硫酸盐侵蚀对不同养护制度UHPC水化产物微结构的影响

采用29Si和27Al MAS NMR、XRD、SEM等测试技术研究了硫酸盐侵蚀对不同养护制度的超高性能混凝土(UHPC)水化产物微结构的影响.结果表明:标准养护和80 ℃高温蒸汽养护条件下,UHPC水化产物主要为C-S-H、Ca(OH)2、AFt、AFm和TAH;210 ℃、2 MPa蒸压养护8 h后,水化产物主要为tobermorite、Ca(OH)2和TAH.硫酸盐侵蚀对不同养护制度的UHPC抗压强度和水化产物微结构的影响微弱,但可促进210 ℃蒸压养护的UHPC胶凝浆体中TAH向AFm和AFt的转化.同时硫酸盐侵蚀180 d时,C-S-H凝胶MCL和Al[4]/Si略有降低,但降低幅度较小,UHPC具有良好的抗硫酸盐侵蚀能力.     

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.     

高温养护下粉煤灰效应机理研究

大体积混凝土施工过程中,为降低水化热而采用大量的粉煤灰替代水泥,故对高掺量粉煤灰水泥的水化硬化机理进行深入系统的研究具有重要的意义.以大掺量粉煤灰胶凝材料硬化浆体为研究对象,结合XRD、FTIR、NMR等测试分析,研究高养护制度下粉煤灰掺量对其水化相C-S-H凝胶硅氧四面体聚合程度的影响规律.结果表明:高温养护的硬化浆体,其水化相C-S-H凝胶硅氧四面体聚合程度和Al原子取代Si原子的程度,在各个养护龄期始终高于常温养护的硬化浆体.     

C3A掺量对C3A-C3S浆体微结构的影响

采用X射线衍射(X-ray Diffraction,XRD)、29Si核磁共振(29Si Nuclear Magnetic Resonance,29Si NMR)、27Al核磁共振(27Al Nuclear Magnetic Resonance,27Al NMR)和BET氮吸附等方法研究了标准养护条件下C3A掺量对C3S-C3A复合浆体微结构的影响.结果表明:C3A的加入可以促进C3S-C3A复合浆体的水化,释放的Al3+可以进入C-S-H凝胶硅氧链上的桥硅氧四面体位置,形成Al掺杂C-S-H凝胶;随C3A掺量增大,复合浆体中C-S-H凝胶的Al[4]/Si和MCL增大;随养护龄期增大,Al掺杂C-S-H凝胶硅氧链上的Al[4]逐渐脱出,进入浆体并转化为Al[6],导致相同C3A掺量下的复合浆体中Al[4]相对含量下降,Al[6]相对含量增长;C3A的加入在降低复合浆体平均孔径的同时,也提高了浆体的孔隙率.     

高炉镍铁渣粉在水泥基复合胶凝材料中的水化特性研究

通过对不同高炉镍铁渣掺量的水泥-高炉镍铁渣粉复合胶凝材料水化放热速率、高炉镍铁渣粉的反应程度、硬化浆体化学结合水含量以及水化产物中C-S-H凝胶Ca/Si的测定,分别研究了水泥-高炉镍铁渣粉复合胶凝材料的早期、中长期水化进程、浆体微观形貌以及水化产物特点等水化特性.研究结果表明:高炉镍铁渣的掺入会降低水化放热速率,并推迟水化加速期放热峰的出现时间;在复合胶凝体系中,随着高炉镍铁渣粉掺量的增大,其反应程度和硬化浆体中化学结合水含量将降低.复合胶凝材料水化生成的C-S-H凝胶的Ca/Si低于水泥,且随着水化的进行呈降低趋势;高炉镍铁渣粉中的Al,在水化过程中会取代部分Si进入C-S-H凝胶中,形成C-A-S-H凝胶.     

