混凝土中Thaumasite硫酸盐侵蚀的形成与特征

介绍了国内外混凝土硫酸盐侵蚀研究的最新动态———Thaumasite硫酸盐侵蚀研究的现状,从微观物相角度分析其与钙矾石硫酸盐侵蚀的异同点,选择其鉴别判断的有效手段,分析了其侵蚀特征、宏观破坏形式及发生条件。结合我国有关工程环境特征和重点建设项目特点,分析混凝土Thaumasite硫酸盐侵蚀在我国工程建设中发生的可能性,提出了深入研究混凝土Thaumasite硫酸盐侵蚀的重要性。

不同温度下Fe^(3+)对Thaumasite合成的影响

研究了不同温度条件下Fe3+离子含量对碳硫硅酸钙型硫酸盐侵蚀的影响。采用直接合成法,在Thaumasite的反应过程中通过添加Fe2O3引入Fe3+离子,放置合成样于5℃、20℃环境条件下,利用XRD、SEM、FTIR的分析方法,分别于3个月、6个月取样观察Thaumasite生成情况。结果表明:在未掺入Fe3+条件下,5℃比20℃更易产生碳硫硅酸钙型硫酸盐侵蚀;5℃和20℃时由于Fe3+的引入阻碍产生碳硫硅酸钙型硫酸盐侵蚀。

Use of Different Barium Salts to Inhibit the Thaumasite Form of Sulfate Attack in Cement-based Materials

We investigated the effects of different barium compounds on the thaumasite form of sulphate attack（TSA）resistance of cement-based materials when they were used as admixtures in mortars.Moreover,we analyzed the inhibition mechanisms within different types of barium salts,namely BaCO_3 and Ba（OH）_2,on the thaumasite formation.The controlcement mortar and mortars with barium salts to cement and limestone weight ratios of 0.5%,1.0%,and 1.5% were immersed in 5%（by weight）MgSO_4 solution at 5 ℃ to mimic TSA.Appearance,mass,and compressive strength of the mortar samples were monitored and measured to assess the generaldegradation extent of these samples.The products of sulphate attack were further analyzed by XRD,FTIR,and SEM,respectively.Experimentalresults show that different degradation extent is evident in allmortars cured in MgSO_4 solution.However,barium salts can greatly inhibit such degradation.Barium in hydroxide form has better effectiveness in protection against TSA than carbonate form,which may be due to their solubility difference in alkaline cement pore solution,and the presence of these barium compounds can reduce the degree of TSA by comparison with the almost completely decomposed controlsamples.

Mechanism of Thaumasite Formation in Concrete

Significant efforts have been made in revealing the mechanism of thaumasite formation in concrete, which continues to be fraught with ambiguities and dissension. Chemical method was employed to synthesize pure C3S, C2S, C3A, ettringite, and thaumasite, and X-ray diffraction（XRD）, Raman spectroscopy and infrared spectroscopy（IR） were used to identify thaumasite from other hydrates. To investigate the direct route of thaumasite formation, C3S, C2S, gypsum, and calcium carbonate were used to prepare a cement paste so that the interference of ettringite formation can be avoided. The indirect route of thaumasite formation was also studied by considering the effect of C3A or ettringite content on thaumasite formation. Results show that thaumasite can be definitely generated in the absence of aluminium-bearing minerals or ettringite under appropriate conditions, while the ettringite presence promotes the thaumasite formation. No evidences support the heterogeneous nucleation route in this work. It is concluded that the method mentioned in this work can surely be used to investigate the mechanism of thaumasite formation, and thaumasite can form by both direct and woodfordite routes.

Effect of Silica Fume on the Thaumasite Form of Sulfate Attack on Cement-based Materials

Thaumasite form of sulfate attack（TSA） can be observed in cement containing limestone under sulfate condition at low temperature. Mixing with suitable mineral admixture could be a good choice to improve the TSA resistance performance of cement-based materials. We investigated the durability performance of limestone-cement mortars reinforced with silica fume（SF） in 5% MgSO_4 solution at 5 ℃. The mortars, which were immersed in aggressive condition, were prepared with 2%, 4%, 6%, 8%, and 10% cement replacement by SF at a fixed water-to-binder ratio. Appearance, compressive strength, change of length and mass and corrosion products were investigated to evaluate the TSA resistance performance of SF based specimens. The results showed that specimens in the absence of SF almost disintegrated. Increasing SF dosage can reduce the degree of deterioration of SF mortars in TSA environment. Mortar mixtures with more than 6% SF merely show slight degeneration in relation to macroscopic and microscopic tests and characterizations.

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.

