温度和氯盐对混凝土硫酸盐化学腐蚀的影响

为揭示混凝土在不同硫酸盐腐蚀环境下的损伤过程及腐蚀机理,进行了硫酸盐浸泡实验,研究了在复合溶液浸泡作用下混凝土的抗压强度演变、腐蚀产物类型及硫酸根离子反应能力.结果表明:混凝土在硫酸钠溶液中抗压强度先增加后降低,且主要腐蚀产物是钙矾石和石膏.在复合溶液腐蚀环境下,腐蚀产物以钙矾石为主,且混凝土亚微观缺陷减少6.46%.当提高腐蚀溶液温度至50℃时,混凝土的抗压强度演变速度加快,硫酸根离子反应能力提高20%,腐蚀产物以石膏为主.     

Durability of asphalt mixture in different corrosion solution

The corrosion to asphalt mixture under different kinds of corrosion solution, such as pH=2 solution, pH=12 solution, pH = 12 solution and 10% Na₂SO₄ solution, was studied. The performance attenuation of asphalt mixture was analyzed under the normal environment and the freeze-thaw environment, and the analysis was given on the sensitivity of the test results to the evaluation index. The experimental results show that the performance of asphalt mixture is attenuated faster under the acidic solution, alkaline solution and sulfate solution. Corrosion factor K _c, freeze-thaw corrosion factor K _f, and freeze-thaw effect factor K _fc are proposed to evaluate asphalt mixture resistance to corrosion in different kinds of corrosion solution. The values of K _c and K _fc decrease with the increasing of corrosion time. The change rule of K _f show that the rate of corrosion is decreased by the action of freeze-thaw in acidic solution and in alkaline solution, but is increased by the action of freeze-thaw in sulfate solution. The microscopic analysis indicates that acid solution reacts with aggregate of asphalt mixture, alkaline solution reacts with asphalt cement of asphalt mixture, the surface tension of sulfate solution and crystallization of sulfate are the main reasons which weak the performance of asphalt mixture.     

Effect of corrosive solutions on C-S-H microstructure in portland cement paste with fly ash

By means of ²⁹Si and ²⁷Al magic angle spinning nuclear magnetic resonance (MAS NMR) combined with deconvolution technique, X-ray diffraction (XRD), scanning electron microscopy (SEM) as well as energy dispersive X-ray system(EDX), the effect of 5 wt% corrosive solutions (viz. 5 wt% Na₂SO₄, MgSO₄, Na2SO4+NaCl and Na₂SO₄+NaCl+Na₂CO₃) on C-S-H microstructure in Portland cement containing 30 wt% fly ash was investigated.The results show that, in MgSO₄ solution, Mg²⁺ promotes the decalcification of C-S-H by SO ₄ ^2- ,increasing silicate tetrahedra polymerization and mean chain length (MCL) of C-S-H. However, the substituting degree of Al³⁺ for Si⁴⁺ (Al[4]/Si) in the paste does not change evidently. Effect of Na²SO⁴ solution on C-S-H is not significantly influenced by NaCl solution, while the MCL and Al[4]/Si of C-S-H in fly ashcement paste slightly change. However, the decalcification of C-S-H by SO ₄ ^2- and CO ₃ ^2- attack, as well as the activation of fly ash by SO ₄ ^2- attack will increase the MCL and Al[4]/Si, which are both higher than that under Na₂SO₄ corrosion, MgSO₄ or Na₂SO₄ +NaCl coordination corrosion.     

海洋环境下混凝土的硫酸盐腐蚀机理

海水中存在的硫酸根离子传输至混凝土内部将导致其腐蚀破坏。针对矿粉掺量0~65%的C40引气混凝土进行海洋潮汐区、大气区和水下区腐蚀1~2 a,测试其水溶和酸溶硫酸根离子浓度分布;分析水泥净浆中的腐蚀产物类型及含量。试验结果表明：海洋不同腐蚀区带混凝土中硫酸根离子传输量及传输深度排序为：潮汐区 > 水下区 > 大气区。混凝土中反应硫酸根离子与总硫酸根离子的关系服从线性函数分布,反应量占总硫酸根离子量的90%以上,反应的硫酸根离子量随腐蚀龄期增加而增加。海洋潮汐区和水下区生成的腐蚀产物量高于大气区,主要是钙矾石和石膏;海洋大气区暴露混凝土的腐蚀产物为钙矾石。对于P.I.52.5水泥制备的C40混凝土而言,掺加65%的矿粉有助于提升混凝土抗海洋硫酸根离子侵蚀能力。     