粉煤灰-水泥水化的核磁共振定量分析

利用高分辨固体核磁共振仪结合去卷积技术,定量分析了粉煤灰水泥浆体中水泥和粉煤灰的水化程度以及C-S-H凝胶中硅氧-铝氧链平均长度,同时研究了粉煤灰火山灰反应对C-S-H结构的影响。结果表明:水化3 d时,系统中约47%的水泥和14%的粉煤灰参与了水化反应,C-S-H平均链长为3.2;水化120d时,水泥和粉煤灰的水化程度分别为89%和33%,C-S-H平均链长约为3.8,远大于纯水泥浆体中C-S-H的平均链长(为2.7)。水化3 d时粉煤灰玻璃相结构中的Si—O—Si,Si—O—和Al—Al共价键断裂,形成了单体硅酸根和单体铝酸根,这些单体结构桥连体系中的二聚体单元进而提高了C-S-H平均链长。粉煤灰掺入并不会因为C-S-H聚合度提高以及ACL增加就能促进粉煤灰水泥浆体强度。     

硫铝酸盐水泥基复合体系的胶凝膨胀性能

研究了硫铝酸盐水泥熟料、二水石膏和氢氧化钙的不同复合胶凝体系水化产物与其膨胀性能及抗压强度的关系，利用XRD及Rietveld全谱拟合法和TG/DTG技术，对水化产物进行定性定量分析，得出硫铝酸盐水泥熟料-二水石膏体系（简称CG体系）和硫铝酸盐水泥熟料-二水石膏-氢氧化钙体系（简称CGL体系）水化产物中钙矾石（AFt）、单硫型水化硫铝酸钙（AFm）、铝凝胶（AH3）等物相含量的变化规律，并进行比较。结果表明，CGL体系水化产物中AH3和AFm生成量多于CG体系，而AFt生成量在二水石膏与硫铝酸钙摩尔比为0.5和1.0时少于CG体系，达到1.5摩尔比时两个体系相差不大；CGL体系中，掺加氢氧化钙会降低试件早期抗压强度，后期其抗压强度赶上甚至超过未掺加氢氧化钙的试件；随着二水石膏掺量增加，CG体系中AFt早期生成速率和试件膨胀率均呈增大趋势，而CGL体系中AFt早期生成速率和试件膨胀率均呈减小趋势。     

矿渣微粉对水泥净浆性能及氯离子固化作用的影响

为解决钢筋混凝土氯离子侵蚀难题，研究了不同掺量矿渣微粉对水泥净浆工作性能、力学性能和氯离子固化性能的影响，并通过物相分析、热重分析、孔结构分布和热力学模拟等方法对氯离子固化机理进行表征分析。结果表明：矿渣微粉能够改善水泥基材料的工作性能，有效提升水泥净浆后期抗压强度和氯离子固化能力，掺量为30%(质量分数)时综合性能最佳；矿渣微粉能够化学结合氯离子，促进体系生成Friedel盐和Kuzel盐，并且能够发生火山灰效应提升C-S-H凝胶含量，细化硬化浆体孔隙结构，提升密实度；水泥净浆氯离子固化能力受氯离子化学结合、物理吸附和阻迁能力共同作用，随着矿渣微粉掺量增加，水泥净浆氯离子化学结合和物理吸附能力逐渐增强，而阻迁能力存在最优掺量。本研究为矿渣微粉水泥基材料在远海岛礁工程建设中的应用提供技术支持和理论支撑。     

不同缓凝剂对水泥超长缓凝作用与水化特性的影响

研究了羟基乙叉二膦酸(HP)、蔗糖(ZT)和葡萄糖酸钠(PN)3种缓凝剂对水泥净浆凝结时间和抗压强度的影响,并利用水化热测试、XRD、热重等手段分析对延缓水泥水化的影响机理.结果表明,随着3种缓凝剂掺量的增大,凝结时间逐渐延长,掺0.3％ 和0.4％ 的ZT出现不凝的现象,掺0.3％ 和0.4％ 的PN和HP均达超缓凝,7 d时无强度,14 d和21 d强度明显低于空白组(KB),但28 d强度接近空白组,到90 d则均高于空白组.HP的超缓凝作用使水泥的水化程度缓慢降低的效果最明显,其水化产物中的AFt略低于KB的,而AFm量极少,远低于KB的,CH以及包括C-S-H凝胶在内的非晶相接近KB的.与PN相比,HP对水泥的水化抑制效果较好,HP的水化产物AFt量略低于PN的,CH以及包括C-S-H凝胶在内的非晶相与PN接近.     

