zhang Y . Preparation of double-core microcapsules and tribological properties of epoxy composites. Tribology International, 2023, 186: 108597

[49] Purohit A , Satapathy A . Processing, characterization, and parametric analysis of erosion behavior of epoxy-LD sludge composites using Taguchi technique and response surface method. Polymer Composites, 2018, 39(S4): E2283–E2297

[50] Zhang G , Lu S , Ke Y . Effects of silica nanoparticles on tribology performance of poly(epoxy resin-bismaleimide)-based nanocomposites. Polymer Engineering & Science, 2019, 59(2): 274–283

[51] Jiang L , Yang J N , Dong J , Nie S B , Xu Y X , Feng X S . Facile synthesis of polyaniline nanorods to simultaneously enhance the mechanical properties and wear resistance of epoxy composites. Frontiers of Chemical Science and Engineering, 2023, 17(9): 1254–1266

[52] Köse S , Ulusal F , Yetgin S H . The effect of modified waste fish bone on mechanical and tribological properties of epoxy composites. Journal of Molecular Structure, 2025, 1326: 141084

[53] Tavadi A R , Nagabhushana N , Vivek Bhandarkar V N , Jagadeesha T , Kerur M R , Rudresha S , Durga Prasad C , Rajesh Kannan A , Mohan D G . Investigation on mechanical and sliding wear behavior of pongamia-oil-cake/basalt fiber-reinforced epoxy hybrid composites. Arabian Journal for Science and Engineering, 2024, 49(2): 2311–2325

[54] Jayasinghe R , Ramos M , Nand A , Ramezani M . Enhancing mechanical and tribological properties of epoxy composites with ultrasonication exfoliated MoS₂: impact of low filler loading on wear performance and tribofilm formation. Nanomaterials, 2024, 14(21): 1744

[55] Alajmi M , Shalwan A . Correlation between mechanical properties with specific wear rate and the coefficient of friction of graphite/epoxy composites. Materials, 2015, 8(7): 4162–4175

[56] Ayatollahi M R , Alishahi E , Doagou-R S , Shadlou S . Tribological and mechanical properties of low content nanodiamond/epoxy nanocomposites. Composites Part B: Engineering, 2012, 43(8): 3425–3430

[57] Vinay S S , Sanjay M R , Siengchin S , Venkatesh C V . Effect of Al₂O₃ nanofillers in basalt/epoxy composites: mechanical and tribological properties. Polymer Composites, 2021, 42(4): 1727–1740

[58] Sukur E F , Onal G . Long-term salt-water durability of GNPs reinforced basalt-epoxy multiscale composites for marine applications. Tribology International, 2021, 158: 106910

[59] Muralidhara B , Babu S P K , Suresha B , Yogesha K K , Vasundhara M G , Kalavathi G K , Goudar D M , Kurahatti R V , Bhat S K . Enhanced mechanical, thermal, and wear performance of halloysite nanotube infused carbon fiber epoxy composites. Scientific Reports, 2025, 15(1): 30019

[60] Li M , Pan B , Liu H , Zhu L , Fan X , Yue E , Li M , Qin Y . Interfacial tailoring of basalt fiber/epoxy composites by metal-organic framework based oil containers for promoting its mechanical and tribological properties. Polymer Composites, 2023, 44(8): 4757–4770

[61] Adarmanabadi S R , Jafari M , Farrash S M H , Heidari M . Effect of nano clay, nano-graphene oxide, and carbon nanotubes on the mechanical and tribological properties of crosslinked epoxy nanocomposite. PLoS One, 2021, 16(11): e0259401

[62] Pawlak Z , Kaldonski T , Pai R , Bayraktar E , Oloyede A . A comparative study on the tribological behaviour of hexagonal boron nitride (h-BN) as lubricating micro-particles: an additive in porous sliding bearings for a car clutch. Wear, 2009, 267(5): 1198–1202

[63] Mu L , Cao D , Zhuang W , Yu Q , Cai M , Shi Y . Stable dispersed zeolitic imidazolate framework/graphene oxide nanocomposites in ionic liquids resulting in high lubricating performance. Advanced Materials Interfaces, 2020, 7(9): 1902194

[64] Hu H , Zhang S . Mechanical and tribological properties of silicon carbide/carbon fiber/epoxy resin based composites. Journal of Engineered Fibers and Fabrics, 2024, 19: 1

[65] Hong J , Liu C , Deng X , Jiang T , Gan L , Huang J . Enhanced tribological properties in core-shell structured SiO₂@GO hybrid fillers for epoxy nanocomposites. RSC Advances, 2016, 6(92): 89221–89230

[66] Chen J , Yang J , Chen B , Liu S , Dong J , Li C . Large-scale synthesis of NbSe₂ nanosheets and their use as nanofillers for improving the tribological properties of epoxy coatings. Surface and Coatings Technology, 2016, 305: 23–28

[67] Domun N , Hadavinia H , Zhang T , Sainsbury T , Liaghat G H , Vahid S . Improving the fracture toughness and the strength of epoxy using nanomaterials: a review of the current status. Nanoscale, 2015, 7(23): 10294–10329

[68] Li Y , Zhou Y , Wang Y , Liu M , Yuan J , Men X . Facile synthesis of WS₂@GO nanohybrids for significant improvement in mechanical and tribological performance of EP composites. Tribology International, 2021, 163: 107148

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