高渗透压-硫酸盐侵蚀下混凝土时空劣化

为了模拟研究混凝土海水环境下的侵蚀损伤及劣化规律,采用质量分数10% Na₂SO₄溶液对混凝土试样进行不同渗透压和不同时长下的室内侵蚀试验. 结合微米压痕试验、CT扫描试验和电子显微镜扫描试验,对高渗透压-硫酸盐耦合侵蚀作用下混凝土的侵蚀损伤及微观力学性能进行研究. 试验结果显示,渗透压加速了离子迁移,主要起到了促进化学侵蚀作用. 渗透压越大,混凝土化学损伤速率越快,侵蚀深度越深;骨料与砂浆胶结处是易侵蚀、易破坏的薄弱点;混凝土内部孔隙易生成水化产物,高渗透压下容易生成大量短柱状石膏晶体及细密的针状钙矾石晶体.     

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.     

干湿交替环境下混凝土受硫酸盐侵蚀劣化机理

通过试验模拟干湿循环作用下混凝土受不同质量分数硫酸钠的侵蚀特点,从不同侵蚀时间后混凝土的表观特征、质量经时变化规律、混凝土中硫酸根离子分布、侵蚀深度、混凝土轴心抗压强度、劈裂抗拉强度经时退化规律、变形经时变化规律等方面全面衡量混凝土的硫酸盐侵蚀损伤特征;讨论硫酸盐溶液质量分数、侵蚀龄期对混凝土损伤累积规律的影响;根据SEM图像分析受蚀混凝土的微观结构特征,揭示了干湿循环和硫酸盐侵蚀共同作用下,不同侵蚀时期后混凝土损伤的演变机理.试验结果表明,在干湿循环作用下硫酸钠对混凝土的侵蚀损伤是侵蚀产物与硫酸盐结晶膨胀共同作用的结果;在侵蚀初期由于晶体的填充密实作用,使得受蚀混凝土的质量、强度与延性增大;随着侵蚀时间的延长,混凝土不仅受到钙矾石、石膏等侵蚀产物的膨胀损伤作用,而且叠加了干湿循环过程中Na2SO4·10H2O的结晶膨胀作用,使得混凝土损伤反复进行并不断累积,加速了混凝土的受蚀劣化速度,质量、强度逐渐降低,脆性变大;由于拉应力的叠加效应,混凝土劈裂抗拉强度对硫酸盐侵蚀损伤更敏感.     

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.     

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.     

Thermodynamic Stability of Sulfate Ions on Calcium Aluminosilicate Hydrate Microstructure

The thermodynamic stability of sulfate ions on synthesized calcium aluminosilicate hydrate(C-A-S-H) microstructure with different Ca/Si ratios and Al/Si ratios was investigated by XRD, SEM-EDS, ~(29) Si and ~(27) Al nuclear magnetic resonance(NMR) and thermodynamic modeling. The results indicate that sulfate attack leads to both decalcification and dealumination for C-A-S-H gels, and the amount of corrosion products(gypsum and ettringite) decreased gradually with decreasing Ca/Si ratios of C-A-S-H. Sulfate ions can also promote the polymerization degree of C-A-S-H gels, improving its resistance to sulfate attack. Moreover, the 4-coordination aluminum(Al[4]) in C-A-S-H, 5-coordination aluminum(Al[5]), 6-ccordination aluminum(Al[6]) in TAH(third aluminum hydrate) and Al[6] in monosulfate or C-A-H(calcium aluminate hydrate) can be transformed into Al[6] in ettringite by sulfate attack. Furthermore, through thermodynamic calculation, the decrease of Ca/Si ratios and increase of Al/Si ratios can improve the thermodynamic stability of C-A-S-H gels under sulfate attack, which agrees well with the experiment results.     

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 (E _rd), 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.     

