Deterioration and Pore Structure Evolution of GO Modified Polymer Cement Mortar under Salt-freeze-thaw Coupling Effects

Abstract

To investigate the pore structure of graphene oxide modified polymer cement mortar (GOPM) under salt-freeze-thaw (SFT) coupling effects and its impact on deterioration, this study modifies polymer cement mortar (EMCM) with graphene oxide (GO). The micro-pore structure of GOPM is characterized using LF-NMR and SEM. Fractal theory is applied to calculate the fractal dimension of pore volume, and the deterioration patterns are analyzed based on the evolution characteristics of capillary pores. The experimental results indicate that, after 25 salt-freeze-thaw cycles (SFTc), SO₄²⁻ ions penetrate the matrix, generating corrosion products that fill existing pores and enhance the compactness of the specimen. As the number of cycles increases, the ongoing formation and expansion of corrosion products within the matrix, combined with persistent freezing forces, and result in the degradation of the pore structure. Therefore, the mass loss rate (MLR) of the specimens shows a trend of first decreasing and then increasing, while the relative dynamic elastic modulus (RDEM) initially increases and then decreases. Compared to the PC group specimens, the G3PM group specimens show a 28.71% reduction in MLR and a 31.42% increase in RDEM after 150 SFTc. The fractal dimensions of the transition pores, capillary pores, and macropores in the G3PM specimens first increase and then decrease as the number of SFTc increases. Among them, the capillary pores show the highest correlation with MLR and RDEM, with correlation coefficients of 0.974 38 and 0.985 55, respectively.

Keywords

graphene oxide / polymer cement mortar / pore structure / fractal dimension

References

[1] Sun Z, Scherer GW. Effect of Air Voids on Salt Scaling and Internal Freezing[J]. Cement and Concrete Research, 2010, 40(2): 260-270

[2] Algourdin N, Nguyen QNA, Mesticou Z, et al.. Durability of Recycled Fine Mortars under Freeze-Thaw Cycles[J]. Construction and Building Materials, 2021, 291: 123 330

[3] Wang P, Zhao G, Zhang G. Mechanism of Redispersible Polymer Powder in Cement Mortar[J]. Journal of the Chinese Ceramic Society, 2018, 46(2): 256-262

[4] Wang M, Wang R, Zheng S, et al.. Research on the Chemical Mechanism in the Polyacrylate Latex Modified Cement System[J]. Cement and Concrete Research, 2015, 76: 62-69

[5] Ramli M, Akhavan Tabassi A. Effects of Polymer Modification on the Permeability of Cement Mortars under Different Curing Conditions: A Correlational Study that Includes Pore Distributions, Water Absorption and Compressive Strength[J]. Construction and Building Materials, 2012, 28(1561-570

[6] Cao R, Yang J, Li G, et al.. Effect of Sulfuric Acid on Cementitious Composites Containing Ethylene-Vinyl Acetate and Styrene-Butadiene Rubber[J]. Journal of Building Engineering, 2023, 80: 108 024

[7] Zhang X, Du M, Fang H, et al.. Polymer-Modified Cement Mortars: Their Enhanced Properties, Applications, Prospects, and Challenges[J]. Construction and Building Materials, 2021, 299: 124 290

[8] Ji G, Peng X, Wang S, et al.. Influence of Magnesium Slag as a Mineral Admixture on the Performance of Concrete[J]. Construction and Building Materials, 2021, 295: 123 619

[9] Wong HS, Barakat R, Alhilali A, et al.. Hydrophobic Concrete Using Waste Paper Sludge Ash[J]. Cement and Concrete Research, 2015, 70: 9-20

[10] Li WW, Ji WM, Wang YC, et al.. Investigation on the Mechanical Properties of a Cement-Based Material Containing Carbon Nanotube under Drying and Freeze-Thaw Conditions[J]. Materials, 2015, 8(12): 8 780-8 792

[11] Gonzalez M, Tighe SL, Hui K, et al.. Evaluation of Freeze/thaw and Scaling Response of Nanoconcrete for Portland Cement Concrete (PCC) Pavements[J]. Construction and Building Materials, 2016, 120: 465-472

[12] Lankone RS, Challis KE, Bi Y, et al.. Methodology for Quantifying Engineered Nanomaterial Release from Diverse Product Matrices under Outdoor Weathering Conditions and Implications for Life Cycle Assessment[J]. Environmental Science: Nano, 2017, 4(9): 1 784-1 797

