Deterioration of concrete in railway tunnel suffering from sulfate attack

For the sake of understanding the deterioration behavior of concrete in actual railway tunnel structures subjected to aggressive sulfate medium in practice,detailed field investigations and tested analysis on sprayed concrete linings of approximately 40-year-old railway tunnels in environments containing sulfate ion were carried out,respectively.The results show that the deterioration of concretes in the investigated area is serious,which involves complicated physicochemical process between the sulfate salt and concrete.Among them,the secondary sulfateminerals such as gypsum formation under very high concentration sulfate ion condition by accumulating and evaporation process dominate,followed by the crystallization of sulfate salt and formation of thaumasite.

Deterioration Mechanism of Sulfate Attack on Concrete under Freeze-thaw Cycles

The experiments of concrete attacked by sulfate solution under freeze-thaw cycles were investigated. The sulfate solution includes two types of 5% Na2SO4 and 5% MgSO4. Through the experiment, microstructural analyses such as SEM, XRD and TGA measurements were performed on the selected samples after freeze-thaw cycles. The corrosion products of the concrete were distinguished and quantitatively compared by the thermal analysis. Besides, the damage mechanism considering the dynamic modulus of elastically of concrete under the coupling effect was also investigated. The experimental results show that, under the action of freeze-thaw cycles and sulfate attack, the main attack products in concrete are ettringite and gypsum. The corrosion products exposed to MgSO4 solution are more than those to Na2SO4 solution. Furthermore, the content of gypsum in concrete is less than that of ettringite in test, and some of gypsum can be observed only after a certain corrosion extent. It is also shown that MgSO4 solution has a promoting effect to the damage of concrete under freeze-thaw cycles. Whereas for Na：SO4 solution, the damage of concrete has restrained before 300 freeze-thaw cycles, but the sulfate attack accelerates the deterioration process in its further test period.

Effect of flexural loading on degradation progress of recycled aggregate concrete subjected to sulfate attack and wetting-drying cycles

The degradation progress of recycled aggregate concrete(RAC) subjected to sulfate attack under wetting-drying cycles and flexural loading is studied. Three different stress ratios(0, 0.3 and 0.5) were applied in this test. The variations of relative dynamic elastic modulus Erd and water-soluble SO2-4 contents in RAC were used to evaluate degradation progress. The changes in mineral products and microstructures of interior concrete were investigated by means of X-ray diffraction(XRD), the environmental scanning electron microscope(ESEM) and X-ray computed tomography(X-CT). The results indicate that flexural loading accelerates the degradation of RAC under sulfate attack and wetting-drying cycles by expediting the transmission of SO2-4 into interior concrete. Furthermore, the accelerated effect of flexural loading is more obvious with the increase of stress ratio, that is because higher stress ratios can accelerate the extension of microcracks and generate more channels for the transmission of SO2-4. Also, more expansive products(gypsum and ettringite) are generated by the reaction of Ca(OH)2 with SO2-4, which can further accelerate the degradation of RAC.

Evaluating Deterioration of Concrete by Sulfate Attack

Effects of factors such as water to cement ratio, fly ash and silica fume on the resistance of concrete to sulfate attack were investigated by dry-wet cycles and immersion method. The index of the resistance to sulfate attack was used to evaluate the deterioration degree of concrete damaged by sulfate. The relationship between the resistance of concrete to sulfate attack and its permeability/porosity were analyzed as well as its responding mechanism. Results show that the depth of sulfate crystal attack from surface to inner of concrete can be reduced by decreasing w/c and addition of combining fly ash with silica fume. The variation of relative elastic modulus ratio and relative flexural strength ratio of various specimens before and after being subjected to sulfate attack was compared.

Influence of Cement Types and Mineral Admixtures on Resistance of Mortar to Sulfate Attack under Lower Temperature

Mortar prisms made with different cements or mineral admixtures plus 30% mass of limes tone filler were stored in 2% magnesium sulfate solution at 5±1 ℃ for 1 year and their visual appearance,strength development were measured at intervals.The formation of thaumasite was checked and confirmed by XRD and FTIR.The results show that the relative resistance to thaumasite form of sulfate attack of the cements is outlined below,from best to worst:sulphoaluminate cement,sulfate resisting Portland cement,OPC.The resistance to thaumasite form of sulfate attack of mortar is remarkably improved by the addition of silica fume or ground granulated blastfurnace slag (SL),and the better the resistance to thaumasite form of sulfate attack,the more the addition of SL is.The thaumasite form of sulfate attack is decreased to a certain degree by a lower replacement of cement with fly ash,but it is accelerated by the addition of a higher amount of fly ash due to its lower reactivity.

