干湿循环下MgSO4侵蚀对UHPC相组成及其微结构的影响机理

UHPC在海洋工程建设中具有良好的应用前景,但海洋环境中存在的腐蚀性离子和干湿循环作用将会影响UHPC的微观结构,进而影响其耐久性能.通过XRD,SEM-EDS,29 Si和27 Al NMR等方法研究了干湿循环下MgSO4侵蚀和养护制度对UHPC微结构的影响.结果表明:干湿循环下MgSO4侵蚀可促进UHPC浆体中AFt和Mg(OH)2生成,降低C-S-H凝胶的Al[4]/Si和Ca/Si,并促进TAH和硅氧链上脱离的Al向AFt和AFm转化;210℃-2 MPa压蒸养护过程可降低UHPC浆体中的Ca(OH)2和SiO2含量,提高UHPC浆体的水化程度和致密度,并形成Al[4]/Si较高且Ca/Si较低的C-S-H凝胶;压蒸养护可减少侵蚀作用下AFt和Mg(OH)2的生成,有效削弱MgSO4干湿循环侵蚀对UHPC浆体中C-S-H凝胶的脱铝和脱钙作用,并减少Al相转化程度.     

卤水侵蚀对水泥粉煤灰浆体微结构影响

采用XRD、29Si和27Al MAS NMR测试技术,研究了粉煤灰掺量和侵蚀龄期对卤水侵蚀下水泥-粉煤灰浆体水化产物相组成、含铝相产物迁移与转变、C-S-H凝胶微结构变化的影响规律.研究结果表明:卤水侵蚀导致浆体Ca (OH)2含量降低,AFm和TAH向AFt转变,同时生成大量Friedel盐,C-S-H凝胶中Al[4]脱出;随粉煤灰掺量增加,浆体中AFt、AFm和TAH生成量降低,C-S-H的MCL和Al[4]/Si增大,Friedel盐生成量先增后减;侵蚀早期,水泥-粉煤灰浆体结构疏松,AFt生成量较纯水泥高,后期浆体致密性提高,抑制卤水侵蚀,AFt生成量较少,C-A-S-H脱铝作用减弱.     

养护制度对高掺花岗岩石粉UHPC性能的影响

研究了三种养护制度条件下,高掺(22％)花岗岩石粉UHPC力学性能(3 d、28 d和180 d抗压/抗折强度)和胶凝浆体C-S-H凝胶微结构(水化程度、平均分子链长(MCL)和直链中的[SiO4](Q2))的变化规律.结果表明:同一龄期抗压/抗折强度、胶凝浆体水化程度、C-S-H凝胶MCL和Q2相对含量变化规律由高到低依次为压蒸养护、蒸汽养护和标准养护;随着养护温度和压力增加,其后期强度和胶凝材料水化程度增幅逐渐降低,且不利于后期C-S-H凝胶MCL发展.高掺花岗岩石粉的UHPC胶凝浆体中常温下的水化产物主要包括C-S-H凝胶、AFt和Ca(OH)2,随着养护温度和压力的升高,AFt和Ca(OH)2相对含量降低;至210℃2 MPa时,XRD图谱中两相消失且出现Tobermorite衍射峰,即高温高压环境促进了C-S-H凝胶向Tobermorite晶体转化.     

铝酸盐水泥-半水石膏二元体系饰面砂浆泛白原因分析

采用碱浸出率法测试了铝酸盐水泥及两种铝酸盐水泥-半水石膏二元体系饰面砂浆浸水后水中物相的质量,并用XRD分析了水化产物及浸水后水中物相成分,得出(1)引起铝酸盐水泥饰面砂浆泛白的主要物相为CaCO3和Al(OH)3,而CaCO3和Al(OH)3是由铝酸盐水泥的水化产物水化铝酸钙碳化分解而生成;(2)铝酸盐水泥-半水石膏二元体系在石膏量为5％时水化产物主要为CAH10和AFm,在石膏量为25％时水化产物主要为AFt,铝酸盐水泥-半水石膏二元体系出现泛白的原因是AFm的碳化,推测主要水化产物为AFt时砂浆未出现泛白的原因是生成AFt的同时有足够的AH3生成并包裹AFt,保护其不被碳化.     