冻融与腐蚀耦合作用下沥青混凝土性能研究

国内外对冻融循环与硫酸盐腐蚀耦合作用下沥青混凝土的性能鲜有研究。鉴于此,在10%Na2SO4溶液加速劣化条件下采用真空饱水冻融劈裂试验,以冻融腐蚀因子评价沥青混凝土在冻融与腐蚀耦合作用下的性能变化规律。试验结果表明硫酸盐腐蚀加剧了冻融循环对沥青混凝土的破坏作用。SEM微观分析表明硫酸盐溶液较水溶液更易于侵入沥青膜与集料界面及沥青混凝土空隙中,并在冻融条件下发生结冰膨胀导致界面强度降低和裂缝的产生与扩展是沥青混凝土性能衰减的主要原因。水镁石纤维具有优良的稳定效应、界面增强效应和加筋桥接效应,掺加水镁石纤维可以有效提高沥青混凝土抗冻融腐蚀性能。     

SO2-4对块体纳米晶铜阳极极化行为的影响

为了揭示SO₂^-4对块体纳米晶铜耐蚀性能的影响规律,利用电化学方法,结合X射线衍射、能谱分析、扫描电镜等表面分析技术,研究了惰性气体沉积原位温压法制备的块体纳米晶铜在不同质量分数（0.3%、1.3%、2.3%、3.3%和4.3%）Na₂SO₄溶液中的阳极极化行为.结果表明,随着SO₂^-4的增多,纳米晶铜的致钝电流密度增大,而致钝电位降低.在0.3%的Na₂SO₄溶液中加入1%的NaCl,纳米晶铜阳极极化行为发生明显变化,Cl^-在纳米晶铜表面形成难溶于水的CuCl保护钝化膜,纳米晶铜致钝电流密度降低,活化-钝化过渡区电流密度下降速率显著减小.     

Evolution and characterization of damage of concrete under freeze-thaw cycles

To study the internal damage of concrete under freeze-thaw cycles, concrete strains were measured using embedded strain gauges. Residual strain and coefficients of freezing expansion (CFE) derived from strain-temperature curves were used to quantify the damage degree. The experimental results show that irreversible residual strain increases with the number of freeze-thaw cycles. After 50 cycles, residual strains of C20 and C35 concretes are 320με and 100με in water, and 120 με and 60 με in saline solution, respectively. In lower temperature range (-10 ℃ to -25 ℃) CFE of C20 and C35 concretes decrease by 9.82×10-6/K and 8.44×10-6/K in water, and 9.38×10-6/K and 5.47×10-6/K in saline solution, respectively. Both residual strains and CFEs indicate that during the first 50 freeze-thaw cycles, the internal damage of concrete in saline solution is less than that of concrete in water. Thus residual strain and CFE can be used to measure the frost damage of concrete.     

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.     

Influence of Thermally Treated Flue Gas Desulfurization （FGD） Gypsum on Performance of the Slag Powder Concrete

The feasibility of flue gas desulphurization （FGD） as concrete admixture was studied. A combined concrete admixture of the thermally-treated FGD gypsum and slag powder was explored. The FGD gypsum was roasted at 200℃ for 60 min and then mixed with the slag powder to form FGD gypsum-slag powder combined admixture in which the SO3 content was 3.5wt%. Cement was partially and equivalently replaced by slag powder alone or FGD gypsum-slag powder, at concentration of 25wt%, 40wt%, and 50wt%, respectively. The setting times, hydration products, total porosity and pore size distributions of the paste were determined. The compressive strength and drying shrinkage of cement mortar and concrete were also tested. The experimental results show that, in the presence of FGD gypsum, the setting times are much slower than those of pastes in the absence of FGD gypsum. The combination of FGD gypsum and slag powder provides synergistic benefits above that of slag powder alone. The addition of FGD gypsum provides benefit by promoting ettringite formation and forms a compact microstructure, increasing the compressive strength and reduces the drying shrinkage of cement mortar and concrete.     

Durability of concrete subjected to the combined actions of flexural stress,freeze-thaw cycles and bittern solutions

Freeze-thaw durabilities of three types of concretesnormal portland cement concrete （OPC）, high strength concrete （HSC） and steel fiber reinforced high strength concrete （SFRHSC） were systemically investigated under the attacks of chemical solution, and combination of external flexural stress and chemical solution. Four kinds of bitterns from salt lakes in Sinkiang, Qinghai, Inner Mongolia and Tibet provinces of China were used as chemical attack solutions. The relative dynamic modulus （RDM） was used as an index for evaluating the damage degree during the course of chemical attack and stress corrosion. The experimental results show that the freeze-thaw durability of concrete is visibly reduced in the present of the flexural stress, i e, stress accelerates the damage process. In order to quantify the stress accelerated effect, a stress accelerating coefficient was proposed. The stress accelerating coefficient is closely related with the types of bitterns and the numbers of freeze-thaw cycles is. The more numbers of freeze-thaw cycles is, the greater the stress accelerating coefficient for various concretes will be. In addition, there also exists a critical ratio of external stress to the maximum flexural stress. If the stress ratio exceeds the critical one, the freeze-thaw durability of various concretes will be greatly decreased compared to the responding concretes without applied stress. The critical stress ratio of OPC, HSC and SFRHSC is 0.30, 0.40 and 0.40, respectively, indicating that HSC and SFRHSC have advantages over OPC and are suitable to use in the bittern erosion regions.     

