碱激发胶凝材料抗硫酸盐侵蚀机理的探讨

对碱-矿渣、碱-粉煤灰、碱-偏高岭土和普通硅酸盐水泥的抗硫酸盐侵蚀机理进行了探讨,其中用普通硅酸盐水泥作为对比样.采用实验室加速试验法(即干湿循环法),并对侵蚀后的碱激发胶凝材料的产物进行X射线衍射(XRD)分析.结果表明:在5%的硫酸钠溶液中,碱激发胶凝材料砂浆主要是由于环境中硫酸钠溶液浸入试块孔隙中,使盐结晶产生体积膨胀而破坏,而普通硅酸盐水泥砂浆主要是由于生成膨胀性产物石膏和硫酸钠盐结晶而破坏.     

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.     

Properties and Acceleration Mechanism of Cement Mortar Added with Low Alkaline Liquid State Setting Accelerator

Low alkaline liquid state setting accelerator(LSA) for Portland cement was prepared in laboratory from aqueous solution of several inorganic sulfate salts and some organic chemical substances. Properties of cement with addition of LSA relating to its setting time and strength development as well as its resistance to sulfate attack for short and long term exposure were experimentally examined. The experimental results showed that 5%-7% addition of LSA significantly accelerated the initial and final setting of Portland cement in the presence or absence of the blending of mineral admixtures, the initial and final setting time being less than 3 min and 6 min respectively. Meanwhile, the early 1 day curing age compressive strength increased remarkably by 20%, while the late 28 th day curing age compressive strength remained almost unchanged as compared with that of the reference accelerator free cement mortar specimen. Furthermore, mortar specimens of cement added with LSA and exposed to 5% Na2SO4 solution showed their excellent resistance to sulfate attack, with their short and long term curing age resistance coefficient to sulfate attack being around 1.04 to 1.17, all larger than 1.0. XRD analysis on hardened cement paste specimens at very early curing ages of several minutes disclosed the existence of more ettringite in specimens added with LSA than that of the reference specimens, meanwhile SEM observation also revealed the existence of well crystallized ettringite at very early hydration stage, suggesting that the accelerated setting of Portland cement can be attributed to the early and rapid formation of ettringite over the whole cement paste matrix due to the introduction of LSA. MIP measurement revealed that hardened cement paste specimens with the addition of LSA presented less medium diameter pores, more proportion of small pores and less proportion of large capillary pores, which is in a very good coincidence with the improvement of strength development of cement mortars added with LSA.     

硅灰对水泥净浆抗硫酸盐侵蚀性能的改善作用

将水泥净浆试件在5%Na2SO4溶液中长期浸泡,用试件强度随浸泡时间的变化和试件中物相的XRD分析,研究了硅灰对水泥净浆抗硫酸盐侵蚀性能的影响.在Na2SO4溶液侵蚀下,普通硅酸盐水泥净浆试件强度随浸泡时间先增长,然后急剧降低;外观和XRD相分析表明,其原因是由于形成了膨胀性钙矾石,造成试件开裂破坏;加入硅灰的水泥净浆试件强度损失明显减小,尤其是抗折强度没有降低,其抵抗强度下降系数还略有增加;原因是由于硅灰的稀释作用和火山灰效应减少了水泥净浆中Ca(OH)2的量,从而降低了水泥净浆试件在硫酸盐溶液侵蚀下形成的膨胀性钙矾石的量.因而,硅灰对水泥混凝土抗硫酸盐侵蚀性能有改善作用.     

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.     

溶液浓度和温度对混凝土硫酸盐侵蚀速度影响

通过大量试验,采用强度损失、试件的长度变化和重量损失3种判定指标研究了溶液浓度和温度对硫酸盐侵蚀速度的影响。结果表明:侵蚀破坏速度随着溶液浓度增大和温度的提高而加快,但当浓度和温度超过某一数值后继续增加,侵蚀破坏的速度反而减慢。在各种影响因素下,硫酸钠侵蚀破坏的速度比硫酸镁侵蚀快。对硫酸钠型侵蚀,采用抗折抗蚀系数作为判定指标较为合理,而对硫酸镁型侵蚀,应该综合考虑抗折抗蚀系数和抗压抗蚀系数。     

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。     

掺矿物掺合料盾构管片混凝土的高温性能研究

混凝土作为盾构隧道中钢筋混凝土管片结构的关键组成部分,与钢筋混凝土结构的稳定性与耐久性密切相关,而不同矿物掺合料制备的混凝土性能存在差异。在800℃条件下,以所设计的混凝土钢筋保护层厚度处(50 mm)温度达到250℃的时间确定为耐火极限,研究了不同矿物掺合料制备的盾构管片混凝土在高温作用下的性能。结果表明:混凝土试件在经历高温作用时,其中心处的温度变化速率包括成峰,波动和平稳三个阶段。掺加25%矿粉试件(J2)的耐火极限为19 min,爆裂面积为7.06 cm2,测试结果优于纯水泥体系试件(J0)和掺加20%粉煤灰试件(J3)。J0,J2和J3达到耐火极限后冷却36 h的物理力学性能损失率相近:抗压强度损失率约为50%,弹性模量损失率约为40%。此外,J0,J2和J3的超声波声速值约为2.5 km/s。     

Influence of Calcium Sulfate State and Fineness of Cement on Hydration of Portland Cements Using Electrical Measurement