丁苯乳液和乳胶粉对水泥水化产物形成的影响

用X射线衍射对晶态水化产物钙矾石(AFt)和Ca(OH)2进行表征,用环境扫描电镜观察水化硅酸钙(C-S-H)凝胶的变化,结合铝酸三钙(C3A)和硅酸三钙(C3S)的变化,分析丁苯乳液和乳胶粉对72 h内水化产物的影响.结果表明:丁苯乳液和乳胶粉促进了水泥浆体中AFt的生成,乳胶粉的效果更明显.丁苯乳液增加了AFt在浆体中的稳定性.丁苯乳液和乳胶粉使Ca(OH)2的生成量减少,乳液的效果更明显;延缓了水泥浆体中C-S-H凝胶的形成.水化72h时,改性浆体结构与未改性浆体差别不大,只是水化产物表面覆盖了一层聚合物薄膜.     

水化环境对粒化高炉矿渣粉水化产物性能影响

利用扫描电镜观察不同水化环境下粒化高炉矿渣粉水化产物微观形貌,并利用能谱分析水化产物的元素组成,计算水化产物的Ca/Si和Ca/(Si+ Al).试验结果表明:在常温养护条件下,矿渣活性较低,水化产物的Ca/Si、Ca/(Si+ Al)较高;高温养护提高了矿渣的活性,水化产物的Ca/Si、Ca/(Si+ Al)有所降低;常温碱激发环境下矿渣活性得到较好的发挥,矿渣颗粒水化较充分,水化产物的Ca/Si、Ca/(Si+ Al)较低;高温养护碱激发环境下,早期矿渣活性即被激发,但阻碍了后期矿渣活性的发挥.     

不同矿物掺合料对蒸养水泥水化产物与力学性能的影响

为探讨矿物掺合料对预制装配式混凝土水化产物与力学性能的影响,采用20％的镍铁渣粉、锂渣粉、钢渣粉与矿渣粉分别取代水泥,在早期80℃蒸养7h条件下制备了水泥净浆与砂浆,对比研究了镍铁渣粉、锂渣粉、钢渣粉与矿渣粉对7h和28 d龄期蒸养水泥水化产物和力学性能的影响.结果 表明:除了C-S-H与Ca(OH)2外,7h蒸养水泥的水化产物主要为AFm与Ca4Al2O6(CO3)0.5(OH)·11.5H2O,28 d蒸养水泥的水化产物主要为Ca4Al2O6(CO3)0.5(OH)·11.5H2O和Ca4Al2O6(CO3)·11H2O,矿物掺合料对蒸养水泥水化产物种类影响较小;掺镍铁渣粉、锂渣粉、钢渣粉、矿渣粉后,7h蒸养水泥的化学结合水含量分别达到了纯水泥的93.27％、102.22％、90.24％、102.22％,28 d蒸养水泥的化学结合水含量分别达到了纯水泥的93.76％、95.08％、86.27％、95.68％,掺锂渣粉与矿渣粉可以显著提高7h蒸养水泥的水化程度,掺钢渣粉的效果最差;此外,掺锂渣粉、钢渣粉、矿渣粉改变了蒸养7h水泥浆体C-S-H的形貌,除了纤维状C-S-H外,掺锂渣粉水泥浆体中还有蜂窝状C-S-H形成,掺钢渣粉水泥浆体与掺矿渣粉水泥浆体中还有球形与薄片状C-S-H形成;掺锂渣粉可以提高早期80℃蒸养7h水泥胶砂的抗压与抗折强度,但四种矿物掺合料均不能改善28 d蒸养水泥胶砂的力学性能.     

