Tracing the Status of Silica Fume in Cementitious Materials Subjected to Deterioration Mechanisms with Raman Microscope
- Carbonation, a deterioration mechanism of concrete, is a chemical reaction between atmospheric carbon dioxide (CO2) and cement hydration products. Whilst virtually almost all of the Ca-bearing hydration products [i.e., calcium silicate hydrate (C–S–H), calcium hydroxide (Ca(OH)2, CH), and various calcium aluminate or ferro-aluminate hydrates] can react with the CO2 to produce calcium carbonate (CaCO3), silica gel, hydrated aluminum, and iron oxides, the dominant reaction is the reaction between calcium hydroxide (CH) and CO2, which will convert CH into calcium carbonate [17,18]. Therefore, carbonation can reduce the pH of the concrete pore solution, which can subsequently trigger the corrosion of reinforcing bars. Additionally, owing to the increased volume from the formation of calcium carbonate, the microstructure of the cement matrix could be densified . On the other hand, due to the carbonation shrinkage, it could also be possible that some microcracks could be formed . All these could potentially affect the stability of the SF agglomerates.
- Sulfate attack occurs when sulfate salts (i.e., SO42−) ingress into the cementitious materials and subsequently react with the hydrates/phases of the cement (e.g., calcium hydroxide, tricalcium aluminate hydrates, monosulfoaluminate, unreacted aluminate, or ferrite phase) to form gypsum or/and ettringite (AFt) [21,22]. The formation of gypsum and ettringite is generally considered to be harmful to the hardened cementitious materials. This is because the formation of ettringite is accompanied by local volume increase and subsequent pressure build-up to the surrounding matrix, leading to the cracking, spalling, and even destruction of cementitious materials . Again, once the cracks are formed [24,25], it could promote further interactions between the cement matrix and surrounding environment. As a result, the stability of the SF agglomerates could be affected.
- Chloride ingress is another severe deterioration mechanism to the steel reinforced concrete, as it could cause the depassivation of the passive film on the steel surface. On the other hand, chloride ions can react with hydrated aluminate phases, yielding the so-called Friedel’s salt (3CaO Al2O3 CaCl2 10H2O) [26,27,28]. As Friedel’s salt occupies more volume than aluminate phases, there is a pore refinement owing to the intrusion of chloride ions. More importantly, the consumption of aluminate hydrates could change the chemistry environment of the cement matrices, which can potentially affect the stability of the SF agglomerates within cementitious materials.
2. Materials and Methods
2.2. Manufacture of SF Blended PC Paste Samples
2.3. Deterioration Regimes
- Carbonation: a modified carbonation chamber (LEEC, Nottingham, UK) was employed in the carbonation test. The chamber was set to maintain a constant temperature of 20 (±1) °C, a carbon dioxide (CO2) concentration of 5 (±0.5)%, and relative humidity (RH) of 60 (±5)%, based on a laboratory established regime .
- Chloride attack: the 165 g/L sodium chloride (NaCl) solution as specified in the NT BUILD 443  was used as the aggressive solution for the chloride ingress test. The 63 µm powders were placed at the bottom of the tank containing NaCl solution. The tank was then closed tightly and placed in the curing room at a constant temperature of 20 (±1) °C.
- Sulfate attack: the sodium sulfate (Na2SO4) solution, with a concentration of 50 g/L as specified in the ASTM C1012 , was used. Similar to the chloride attack, the 63 µm powders were immersed in the Na2SO4 solution for 3 months and then removed from the tank.
2.4. Raman Microscope Test
3. Results and Discussion
3.2. Chloride Attack
- Cl− ions, compared to OH−, have a relatively smaller ionic size and a greater tendency to diffuse inside the ‘membrane’ (e.g., adsorption/coating of Ca2+ on hydrated C3S), which could facilitate the build-up of internal pressure. This hence causes an early rupture of the ‘membrane’, leading to the unlocking of the C3S phase, which comes in contact with water and promotes the hydration reaction .
- The NaCl (used during deterioration) could react with CH in the pore solution and increase the amount of CaCl2 in the cement matrix. The CaCl2 is a well-established inorganic chloride-based accelerator and can flocculate hydrophilic colloids (e.g., C–S–H), facilitating the diffusion of ions and water through the initial C–S–H layer and thus allowing a higher rate of hydration during the early diffusion-controlled period .
- The CaCl2 could enhance the C–S–H nucleation by a homogeneous precipitation, and this accelerates the hydration .
3.3. Sulfate Attack
- The amorphous silica was identified in the SF–PC blends exposed to the carbonation and sulfate attack, as evidenced by the Raman bands at about 350–540 cm−1. No silica phases were identified in the chloride attacked SF–PC blends, which could be attributed to the enhanced hydration of cement and hence continued hydration of SF. These results indicate that there is a potential hazard to the living system, especially the long-term servicing structures exposed to a contiguous deterioration environment.
- This study clearly demonstrated the potential of employing the Raman microscope for tracing the status of silica fume in cementitious materials subjected to deterioration mechanisms, indicating that the use of Raman microscopes could be an effective approach to monitoring the status of nanomaterials, such as SF, in concrete structures.
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
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|Deterioration Mechanisms||Raman Bands (cm−1)||Assignments|
|Chloride attack||210/250, 356/395, 513/530, 778||Friedel’s salt|
|Sulfate attack||400–540||amorphous silica|
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Yue, Y.; Wang, J.; Bai, Y. Tracing the Status of Silica Fume in Cementitious Materials Subjected to Deterioration Mechanisms with Raman Microscope. Materials 2022, 15, 5195. https://doi.org/10.3390/ma15155195
Yue Y, Wang J, Bai Y. Tracing the Status of Silica Fume in Cementitious Materials Subjected to Deterioration Mechanisms with Raman Microscope. Materials. 2022; 15(15):5195. https://doi.org/10.3390/ma15155195Chicago/Turabian Style
Yue, Yanfei, Jingjing Wang, and Yun Bai. 2022. "Tracing the Status of Silica Fume in Cementitious Materials Subjected to Deterioration Mechanisms with Raman Microscope" Materials 15, no. 15: 5195. https://doi.org/10.3390/ma15155195