Application of Image Analysis Based on SEM and Chemical Mapping on PC Mortars under Sulfate Attack

The degradation mechanisms of cementitious materials exposed to sulfate solutions have been controversial, despite considerable research. In this paper, two methodologies of image analysis based on scanning electron microscope and chemical mapping are used to analyse Portland cement mortars exposed to sodium sulfate solution. The effects of sulfate concentration in solution and water to cement ratio of mortar, which are considered as the most sensitive factors to sulfate attack, are investigated respectively by comparing the macro expansion with microstructure analysis. It is found that the sulfate concentration in pore solution, expressed as sulfate content in C-S-H, plays a critical role on the supersaturation with respect to ettringite and so on the expansion force generated.

Sulfate Attack on Concrete in an Inland Salt Lake Environment

Several cracks were found on the surface of the concrete foundations that support the steel towers of the Luohe （漯河）-Huaiyung （淮阳） high-voltage electricity transmission line that is 20 years old and situated in an inland salt lake environment in North China. To analyze the deterioration mechanism that led to this condition, field investigations were carried out and several tests were conducted on the soil and the affected concrete, including XRD （X-ray diffraction）, electric probe analysis, and chemical analysis. The results show that the concentration of sulfates is very high （0. 39% wt. -0.67% wt. ） in both the surrounding soil and the material around the coarse aggregates inside the concrete. Hence, sulfate attack could be one of the main causes of concrete deterioration. The percentage of sulfates in the surface layer of the concrete was higher than that in the inner layers of the concrete. The sulfates penetrate into the concrete and react with the hydrates of cement to form ettringite （AFt）, which leads to increase in the volume and cracking of the concrete.

Ultrasonic testing and microscopic analysis on concrete under sulfate attack and cyclic environment

The damage process of concrete exposed to sodium sulfate attack and drying-wetting cycles was investigated. The water to binder(W/B) ratio and the concentration of sulfate solution were taken as variable parameters. Through the experiment, visual change, relative dynamic modulus of elasticity(RDME) and the surface damage layer thickness of concrete were measured.Furthermore, SEM and thermal analysis were used to investigate the changing of microstructure and corrosion products of concrete.The test results show that the ultrasonic velocity is related to the damage layer of concrete. It approves that an increase in damage layer thickness reduces the compactness and the ultrasonic velocity. The deterioration degree of concrete could be estimated effectively by measuring the surface damage layer and the RDME of concrete. It is also found that the content of gypsum in concrete is less than that of ettringite in test, and some gypsum is checked only after a certain corrosion extent. When the concrete is with high W/B ratio or exposed to high concentration of sulfate solution, the content of ettringite first increases and then decreases with corrosion time. However, the content of gypsum increases at a steady rate. The content of corrosion products does not correspond well with the observations of RDME change, and extensive amount of corrosion products can be formed before obvious damage occurs.

Influence of Temperature on Sulfate Attack of Limestone Filler Cement Mortar

Mortar prisms were made with three different cementitious materials (with or without mineral admixture) plus 30% mass of limestone filler. After 28 days of curing in water at room temperature, the mortars were submerged in 2% magnesium sulfate solution at different temperatures (5℃, 20℃and alternate temperature between 5℃and 20℃) for a year. The appearance and strength development were measured on these immersed prisms at intervals, and samples selected from the surface of prisms were examined by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). The results show that the influence of temperature on the resistance to sulfate attack of mortar is related to the binder compositions. A higher temperature leads to a quicker strength loss and appearance deterioration of the mortar without mineral admixture. For blended cements, a higher temperature is favorable for the pozzolanic reaction of mineral admixture and the overall deterioration of mortar is reduced with the increasing temperature. When the mineral admixture has a lower reactivity, such influence of temperature on the resistance to sulfate attack of mortar containing admixtures becomes greater. At the three different solution temperatures, two blended cements show significantly improved resistances to sulfate attack. After 1 year of exposure to magnesium sulfate solutions, the formation of thaumasite was checked in the OPC mortars at both 5℃and 20℃. It is concluded that the thaumasite formation is not limited to structures at low temperature (less than 15℃).

Form and Mechanism of Sulfate Attack on Cement-based Material Made of Limestone Powder at Low Water-binder Ratio under Low Temperature Conditions

The development of strength and the form of attack of cement-based material made of limestone powder at low water-binder ratio under low-temperature sulfate environment were studied. The results indicate that when water-binder ratio is lower than 0.40, the cement-based material with limestone powder has insignificant change in appearance after being soaked in 10% magnesium sulfate solution at low temperature for 120 d, and has significant change in appearance after being soaked at the age of 200 d. Expansion damage and exfoliation occur on the surface of concrete test cube at different levels. When limestone powder accounts for about 28 percent of cementitious material, with the decrease of water-binder ratio, the compressive strength loss has gradually decreased after the material is soaked in the magnesium sulfate solution at low temperature at the age of 200 d. After the specimen with the water-binder ratio of less than 0.4 and the limestone powder volume of greater than 20% is soaked in 10% magnesium sulfate solution at low temperature at the age of 200 d, gypsum attack-led destruction is caused to the concrete test cube, without thaumasite sulfate attack.

