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.

The Impact of Aluminum- and Iron-Bearing Admixtures on the Resistance of Portland Cement Mortars to Alkali-Silica Reaction and Sulfate Attack

Study of sulfate resistance of mortars with aluminum- and iron-bearing admixtures (Al(OH)3, Al2(SO4)3, FeSO4, Fe2(SO4)3) in conditions close to those established in ASTM C 1012, and the study of the mitigation effect of these admixtures on alkali-silica reaction in accordance with accelerated “mortar bar” test ( GOST 8269.0, ASTM C 1260) were performed. Iron (II) and (III) sulfates show ability for mitigation alkali-silica reaction, while also, in contrast with Al-bearing substances, do not induce the drastic reducing of the initial setting time and do not promote the progress of sulfate corrosion. Compared with FeSO4, iron (III) sulfate has moderate deleterious impact on the early strength of cement paste and can be of interest alone as an inhibitor of ASR. Iron (II) sulfate may be used together with aluminum sulfate to offset the accelerating effect of the latter on the setting of cement paste and to reduce a risk of sulfate corrosion. During prolonged water storage, the mortar elongation and secondary ettringite formation do not occur, even when Al2(SO4)3 is available. Therefore, the investigated admixtures cannot act as agents of internal sulfate attack, however, Al2(SO4)3 can enhance the outer sulfate attack.

Influence of Benzenediols—Pyrocatechol and Resorcinol—On the Resistance of Portland Cement Mortars with Aluminum Sulfate to Sulfate Attack

The effect of benzene-1,2-diol (pyrocatechol) and benzene-1,3-diol (resorcinol) on the development of sulfate attack in Portland cement mortars containing alkali-free setting accelerator (aluminum sulfate) was studied. It has been found that these compounds (especially pyrocatechol—due to its ability to form chelate complexes with aluminum ions) restrain destructive deformations of Portland cement mortars with aluminum sulfate admixture when under test conditions a constant supply of sulfate ions from external source is provided. According to 27Al-MAS NMR data, pyrocatechol does not influence the amount of ettringite formed in Portland cement paste during its store in sodium sulfate solution. Presumably, in presence of benzenediols, in cement mortars with aluminum sulfate admixture the formation of ettringite crystals with a less pronounced destructive effect takes place.

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 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.

Effect of Limestone Powder and Fly Ash on Magnesium Sulfate Resistance of Mortar

The effect of limestone powder and fly ash on magnesium sulfate resistance of mortar was studied by testing on the strength, expansion and hydration products of the specimens stored in MgSO4 solution at certain periods. The experimental results show that the strength of mortar stored in MgSO4 solution increases a little before 28 d, but decreases fast subsequently. The more the contents of limestone powder and fly ash, the less the strength losses. Mortar swells in the MgSO4 solution with the soaking time. And the more the contents of limestone powder and fly ash, the less the expansion rate is. The expansion or strength loss of mortars results from the expansion of gypsum, as well as the loss of Ca（OH）2 and other hydration products of cement. The magnesium sulfate resistance of the mortars containing limestone powder and fly ash is high.

Grey Clustering Theory to Assess the Effect of Mineral Admixtures on the Cyclic Sulfate Resistance of Concrete

Concrete specimens made with ordinary portland cement or ordinary portland cement incorporating fly ash with the replacement of 10% or 20%, ground blast furnace slag with the replacement of 15% or 30%, or 15% fly ash and 15% ground blast furnace slag were made and exposed to a cyclic sulfate environment. Concrete properties including relative dynamic elastic modulus, chloride ion diffusion coefficient, compressive strength and flexural strength were measured. Effect of mineral admixtures on the cyclic sulfate resistance of concrete was assessed based on the grey clustering theory. The experimental results indicate that the cyclic sulfate resistance of concrete incorporating ground blast furnace slag belongs to the higher grey grade, which exhibits that it possesses excellent cyclic sulfate resistance. With increasing addition of fly ash, the cyclic sulfate resistance of concrete changes from the medium grey grade to the lower grey grade, which shows that incorporation of fly ash is disadvantageous for the cyclic sulfate resistance of concrete.