[13] Birenboim M, Nadiv R, Alatawna A, et al.. Reinforcement and Workability Aspects of Graphene-Oxide-Reinforced Cement Nanocomposites[J]. Composites Part B: Engineering, 2019, 161: 68-76

[14] Lv S, Ma Y, Qiu C, et al.. Effect of Graphene Oxide Nanosheets of Microstructure and Mechanical Properties of Cement Composites[J]. Construction and Building Materials, 2013, 49: 121-127

[15] Ruan C, Lin J, Chen S, et al.. Effect of Graphene Oxide on the Pore Structure of Cement Paste: Implications for Performance Enhancement[J]. ACS Applied Nano Materials, 2021, 4(10): 10 623-10 633

[16] Zeng H, Lai Y, Qu S, et al.. Exploring the Effect of Graphene Oxide on Freeze-Thaw Durability of Air-Entrained Mortars[J]. Construction and Building Materials, 2022, 324: 126 708

[17] Naseem Z, Shamsaei E, Sagoe-Crentsil K, et al.. Antifoaming Effect of Graphene Oxide Nanosheets in Polymer-Modified Cement Composites for Enhanced Microstructure and Mechanical Performance[J]. Cement and Concrete Research, 2022, 158: 106 843

[18] Naseem Z, Shamsaei E, Sagoe-Crentsil K, et al.. Microstructural and Polymer Film Interaction Mechanisms: Insights of GO-Reinforced Polymer-Modified Cement Composites[J]. Journal of Building Engineering, 2023, 80: 107 962

[19] Li L, Li Z, Cao M, et al.. Nanoindentation and Porosity Fractal Dimension of Calcium Carbonate Whisker Reinforced Cement Paste after Elevated Temperatures (up to 900 °C)[J]. Fractals, 2021, 29(02): 2 140 001

[20] Tang SW, Cai XH, Zhou W, et al.. In-Situ and Continuous Monitoring of Pore Evolution of Calcium Sulfoaluminate Cement at Early Age by Electrical Impedance Measurement[J]. Construction and Building Materials, 2016, 117: 8-19

[21] Sun M, Zou C, Xin D. Pore Structure Evolution Mechanism of Cement Mortar Containing Diatomite Subjected to Freeze-Thaw Cycles by Multifractal Analysis[J]. Cement and Concrete Composites, 2020, 114: 103 731

[22] Huo J h, Peng Z g, Ye Z, et al.. Characterising the Hydration Process of Cement Slurry System Based on Low-Field NMR[J]. Advances in Cement Research, 2020, 32(112-19

[23] She A, Ma K, Liao G, et al.. Investigation of Hydration and Setting Process in Nanosilica-Cement Blended Pastes: In Situ Characterization Using Low Field Nuclear Magnetic Resonance[J]. Construction and Building Materials, 2021, 304: 124 631

[24] Li J, Zhu L, Zhou K, et al.. Non-Linear Creep Damage Model of Sandstone under Freeze-Thaw Cycle[J]. Journal of Central South University, 2021, 28(3954-967

[25] Jiang Z, Cai G, Tian G, et al.. Effect of Aggregate Particle Size on Mortar Pore Structure[J]. Construction and Building Materials, 2022, 352: 128 988

[26] Zhao K, Ma C, Yang J, et al.. Pore Fractal Characteristics of Fiber-Reinforced Backfill Based on Nuclear Magnetic Resonance[J]. Powder Technology, 2023, 426: 118 678

[27] Ji Y, Sun Z, Jiang X, et al.. Fractal Characterization on Pore Structure and Analysis of Fluidity and Bleeding of Fresh Cement Paste Based on 1H Low-Field NMR[J]. Construction and Building Materials, 2017, 140: 445-453

[28] Liu J. Effect of Multilayer Graphene Oxide on the Hydration and Early Mechanical Strength of Cement Mortar in Low Temperature[J]. Construction and Building Materials, 2023, 364: 129 997

[29] Li H, Gu L, Dong B, et al.. Improvements in Setting Behavior and Strengths of Cement Paste/Mortar with EVA Redispersible Powder Using C-S-Hs-PCE[J]. Construction and Building Materials, 2020, 262: 120 097

[30] Gao Y, Jing HW, Chen SJ, et al.. Influence of Ultrasonication on the Dispersion and Enhancing Effect of Graphene Oxide-Carbon Nanotube Hybrid Nano-Reinforcement in Cementitious Composite[J]. Composites Part B: Engineering, 2019, 164: 45-53