苯丙共聚物改性硫铝酸钙胶结料-无水石膏复合体系的水化

采用量热仪、X射线衍射仪、热重、扫描电镜、电感耦合等离子光谱等方法研究了苯丙共聚物（SA）对硫铝酸钙胶结料-无水石膏复合体系早期水化的影响。结果表明:SA会延缓水化进程,减少水化加速期钙矾石（AFt）、单硫型水化硫铝酸钙（AFm）和Al（OH）₃ （AH₃）含量,促进AH₃与石膏和氢氧化钙反应生成AFt,并促进水化后期AFt向AFm转变。同时,SA会迅速降低体系孔溶液的表面张力,随着水化反应进行表面张力趋于稳定;SA也提高了孔溶液的p H值,增大OH^–浓度,影响了体系中Ca²⁺、SO₄^2–和[Al（OH）₄]^–的浓度和比例,减小水化初期水化产物的离子浓度积,降低水化产物析出速率,进而延缓水化进程、减少水化产物。     

大掺量矿渣石膏水泥基复合材料的水化特性

通过测试宏观抗压强度,同时采用XRD和TG-DTA技术对大掺量矿渣石膏水泥基复合材料的水化特性进行了研究,研究表明:大掺量矿渣石膏水泥基材料早期强度远低于纯水泥,但其强度发展较快,尤其是7～28 d阶段,28 d强度基本达到42.5 MPa水平,90 d龄期强度除SG-4试件均超过纯水泥水平.试件早期强度随着熟料含量的增加而增长,而后期强度并不遵循这一规律,水化后期主要是矿渣粉中活性Al2O3与活性SiO2参与水化反应,提高了体系抗压强度.SG系列水化产物主要为C-S-H凝胶和AFt,而纯水泥试样有大量Ca(OH)2而几乎无AFt存在.熟料含量对早期水化产物数量影响较大,而对水化产物种类及水化后期产物数量影响不大.     

磨细钢渣对水泥水化性能的影响

采用XRD分析了掺入钢渣水泥的水化产物,并从标准稠度用水量、凝结时间、强度几方面论证了磨细钢渣对水泥水化性能的影响。结果表明:适度磨细的钢渣能减小水泥的标准稠度用水量,但过度磨细后会增加标准稠度用水量,凝结时间也有类似的结果;钢渣的最佳掺量为10%,此时28d强度达54.5MPa,物相主要为C2SH(C),AFt和Ca(OH)2,养护90d未见Aft向AFm转变。     

Analytical Electron Microscopy of Cement Pastes: II, Pastes of Portland Cements and Clinkers

Three hundred sixty-five particles of C-S-H, Ca(OH)₂, AFm phase, and AFt phase from pastes of normally ground portland cements and of finely ground cements and clinkers were analyzed. All the phases, except the Ca(OH)₂, showed significant variation in composition among paste specimens and among particles within each specimen. The C-S-H contains significant amounts of Al, Fe, and S; for that of a normally ground portland cement paste, cured for 28 days, the median Si:AI, Si:Fe, and Si:S ratios were 11, 43, and 15, respectively, whereas the mean Ca:Si ratio for all the particles analyzed was 2.0. The AFm phase in cement pastes is not pure monosulfate but has a mixture of sulfate, hydroxide, and Al- and Si-bearing ions in its interlayer sites; the AFt phase is not pure ettringite but contains Si and its sulfate is probably partly replaced by hydroxide. The Al and Fe contents in the C-S-H and the Si contents in the AFm and AFt phases are greater when finely ground starting materials are used. This fact, together with the marked variation among particles, emphasizes the difficulty of ionic transport in cement pastes.     

微观表征法研究煤矸石改性水泥砂浆水化机理

在水泥胶砂中掺入适当配比的煤矸石可以增加水泥砂浆的强度,尤其是早期强度.与不添加煤矸石的基准砂浆相比,煤矸石的掺量为9%时,砂浆3 d抗压强度提高1.0 MPa,28 d抗压强度提高2.0 MPa.XRD、TGA-DTA和SEM分析证实:加入煤矸石促进了水泥砂浆7 d早期水化反应,生成水化产物钙矾石、C-S-H凝胶、AFm和氢氧化钙,且水化产物的数量亦不同,各产物的晶型结构也不相同,改性后水化产物增多,水化速率加快,因而影响砂浆的宏观力学强度.     