硫酸盐侵蚀下轴心受压钢筋混凝土柱应力时变过程的数值分析

针对荷载和硫酸盐耦合作用过程中钢筋混凝土柱的应力分析问题,在已有混凝土内硫酸根离子扩散反应模型的基础上,进一步给出了硫酸盐侵蚀引起的混凝土损伤程度与硫酸根离子浓度及腐蚀时间之间的关系,建立了与损伤程度相关的混凝土腐蚀本构模型及轴压混凝土柱截面应力的计算方法,并通过数值模拟分析了柱截面内硫酸根离子传输、腐蚀损伤程度变化、截面应变和应力分布规律。结果表明：硫酸根离子浓度和混凝土损伤程度在柱截面内呈梯度分布,且受二维交互效应的影响明显;随腐蚀时间的增加,截面损伤区逐渐向内移动且其宽度增加,而混凝土应力在损伤区呈先增加后逐渐降低、在未损伤区基本呈线性增加的趋势。硫酸盐侵蚀过程中,轴压混凝土柱截面应力发生了明显的重分布现象。     

毛细作用下硫酸钠半浸泡水泥基材料抗氯离子渗透性研究

硫酸盐和氯盐复杂盐蚀环境中的服役结构会受到两者产生的耦合作用。研究毛细作用下硫酸钠半浸泡混凝土试样的抗氯离子渗透性能,设计不同水灰比、不同硫酸钠溶液浓度的砂浆毛细上升试验,测试硫酸钠半浸泡混凝土试样的扫描电镜（SEM）、X射线衍射（XRD）和氯离子电通量。结果表明：硫酸钠半浸泡混凝土抗氯离子渗透性能劣化,前期劣化严重,随着半浸泡时间的延长,抗氯离子渗透性能有所回升,但依然比未浸泡试样的差。结合微观测试结果可知,混凝土抗氯离子渗透性能劣化的主要原因是：前期,在毛细作用下硫酸钠溶液填充了混凝土孔隙,减弱了固化氯离子的结合能力,释放了较多自由氯离子,从而增大了氯离子的扩散量;后期,随着浸泡时间的延长和环境湿度的变化,孔隙中的硫酸钠溶液过饱和后,形成无水Na₂SO₄和Na₂SO₄·10H₂O结晶体的混合物,结晶混合物沉淀于孔壁,部分阻碍了氯离子的扩散,从而减缓了抗氯离子渗透性能的劣化。硫酸钠溶液浓度超过5%以后,随着硫酸钠溶液浓度的升高,毛细上升速度减缓,混凝土抗氯离子渗透性能相应提高。硫酸钠溶液半浸泡下,水泥基材料毛细上升快慢可作为衡量混凝土抗氯离子渗透性能好坏的指标。硫酸钠和氯化钠的复合溶液对硫酸钠毛细上升有延缓作用,会改善混凝土的抗氯离子渗透性能。     

Damage Evolution of Concrete under the Actions of Stray Current and Sulphate

Based on the mechanism of stray current generation in underground structures,the concrete durability test device for stray current and sulphate in typical soil environment was designed to study the damage of concrete under the action of stray current and sulphate.The deterioration law of concrete under the action of stray current and sulphate was studied by microscopic techniques such as scanning electron microscopy (SEM) and X-ray diffraction (XRD).The microstructure of corroded concrete was observed to determine the phase composition of erosion products.The damage performances such as quality,strength,and dynamic elastic mode of corroded concrete were performed.The experimental results show that,under the action of stray current,the products of sulfate-eroded concrete are mainly gypsum,ettringite,and thaumasite;the stray current accelerates the hydration process of cement and the erosion of concrete by sulfate;when the concrete pores are filled with the erosion product,there is an increase of approximately 10% in the concrete compressive strength and dynamic elastic modulus;and the concrete compressive strength is more sensitive to the stray current electrification period than the current intensity.