[31] Zhao X, Qiao H, Li S, et al.. Effects of Nano-Graphene Oxide and Ethylene-Vinyl Acetate Rubber Powder on Mechanical Properties and Microstructure of Mortar[J]. Acta Materiae Compositae Sinica, 2025, 42(63 318-3 331

[32] Zhang R, Long Z, Long G, et al.. Mechanism of Graphene Oxide Concrete Macro-Micro Properties Evolution under Large Temperature Difference Freeze-Thaw Action[J]. Construction and Building Materials, 2024, 415: 135 019

[33] Cai Y, Wang PM, Zhong SY. Influence of Coagulation of Polymer Dispersion on the Properties of Polymer-Modified Mortar[J]. Advanced Materials Research, 2015, 1129: 162-168

[34] Nguyen H D, Zhang Q, Sagoe-Crentsil K, et al.. Graphene Oxide-Coated Sand for Improving Performance of Cement Composites [J]. Cement and Concrete Composites, 2021, 124: 104 279

[35] Yu L, Bai S, Guan X. Effect of Graphene Oxide on Microstructure and Micromechanical Property of Ultra-high Performance Concrete [J]. Cement and Concrete Composites, 2023, 138: 104 964

[36] Qian J, Zhou LQ, Wang X, et al.. Degradation of Mechanical Properties of Graphene Oxide Concrete under Sulfate Attack and Freeze-Thaw Cycle Environment[J]. Materials, 2023, 16(216 949

[37] Wang R, Zhang Q, Li Y. Deterioration of Concrete Under the Coupling Effects of Freeze-Thaw Cycles and Other Actions: A Review[J]. Construction and Building Materials, 2022, 319: 126 045

[38] Wang Y, Yang W, Ge Y, et al.. Analysis of Freeze-Thaw Damage and Pore Structure Deterioration of Mortar by Low-Field NMR[J]. Construction and Building Materials, 2022, 319: 126 097

[39] Jin S, Zheng G, Yu J. A Micro Freeze-Thaw Damage Model of Concrete with Fractal Dimension[J]. Construction and Building Materials, 2020, 257: 119 434

[40] Xue W, Peng X, Alam MS, et al.. Pore Structure, Mechanical Property and Permeability of Concrete under Sulfate Attack Exposed to Freeze-Thaw Cycles[J]. Archives of Civil and Mechanical Engineering, 2024, 24(2130

[41] Zhang L. Fractal Characteristics of Pore Structure of Hardened Cement Paste Prepared by Pressurized Compact Molding[J]. Construction and Building Materials, 2020, 2020, 259: 119 856

[42] Yang J, Huang J, He X, et al.. Segmented Fractal Pore Structure Covering Nano- and Micro-Ranges in Cementing Composites Produced with GGBS[J]. Construction and Building Materials, 2019, 225: 1 170-1 182

[43] Porteneuve C, Korb JP, Petit D, et al.. Structure-Texture Correlation in Ultra-High-Performance Concrete A Nuclear Magnetic Resonance Study[J]. Cement and Concrete Research, 2002, 32: 97-101

[44] Zhang C, Liu T, Jiang C, et al.. The Freeze-Thaw Strength Evolution of Fiber-Reinforced Cement Mortar Based on NMR and Fractal Theory: Considering Porosity and Pore Distribution[J]. Materials, 2022, 15(207 316

[45] Yang S, Han M, Chen X, et al.. Effect of Sulfate Crystallization on Uniaxial Compressive Behavior of Concrete Subjected to Combined Actions of Dry-Wet and Freeze-Thaw Cycles[J]. Journal of Cold Regions Engineering, 2023, 37(104 022 015

[46] Zhao L, Guo X, Ge C, et al.. Investigation of the Effectiveness of PC@GO on the Reinforcement for Cement Composites[J]. Construction and Building Materials, 2016, 113: 470-478

[47] Yao Y, Liu C, Liu H, et al.. Deterioration Mechanism Understanding of Recycled Powder Concrete under Coupled Sulfate Attack and Freeze-Thaw Cycles[J]. Construction and Building Materials, 2023, 388: 131 718

RIGHTS & PERMISSIONS

Wuhan University of Technology and Springer-Verlag GmbH Germany, Part of Springer Nature