养护温度对凝灰岩基胶凝材料力学性能的影响机理

凝灰岩是经过火山喷出散落在地面,经过压结和水化胶结固化而形成的一种火山灰碎屑岩,具有一定的火山灰活性。本文研究养护温度对凝灰岩基胶凝材料力学性能的影响,并借助FTIR、TG、SEM和MIP等对凝灰岩基胶凝材料水化产物的微观结构进行分析。结果表明,提高养护温度对凝灰岩基胶凝材料的力学性能具有一定的增强作用,提高养护温度不仅能提高早期强度,还可以提高后期强度,凝灰岩基胶凝材料的最佳养护温度为50 ℃。提高养护温度后凝灰岩基胶凝材料中没有生成新的水化产物,AFt和C-S-H等水化产物含量增加,Ca(OH)₂的含量减少。提高养护温度有利于增加凝胶孔和过渡孔占比,细化孔径结构,降低孔隙率,提高基体结构的致密度。     

Variation in the Composition of C-S-H Gel in Portland Cement Pastes Cured at Various Temperatures

Variation in the composition of C-S-H gel, the main hydration product of portland cement, cured at various temperatures, was studied using scanning electron microscopy with energy dispersive X-ray spectroscopy. Samples of two cement pastes were cured isothermally under water at 10°, 30°, and 60°C for one year. For the inner-product C-S-H gel of both cement pastes, increased curing temperature decreased the Ca/Si and Al/Ca ratios, but increased the S/Ca ratio. The Al/S and (Al + Fe)/S ratios decreased with increased curing temperature. Sulfur, probably in the form of sulfate ions, could be sorbed by the C-S-H gel at higher temperatures.     

Early hydration properties and microstructure evolutions of MgO-activated slag materials at different curing temperatures

This study reports on the early hydration properties and microstructure evolutions of MgO-activated slag at five curing temperatures (20 °C, 40 °C, 50 °C, 60 °C, and 80 °C) and three MgO types (S-MgO, M ? MgO, and R-MgO). The results indicated that high-temperature curing substantially increased the compressive strength of the specimens. Particularly, the highest strength was obtained at 40 °C and 60 °C for the S-MgO and M-MgO-activated slag specimens, respectively, and the high curing temperature for the R-MgO-activated slag specimen was 40 °C. We focused on the relationship between the mechanical properties, pore structure characteristics, and hydration products. The combination of calcium-silicate-hydrate (C-S-H) gel and Al increased under high-temperature curing conditions. XRD, FT-IR, TG-DTG, and ²⁷Al MAS-NMR results showed a high Al content in the formation of calcium silicate hydrate with Al in its structure (C-A-S-H gel) for the R-MgO-activated slag pastes under high-temperature curing; however, the microstructure was loose owing to the formation of excessive brucite. For the S-MgO-activated slag specimen, the Ca/Si ratio was high, with more Mg²⁺ penetrating the C-S-H gel interlayer, forming more hydrotalcite-like phases and increasing the chain length of the C-S-H gel. The microstructure showed good compatibility of the hydration products interweaving to form dense microstructures.     