1 IntroductionThe calcium sulfate state includes gypsum, hemi-hydrate and anhydrite .Inthe modern Portland cement in-dustry,the gypsumis used as a setting retarder for reac-tion with C3A[1]. With the presence of gypsumin theformof CaSO4·2H2O,the gypsum dissolves and reactsprimarily with C3A and C4AF to form ettringite . Thisettringite isinitiallyformed with a veryfine-needle crystalstructure ,whichforms a diffusion barrier onthe surface ofthe cement . This coating avoids the unwanted fl…     

Diffusion characteristic of sulfate anion in surface region of cement mortar at early stage

The SO_4~(2-)concentration distributions in surface region of cement mortar immersed in sulfate solution at early stage were measured by layered sampling method combined with chemical analysis, and the diffusion coefficients of SO_4~(2-)anions in surface region of mortar into internal area were calculated by means of instantaneous plane diffusion theory. The experimental results showed that the SO_4~(2-)concentration gradually reduced when the diffusion depth increased in the surface region of mortar. Diffusion coefficient(D) was relevant with the concentration and kind of environmental sulfate solution, which reduced with immersion time at the beginning, and then rose slowly after a period of time. The calculation of initial diffusion coefficient(D_0) and starting time of deterioration(t_∞) caused by sulfate attack was further attempted based on the data of diffusion coefficient, and it was found that D_0 and t∞ were all relevant with concentrations of sulfate and different kind of sulfate as well.     

Effect of fly ash and early strength agent on durability of concrete exposed to the cyclic sulfate environment

The effect of fly ash and early strength agent on resistance of concrete to the cyclic sulfate environment was studied. Concrete specimens made with ordinary portland cement or ordinary portland cement incorporating fly ash with the replacement of 10% or 20%, or 1% early strength agent and fly ash with the replacement of 20%, were made and subjected to 250 cycles of exposure to the cyclic sulfate environment. Concrete properties including loss of mass, chloride ion diffusion coefficient, compressive strength and flexural strength were measured. Microstructure and chemical component of samples were determined by means of X-ray diffraction, scanning electron microscopy and energy dispersive spectroscopy. The experimental results indicated that effect of fly ash on the cyclic sulfate resistance of concretes was mostly dependent on the amount of fly ash. Early strength agent improved performances of concrete with 20% fly ash exposed to cyclic sulfate environment.     

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.     

中性钠盐碱矿渣水泥抗化学侵蚀性能研究

研究了中性钠盐碱矿渣水泥在酸性溶液、硫酸盐溶液和海水中的抗化学侵蚀性能。借助X-射线衍射和压汞测孔法考察了中性钠盐碱矿渣水泥的水化产物及水泥石孔结构特征, 并指出高稳定性的水化产物和优良的孔结构是其具有优异抗化学侵蚀性能的主要原因。     

酸碱环境下硫酸钠侵蚀对水泥土的力学特性影响

为了探究硫酸钠对不同酸碱环境中水泥土构件的腐蚀情况,采用正交试验以不同浓度的硫酸钠溶液来养护水泥土,分析水泥土经酸碱溶液与硫酸钠腐蚀后的强度变化规律,以及在一定范围内各因素对水泥土强度劣化的影响程度,并拟合水泥土强度随各因素的变化曲线.通过对试验结果进行极差和方差分析,在不同酸碱条件下对水泥土强度影响最大的为水泥掺量,其次为养护龄期,硫酸钠溶液影响最小.利用试验数据建立水泥土强度与三因素的回归方程,可以对实际工程中相应条件下水泥土强度预测提供试验依据.     

混凝土表面氯离子浓度时变规律试验研究

采用氯盐浸泡试验,定期检测了混凝土表面处的氯离子浓度,并对数据进行了拟合分析,研究了混凝土表面氯离子浓度随时间的变化规律,分析了氯盐溶液浓度、水灰比和粉煤灰掺量对表面氯离子浓度大小及其累积速率的影响。结果表明,表面氯离子浓度随时间的增加逐渐增长并最终达到稳定状态。随着氯盐溶液浓度的增加,表面氯离子浓度将更快地达到稳定状态,表面氯离子浓度也相应增大;水灰比越大,表面氯离子浓度累积速率越快,表面氯离子浓度越大;掺入粉煤灰可加快表面氯离子浓度的累积速率,表面氯离子浓度随粉煤灰掺量的增加而增大。通过对现有模型的比较与修正,提出了一个更为完善的模型。     

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.     

氯氧镁水泥抗水性研究

讨论了硅粉、粉煤灰、磷酸盐、硫酸盐、复合外加剂等对提高氯氧镁水泥抗水性的作用；对氯氧镁水泥抗水性的微观结构进行了分析．分析结果认为，使用复合抗水剂效果最好．     

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 sulfa...     

镁氧类油井水泥膨胀剂膨胀机理的研究

基于膨胀剂原地反应模型和化学热力学原理,讨论了晶体生长压的源动力及水泥浆体体积膨胀与结晶压的关系。经过分析得知：膨胀驱动力来自于水化体系化学势的降低而产生的结晶膨胀压,即化学能被转化成机械功。采用镁氧油井水泥膨胀剂和高抗硫Ｇ级油井水泥,考察了油井水泥浆塑性体的塑性强度和膨胀的关系以及硬化体的膨胀性能,为理论分析提供了有力的实验证据。结果表明：水泥浆体产生膨胀的充要条件是①浆体的塑性强度足够大（受限的晶体生长）;②在水泥浆体中反应物的局部浓度过饱和（反应产物的溶度积比标准状态下大）。     

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.