Effects of Thaumasite Formation on the Performance of Portland-limestone Concrete Stored in Magnesium Sulfate Solution

The influence of theaumasite formation on the performance of Portland-limestone cement concrete stored in magnesium sulfate solution was studied.The experimental results show that the deterioration of Portlandlimestone cement concrete is higher than that of Portland cement concrete.The more the content of limestone,the more serious the deterioration of concrete,and also the lower the temperature,the earlier the deterioration of concrete.Thaumasite was detected to form in the Portland-limestone pastes when stored in 10wt% MgSO4 solution at 3-10℃ and is was easy to form at lower temperatures.

Influence of Curing Duration on Thaumasite Formation of Portland-limestone Cement Pastes

Extensive researches have been carried out on the conventional sulfate attack, while it has been found that the thaumasite form of sulfate attack（TSA）, sulfate attack at low temperature, has just been discovered and its mechanism is not well understood so far. In this study, the sulfate attack of cement paste incorporating 30% mass of limestone powder was investigated. After 20 ℃ water cured for 7, 14, and 28 days,respectively, 20 mm cube specimens were exposed in a 5% magnesium sulfate solution at（6 ±1） ℃ for periods up to 240 days. Their appearance change, compressive strength development were examined at different storage time, and selected paste samples were examined by X-ray diffraction（XRD）, Fourier transform infrared spectroscopy（FTIR）, scanning electron microscopy（SEM） and energy dispersive spectroscopy（EDS）. The results indicate that all Portland-limstone cement pastes suffer from appearance deterioration to some extent. The compressive strength of cement paste initially increases and after 120 days decreases with increasing exposed period. In addition, the cement paste with short curing time is more susceptible to sulfate attack, which directly leads to the formation of non-binder thaumasite crystal accompanied by the formation of ettringite, gypsum and brucite, and becomes a white, mushy, and incohesive matrix. Additionally, the extent of sulfate attack is greater and the formation of thaumasite is observed earlier for shorter curing time.

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.

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 ℃).

Effect of Fly Ash on TSA Resistance of Cement-based Material

Thaumasite form of sulfate attack（TSA）is a major concern in evaluating durability of concrete structures subjected to sulfate and carbonate ions.By means of Fourier transform infrared spectroscopy （FT-IR）,X-ray diffraction（XRD）,scanning electron microscopy（SEM）,and energy dispersive spectrum（EDS） as well as Raman spectra of erosion substances,effect of fly ash on TSA resistance of Portland cement-based material were investigated.Immersed in magnesium sulfate solution with 33 800 ppm mass concentration of SO 4 2-at 5±2℃for 15 weeks,ratio of compressive strength loss decreased as binder replacement ratio of fly ash increased.Furthermore,when binder replacement of fly ash was 60%,compressive strength increased.When thaumasite came into being in samples with 0,15%binder replacement ratio of fly ash,ettringite and gypsum appeared in those with 30%,45%,60%binder replacement ratio of fly ash.Results mentioned above showed that fly ash can restrain formation of thaumasite and improve TSA resistance of Portland cement-based material sufficiently.

掺聚合物胶粉的硫铝酸盐水泥砂浆耐久性研究

通过测试不同聚合物胶粉种类、不同聚合物胶粉掺量硫铝酸盐水泥砂浆在硫酸盐、Thaumasite盐以及海水浸泡条件下的抗侵蚀变化规律,研究了聚合物胶粉种类、掺量对硫铝酸盐水泥砂浆耐久性的影响。结果表明:聚合物胶粉能够改善硫铝酸盐水泥砂浆的耐久性,浸泡180d后,当聚合物胶粉掺量为2%时,砂浆抗硫酸盐侵蚀的Kp值提高了5.83%;当聚合物胶粉掺量为4%时,砂浆抗Thaumasite盐侵蚀的Kp值提高了20.41%;当聚合物胶粉掺量为3%时,砂浆抗海水侵蚀的Kp值提高了18%。

Attack of Limestone Cement-based Material Exposed to Magnesium Sulfate Solution at Low Temperature

Limestone in cement could be a source of CO3^2- needed for thaumasite formation which will result in thanmasite form of sulfate attack （TSA） probably. TSA has more deterioration than ettringite or gypsum form of sulfate attack because it targets the calcium silicate hydrates （C-S-H） which is the main binder phase in all Portland cement-based materials. By means of physical and mechanical property testing as well as erosion phases analysis, magnesium sulfate attack of cement-based material containing 35% limestone powder by mass at 5 ± 2 ℃ is investigated. The compressive strength and flexural strength of mortar specimen immersed in MgSO4 solution increase firstly, then decrease rapidly with the immersing age. Relative dynamic elastic modulus of mortar specimen changes in a phased process. After immersing in MgSO4 solution for 15 weeks, the main erosion phases in paste specimen change from four phases compounds, three phases compounds to two phases compounds from surface to inside. Deterioration course of limestone cement-based material exposed to magnesium sulfate aggressive environment appears progressive damage layer by layer, and every layer probably suffers four stages, which are property strengthening stage, initial degradation stage, thaumasite formation stage and cementation loss stage, respectively.