利用煅烧硅藻土制备高稳态超高性能混凝土基体研究

超高性能混凝土(UHPC)早期自收缩大,使结构存在收缩开裂风险,掺入天然多孔活性粉料以激发其火山灰和内养护协同效应可有效降低UHPC自收缩,改善基体体积稳定性。本文利用煅烧硅藻土以一定体积分数(3%、6%、9%)置换水泥制备UHPC基体,并对其新拌性能、力学性能、自收缩、耐久性能及孔结构与微观结构进行了系统评价。结果表明:掺入煅烧硅藻土能显著改善UHPC力学性能和体积稳定性,并进一步提升其耐久性能;掺入煅烧硅藻土UHPC基体孔结构得到优化,孔隙率降低,孔径细化;掺入煅烧硅藻土UHPC基体中C-S-H凝胶平均Ca/Si比下降,C-S-H(I)占比提高,水化产物结构及致密性改善。优化设计条件下,UHPC基体56 d抗压强度提高9%,56 d抗折强度提高18%,7 d自收缩下降29%,28 d快速氯离子迁移系数下降35%,28 d电通量下降27%。     

石膏对贝利特-硫铝酸钡钙水泥强度和硬化浆体结构的影响

研究了石膏对贝利特-硫铝酸钡钙水泥强度和硬化浆体结构的影响.结果表明:贝利特-硫铝酸钡钙水泥熟料的矿物组成主要有C3S、C2S、C,A、C4AF和C2.7B1.25A3S;当水泥中石膏掺量为10%时,贝利特-硫铝酸钡钙水泥的3d、7 d、28 d和90 d抗压强度分别达到了45.0、61.9、82.1和85.6 MPa;贝利特.硫铝酸钡钙水泥的水化产物主要有AFt、Ca(OH)2、C-S-H凝胶等,随石膏掺量的增加,AFt的数量逐渐增加,水化后期的Ca(OH)2数量逐渐减少.用XRD和SEM来分析硬化水泥浆体组成和结构.     

Factors Influencing the Stability of AFm and AFt in the Ca–Al–S–O–H System at 25°C

The stabilities of Al₂O₃–Fe₂O₃‐mono (AFm) and ‐tri (AFt) phases in the Ca–Al–S–O–H system at 25°C are examined using Gibbs energy minimization as implemented by GEM‐Selektor software coupled with the Nagra/PSI thermodynamic database. Equilibrium phase diagrams are constructed and compared to those reported in previous studies. The sensitivity of the calculations to the assumed solid solubility products, highlighted by the example of hydrogarnet, is likely the reason that some studies, including this one, predict a stable SO₄‐rich AFm phase while others do not. The majority of the effort is given for calculating the influences on AFm and AFt stability of alkali and carbonate components, both of which are typically present in cementitious binders. Higher alkali content shifts the equilibria of both AFt and AFm to lower Ca but higher Al and S concentrations in solution. More importantly, higher alkali content significantly expands the range of solution compositions in equilibrium with AFm. The introduction of carbonates alters not only the stable AFm solid solution compositions, as expected, but also influences the range of solution pH over which SO₄‐rich and OH‐rich AFm phases are dominant. Some experimental tests are suggested that could provide validation of these calculations, which are all the more important because of the implications for resistance of portland cement binders to external sulfate attack.     

海水对高贝利特硫铝酸盐水泥水化过程和力学性能的影响

研究了海水拌和与海水养护条件下高贝利特硫铝酸盐水泥(HB-CSA)和普通硅酸盐水泥(OPC)胶砂的抗压强度和抗折强度,采用等温量热法、X射线衍射分析法和热重分析法表征了两种水泥的水化过程和水化产物,分析了海水对HB-CSA水化过程和力学性能的影响。结果表明:海水拌和未明显影响HB-CSA的早期水化过程,海水拌和与海水养护未改变其主要水化产物类型;海水拌和显著加快了OPC的早期水化,海水中的氯盐与OPC的水化产物反应,导致水化氯铝酸钙(Friedel盐)的生成。海水拌和与海水养护对HB-CSA的抗压强度影响较小,但降低了OPC的后期抗压强度。海水养护对HB-CSA和OPC抗折强度的提高较为明显,钙矾石(AFt)含量的增加是抗折强度提高的主要原因。HB-CSA的水化产物中未见Ca(OH)₂和单硫型水化硫铝酸钙(AFm),避免了海水侵入后过量CaSO₄·2H₂O和AFt生成造成的混凝土膨胀开裂和强度下降的危害。