Mechanism and Process of Sulfate Attack on Roller Compacted Concrete with MgO Expansive Agent

The mechanisms and processes of sulfate attack on roller compacted concrete(RCC)with MgO expansive agent are proposed by investigating the microstructure and hydration products in specimens immersed in 5%sodium sulfate solution for one year with the optical micrograph,scanning electron microscopy(SEM)and scanning electron microscopy-energy dispersive spectrometer(SEM-EDS).The results show that the deterioration of concrete due to the sulfate attack is mainly loss of stiffness,strength and adhesion,and expansion cracking is mainly caused by the formation of gypsum and ettringite.In the presence of MgO expansive agent,the microstructures of RCC can be improved by hydration and un-hydrated products,the large pores and permeability are reduced,and the resistance to sulfate corrosion of concrete and durability of hydraulic structure are improved slightly.

Investigation of Sulfate Attack Resistance of Shotcrete under Dry-wet Cycles

In order to research the sulfate attack resistance of shotcrete, the sulfate attack of shotcrete in the presence and absence of steel fiber was experimentally studied by using dry-wet cycle method. Meanwhile, compared with ordinary concrete by the same mixture, the difference of sulfate attack resistance of shotcrete was studied. The experimental results showed that, with dry-wet cycles increasing, the changes of loss rate of relative dynamic elastic modulus and mass loss rate of specimens included three stages： initial descent stage, stable stage, and rapid descent stage, respectively. However, the changes of mechanical properties first increased and then decreased. Furthermore, the corrosion products of shotcrete after sulfate attack were observed by using the method of XRD, thermal analysis, and SEM, respectively, and the failure mode of shotcrete turned from ettringite destruction to ettringite-gypsum comprehensive failure. Meanwhile, the contents of ettringite and gypsum increased with increasing dry-wet cycle. Simultaneously, the stratified powders drilled from shotcrete under 150＇s dry-wet cycle were analyzed for the mineral phase composition and thermal analysis. With the drywet cycle increasing, the content of ettringite first increased and then decreased and tended to stable. However, the determination of gypsum decreased gradually and even to 0 when the depth was more than 12 mm.

Effect of Al in Slag Blended Cement Paste under Sulfate Attack

Unilateral sulfate attack of cementitious materials containing 40% slag with different water to binder ratios was investigated. The results showed that the degradation of slag blended cement pastes was nearly from the corners of paste surface with cracking and spallings, water-to-binder（w/b） ratio made a significant sense to the damage that low w/b ratio led to little weight loss, less cracking and spalling damage and vice versa. Microstructural experimental results demonstrated that in the three different stages of sulfate attack, degradation of pastes was primarily associated with the migration behavior and bonding configuration of aluminum, in the early ages Al was mostly present in C-（A）-S-H, and thus, the damage of pastes hardly appeared while at later ones Al had been largely transferred from C-（A）-S-H into AFt, leading to expansive damage.

Mechanism of Expansion of Mortars with Limestone Filler due to External Sulfate Attack

The mechanism of expansion of mortars and pastes with limestone filler due to external sulfate attack was studied.Mortars and pastes made at water to solid ratios of 0.45, 0.5, 0.6 from Portland Cement (OPC) with 0%, 20% or 30% (w/w) limestone filler (LF) were cured in a 95±1% RH moist room at 20±1℃for 14 or 28 days. They subsequently were immersed in 5% Na2SO4(0.35 M) solution at ambient temperature (1-35℃). The expansion of the specimens was measured every month, and selected samples were examined by X-ray diffraction (XRD) and scanning electron microscope (SEM). The results indicate that mortars with 20% LF show larger expansion than that of OPC mortars at up to 9 months of exposure, and the amount of gypsum in both mortars and pastes with LF is much more than that in mortars and pastes without LF. Therefore, it is reasonable to conclude that the formation of massive gypsum leads to the lager expansion of the mortars and pastes containing 20% LF. These behaviors may be explained by the changes in hydration products due to the addition of LF.

