The research team, led by Tongning Cao and colleagues including Han Wang, Qi Dong, Fengjuan Wang, Zhiyong Liu, Chenyun Yu, Bin Peng, and Jinyang Jiang, set out to close a persistent gap in concrete durability science. Most laboratory studies of sulfate attack have been performed under simple immersion, wet-dry cycling, or atmospheric pressure conditions. Those regimes capture shallow-marine and terrestrial exposure reasonably well, but they ignore the defining feature of the deep-sea environment: sustained hydrostatic pressure ranging from several to tens of megapascals. At such pressures, the state of pore water, the morphology of the pore network, and the very mechanisms of ion transport inside concrete may be fundamentally altered, making conventional durability predictions unreliable for deep-water structures.

To probe these coupled effects, the researchers built a custom hydrostatic pressure-sulfate erosion apparatus capable of simultaneously controlling pressure, temperature, and sulfate exposure. The system, rated to a maximum of 25 megapascals with a pressure resolution of 0.1 megapascals, centers on a one-liter high-pressure reaction vessel pressurized by nitrogen gas. Cubic cement paste specimens with a water-to-binder ratio of 0.4 were cast, cured for 28 days, and then sealed with epoxy resin on five faces, leaving a single 20 by 20 millimeter face exposed. This clever geometry forced sulfate ions to travel along one well-defined direction, simplifying the interpretation of the depth-resolved measurements that followed.

Specimens were exposed to a 5 percent sodium sulfate solution at three gauge pressures: 0, 1.2, and 2.4 megapascals, for a total of 150 days. The solution was refreshed every 15 days to maintain aggressive conditions. At 60, 90, 120, and 150 days, replicate specimens were retrieved, sectioned into 2-millimeter-thick slices along the exposure direction, and treated with isopropanol to halt hydration. All sample handling took place in a nitrogen-controlled glove box to prevent carbonation from contaminating the chemistry. One portion of each powdered slice was analyzed for sulfate ion content by gravimetric barium sulfate titration, while the other was subjected to quantitative X-ray diffraction with Rietveld refinement, using aluminum oxide as an internal standard, to measure the amount of ettringite, also known as AFt, formed at each depth.

The results reveal a striking pressure dependence. At a depth of 9 millimeters, the sulfate concentration after 150 days rose from 1.6 percent under atmospheric pressure to 2.7 percent at 2.4 megapascals. Deeper in the material the contrast became even more dramatic: at 19 millimeters, the sulfate content after 150 days was 0.5 percent at 0 megapascals, but 0.9 percent at 1.2 megapascals and 1.2 percent at 2.4 megapascals. In other words, moderate pressures that are routine in coastal and shallow offshore engineering already boost sulfate penetration by roughly 50 to 80 percent, and the enhancement grows with both depth and time. Ettringite formation followed the same pattern, accumulating preferentially near the exposed surface and decaying inward, with concentrations at 5 millimeters reaching 1.69 percent at 0 megapascals, 2.6 percent at 1.2 megapascals, and 3.1 percent at 2.4 megapascals after 120 days.

Microscopy and porosimetry explained why. Field-emission scanning electron microscopy showed the corrosion products as interwoven needle-like and rod-like crystals, the classic habit of ettringite, while energy-dispersive spectroscopy confirmed the enrichment of calcium, aluminum, sulfur, and oxygen in ratios matching the mineral’s stoichiometry. Notably, ettringite crystals clustered around portlandite, suggesting that as sulfate ions consume calcium from the pore solution, portlandite dissolves to replenish it, sustaining the reaction and progressively degrading the matrix. Mercury intrusion porosimetry then quantified the structural toll: total porosity climbed from 14.93 percent at 0 megapascals to 19.02 percent at 1.2 megapascals and 25.81 percent at 2.4 megapascals, with the pore-size distribution shifting toward larger, better-connected channels.

This pore-structure evolution sets up a vicious feedback loop. Pressure-enhanced sulfate transport delivers more reactant deeper into the material, accelerating ettringite formation, which coarsens and connects the pore network. The modified network in turn raises the effective diffusion coefficient, allowing still faster sulfate ingress. According to Fick’s law, this increase in effective transport capacity strengthens concentration-gradient-driven migration, producing deeper penetration and higher interior sulfate contents. The authors’ simulations capture this nonlinear amplification: after 150 days, predicted sulfate concentrations at 20 millimeters were 112 percent higher at 1.2 megapascals and 290 percent higher at 2.4 megapascals than under atmospheric pressure. From a crystallization-pressure perspective, the elevated sulfate supply also drives the pore solution to supersaturation sooner, triggering earlier ettringite crystallization and shortening the material’s latent expansion period.

To turn these observations into a predictive tool, the team constructed a coupled sulfate transport-reaction model grounded in Fick’s second law and mass conservation. The model treats sulfate ions as either free in the pore solution or consumed by reaction with calcium and aluminate-bearing hydration products to form ettringite, following the stoichiometry that one mole of AFt requires two moles of external sulfate. The effective diffusion coefficient is computed from porosity, tortuosity, and the Stokes-Einstein estimate of sulfate diffusivity in water, with a phenomenological pressure term linking hydrostatic stress to porosity change through the circumferential tensile stress around idealized cylindrical pores. The equations were solved numerically with the finite volume method on hexahedral grids, accelerated by a multigrid V-cycle scheme implemented in MATLAB.

Validation against the 1.2 megapascal experiments showed good agreement between predicted and measured sulfate and ettringite profiles across the full 150-day exposure and the entire penetration depth, with minor discrepancies attributed to the finite thickness of the sliced samples. The framework provides, for the first time, an experimentally supported quantitative link between hydrostatic pressure, sulfate transport, reaction kinetics, and pore-structure evolution in cementitious materials. The authors caution that the study used cement paste under controlled laboratory conditions rather than full concrete in service, and that further validation across broader materials, environments, and timescales is needed before deep-ocean application. Even so, the message for engineers is clear and urgent: durability assessments for submerged and deep-buried structures that ignore hydrostatic pressure may substantially underestimate how fast sulfate attack proceeds, and how soon the ocean’s quiet chemistry begins to dismantle the concrete we trust to hold it back.

Subject of Research: Effect of hydrostatic pressure on sulfate transport and ettringite formation in cement paste

Article Title: Effect of hydrostatic pressure on transport-reaction processes of cement paste under sulfate attack

Article References: Cao, T., Wang, H., Dong, Q., Wang, F., Liu, Z., Yu, C., Peng, B., & Jiang, J. (2026). Effect of hydrostatic pressure on transport-reaction processes of cement paste under sulfate attack. Case Studies in Construction Materials, 25, Article e06588. https://doi.org/10.1016/j.cscm.2026.e06588

Image Credits: AI Generated

DOI: 10.1016/j.cscm.2026.e06588

Keywords: sulfate attack, hydrostatic pressure, cement paste, ettringite, concrete durability, deep-sea environment, ion transport, porosity, XRD-Rietveld, transport-reaction model, marine engineering, pore structure