SULFATE RESISTANCE MECHANISM OF HIGH- PERFORMANCE CONCRETE CONTAINING NCI

It is found that the incorporation of Nitrite Corrosion Inhibitor (NCI) greatly weakens the resistance of mixtures to sulfate attack. To study the mechanism of this phenomenon, in this paper, the influence of NCI addition on the cement paste and microstructure change of high performance concrete specimens is studied by means of quantitative XRD, SEM tests. The results demonstrate that the incorporation of NCI accelerates the formation of calcium hydroxide and ettringite crystals, and weakens the pore refinement effect caused by the secondary hydration reaction of fly ash and microsilica. At the age up to one year, the relative crystal quantity in mixture containing NCI is always higher than that in control mixture. The reasons for the degradation in sulfate resistance of mixtures may be attributed to the increase and stability of the calcium hydroxide and ettringite crystals formed and the weakening of secondary hydration reaction. Based on the results, conclusion can be drawn that NCI should be used cautiously in practical engineering where high resistance to sulfate attack is required. (Author abstract) 7 Refs.

The Impact of Aluminum-Containing Set Accelerators on Sulfate Resistance of Portland Cement Compositions

This study contains comparative research of sulfate resistance of ordinary Portland cement pastes with addition of basic aluminum sulfate (hydroxosulfate, Al(OH)1.78(SO4)0.61) and amorphous Al(OH)3. Over 3 months of storing in sodium sulfate solution, the most significant expansion and deterioration occur in case of samples with aluminum hydroxide. During sulfate resistance test, the ratio between aluminum nuclei in AFt (ettringite) and AFm phases was studied by 27Al-MAS NMR, and the impact of aluminum-containing admixtures on this ratio was specified. In accordance with NMR data, in samples with Al(OH)3, the rate of secondary ettringite formation becomes noticeable after one month of storing in sulfate solution. For samples with Al(OH)1.78(SO4)0.61, the rate of elongation and temper of changes in molar ratio between sulfoaluminate phases were comparable with reference samples without admixtures.

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.

Deterioration Mechanisms of Sulfate Attack on Concrete under Alternate Action

By micro- and macro-observations, the deterioration mechanisms of concrete under alternate action between repeated sub-high temperature/cooling by water and sodium sulfate solution attack （TW-SA） were studied; meanwhile, the single sodium sulfate solution attack （SA） was also done as comparison. Micro-observations included the analysis of attack products by thermal analysis method and the determination of sulfate-ion content from surface to interior by chemical titrating method （modified barium sulfate gravimetric method）. Macro-observations mainly included the mechanical behaviors such as compressive strength, splitting strength. The experimental results indicate, in both cases, the main attack product is ettringite, only in the first layer of case SA some gypsum is checked; in case SA, the sulfate ions mainly concentrate in the surface layer, so the attack is relatively mild; but in case TW-SA, the repeated sub-high temperature/cooling by water promotes the sulfate ions diffusing inwards, which leads to obvious strength degradation.

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.

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.

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.

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.

Unraveling the Stray Current-Induced Interfacial Transition Zone(ITZ)Effect on Sulfate Corrosion in Concrete

The rail transit in sulfate-rich areas faces the combined effects of stray current and salt corrosion;however,the sulfate ion transport and concrete degradation mechanisms under such conditions are still unclear.To address this issue,novel sulfate transport and mesoscale splitting tests were designed,with a focus on considering the differences between the interfacial transition zone(ITZ)and cement matrix.Under the influence of stray current,the ITZ played a pivotal role in regulating the transport and mechanical failure processes of sulfate attack,while the tortuous and blocking effects of aggregates almost disappeared.This phenomenon was termed the“stray current-induced ITZ effect.”The experimental data revealed that the difference in sulfate ion transport attributed to the ITZ ranged from 1.90 to 2.31 times,while the difference in splitting strength ranged from 1.56 to 1.64 times.Through the real-time synchronization of splitting experiments and microsecond-responsive particle image velocimetry(PIV)technology,the mechanical properties were exposed to the consequences of the stray currentinduced ITZ effect.The number of splitting cracks in the concrete increased,rather than along the central axis,which was significantly different from the conditions without stray current and the ideal Brazilian disk test.Furthermore,a sulfate ion mass transfer model that incorporates reactivity and electrodiffusion was meticulously constructed.The embedded finite element calculation exhibited excellent agreement with the experimental results,indicating its reliability and accuracy.Additionally,the stress field was determined utilizing analytical methods,and the mechanism underlying crack propagation was successfully obtained.Compared to the cement matrix,a stray current led to more sulfates,more microstructure degradation,and greater increases in thickness and porosity in the ITZ,which was considered to be the essence of the stray current-induced ITZ effect.

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℃).

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.

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.