Mechanism and Preventive Technology of the Thaumasite Form of Sulfate Attack on Cement Mortars

The deterioration mechanism of thaumasite towards cement or concrete structure and the deterioration pattern of in-situ construction caused by the formation of thaumasite were studied in this paper. To improve the TSA (the thaumasite form of sulfate attack) resistance, the cement type, water to cement ratios, the mineral admixture and the circumstance factors should be taken into consideration.

On the Ettringito Form of Sulfate Attack: Part 2. The Expansive Mechanism of Concrete Caused by Secondary Ettringite

In part 1 of this two-part series, the formation mechanism of secondary ettringite has been discussed. In this part, the expansive mechanisms of secondary ettringite due to the ettringite form of sulfate attack were reviewed and analyzed. Three theories have been proposed for explaining the expansive mechanism of secondary ettringite, that is, the crystallization pressure theory (or the crystal growth theory), the theory increasing in solid volume and the swelling theory. According to the analysis, swelling theory should be responsible for the expansion of secondary ettringite. The experimental results also verified that the expansion, subsequent the cracking and spalling of concrete can be caused by the swelling of fine ettringite particles formed at the interface zone of coarse aggregate particles.

On the Ettringite Form of Sulfate Attack: Part 1. The Formation Mechanism of Secondary Ettringite in Concrete due to Sulfate Attack

Two different mechanisms have been proposed for the formation of ettringite, i.e. through-solution reaction and topochemical reaction. In this paper, the formation mechanism of secondary ettringite in concrete due to sulfate attack was reviewed and analyzed. It was deduced that the formation mechanism of secondary ettringite is mainly by topochemical mechanism. The sample made from AFm (4CaO·Al2O3·CaSO4·12H2O) and Ca (OH)2 was immersed in 5% sodium sulfate at 20℃for 20 days. X-ray diffraction (XRD) was used to analyze the sample. The results verified that the formation mechanism of secondary ettringite should be attributed to topochemical reaction.

A Modulus Variation Model of Concrete under External Sulfate Attack:New Perspective from Statistical Evolution of Microcracks

A numerical model was proposed to describe the modulus variation of mortar exposed to external sulfate attack and the effectivity was verified by experiments. The model joints statistical evolution of microcracks to effective elastic modulus with microcracks and is applied to predict the damage degree of mortar attacked by sulfate. The experimental results show that the model can predict the modulus variation development of the specimen and the microcraks density. The elastic modulus values calculated by the model are consistent with that measured by experiments. The model focuses on nucleation of microcracks and finds that the theoretical results of microcracks number density show a linear growth over time in mortar. Compared with other sulfate attack damage model, this model provides a more suitable damage evolution equation that can be used to analyze the chemically assisted damage.

Effect of Polymer-based Grinding Aid on Sulfate Attacking Resistance of Concrete

Influences of polymer-based grinding aid（PGA） on the damage process of concrete exposed to sulfate attack under dry-wet cycles were investigated. The mass loss, dynamic modulus of elasticity（Erd）, and S and Ca element contents of concrete specimens were measured. Scanning electron microscopy（SEM）, mercury intrusion porosimetry（MIP）, and X-ray diffractometry（XRD） were used to investigate the changing of microstructure of interior concrete. The results indicated that PGA was capable of reducing the mass loss and improving the sulfate attack resistance of concrete. X-ray fluorescence（XRF） analysis revealed that PGA delayed the transport process of sulfate ions and Ca ions. In addition, MIP analysis disclosed that the micropores of concrete with PGA increased in the fraction of 20-100 nm and decreased in the residues of 200 nm. Compared with the blank sample, concrete with PGA had more slender and well-organized hydration products, and no changes in hydration products ratio or type were observed.

A time−space porosity computational model for concrete under sulfate attack

The deterioration of the microscopic pore structure of concrete under external sulfate attack(ESA)is a primary cause of degradation.Nevertheless,little effort has been invested in exploring the temporal and spatial development of the porosity of concrete under ESA.This study proposes a mechanical–chemical model to simulate the spatiotemporal distribution of the porosity.A relationship between the corrosion damage and amount of ettringite is proposed based on the theory of volume expansion.In addition,the expansion strain at the macro-scale is obtained using a stress analysis model of composite concentric sphere elements and the micromechanical mean-field approach.Finally,considering the influence of corrosion damage and cement hydration on the diffusion of sulfate ions,the expansion deformation and porosity space−time distribution are obtained using the finite difference method.The results demonstrate that the expansion strains calculated using the suggested model agree well with previously reported experimental results.Moreover,the tricalcium aluminate concentration,initial elastic modulus of cement paste,corrosion damage,and continuous hydration of cement significantly affect concrete under ESA.The proposed model can forecast and assess the porosity of concrete covers and provide a credible approach for determining the residual life of concrete structures under ESA.