地热环境下AFt和AFm的转化机制

在地热环境下水泥水化初期，单硫型硫铝酸盐(AFm)易与硫酸根在孔隙或界面处生成延迟钙矾石(DEF),导致混凝土膨胀开裂。本文采用溶液法模拟钙矾石(AFt)生成的温湿耦合液相环境，通过分子动力学模拟方法研究AFt在常温和地热环境下的内部结构变化，确定DEF的生成温度界限和水泥中石膏临界掺量。结果表明，地热高温环境会影响AFt晶体在(100)、(110)晶面上的生长，导致AFt生成量随温度升高逐渐减少；70～75℃为AFt转变为AFm的关键温度区间，但在75℃以上液相环境中AFt依然能够生成，转化的AFm含量会随温度增加而逐渐增多；高温对水泥早期水化生成AFt具有促进作用，但随着养护龄期增长，高温会造成早期生成的AFt逐渐转化为AFm;混凝土中AFt生成量随石膏掺量增大而增加，质量分数为4%左右的石膏是适宜掺量；分子动力学模拟结果同样表明AFt在常温下结构稳定，而在地热条件下结构发生改变。     

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.     

粉煤灰对碱激发矿渣/粉煤灰体系的作用机理研究

碱激发胶凝材料是以工业固体废弃物为原料制备的一种绿色无机胶凝材料,具有良好的力学性能与耐久性能。粉煤灰因其独特的球体微观结构与其他固废微粉存在本质区别,因此粉煤灰在碱激发胶凝材料体系中的作用机理亟待研究。以矿渣与粉煤灰为原料,利用碱激发剂制备胶凝材料,并对材料进行抗压强度测试,最后采用XRD、FTIR和SEM探究碱激发矿渣/粉煤灰体系的水化反应机理,研究粉煤灰对矿渣/粉煤灰体系的作用机理。结果表明:外掺3%(质量分数)NaOH作为碱激发剂,水固比为0.4时,随粉煤灰掺量减少,抗压强度呈现先上升后下降的趋势;m(矿渣):m(粉煤灰)为4:1时,28 d抗压强度达到峰值(37.1 MPa)。粉煤灰颗粒在不同龄期形成具有不同反应程度与尺寸的嵌入式微观结构,对材料力学性能起到不利影响;但粉煤灰的活化程度随龄期延长逐渐变大,对后期强度发展有持续贡献。碱激发矿渣/粉煤灰体系水化产物中含有Friedel盐、托贝莫来石、钙矾石、C-S-H/C-A-S-H凝胶,以及粉煤灰中残留的α石英相。随粉煤灰掺量增加,托贝莫来石生成量减少,钙矾石向Friedel盐转变,钙矾石生成量减少,Friedel盐生成量增多。     

The role of calcium carbonate in cement hydration

Limestone, mainly consisting of calcite, is a permitted additive to Portland cements often up to a 5 wt.% limit. It is shown by experiment and calculation that much, if not all, of this calcite is reactive and affects the distribution of lime, alumina and sulfate and thereby alters the mineralogy of hydrated cement pastes. Calcite affects the mineralogical variant of the AFm phase(s). Calcite additions affect the amount of free calcium hydroxide as well as the balance between AFm and AFt phases, although C-S-H is unaffected in much of the range of compositions. Generic data are shown in graphical form to quantify these mineralogical changes as functions of cement composition and amount of added calcite. Calculations of the specific volume of solids as a function of calcite addition suggest that the space-filling ability of the paste is optimised when the calcite content is adjusted to maximise the AFt content. However, before the calculated data can be used uncritically, certain kinetic constraints on reactivity also need to be assessed. Progress towards the quantification of paste mineralogy suggests that (i) elucidation of the mineralogy of pastes, particularly blended cement pastes, is facilitated by using both theoretical and experimental approaches and (ii) that the ultimate goal, of calculating paste mineralogy from the bulk chemistry, is attainable.     

Analytical Study of Pure and Extended Portland Cement Pastes: II, Fly Ash- and Slag-Cement Pastes

A range of pastes of portland cement interground with low-calcium fly ash or granulated blast furnace slag was studied by X-ray diffraction, analytical electron microscopy, thermo-gravimetry, and determinations of CO₂ and of unreacted fly ash or slag. Partial replacement of clinker by fly ash results in increased reaction of the alite from at least as early as 3 d. The amount of Ca(OH)₂ formed from a given weight of clinker increases at 3 d due to the enhanced reaction, but from 28 d onward, it decreases due to the pozzolanic reaction. The mean Ca/SI ratio of the C-S-H decreases with time or fly ash content, toward a lower limit of ∼1.4. Partial replacement of clinker by slag also decreases both the amount of Ca(OH)₂ formed from a given weight of clinker and the mean Ca/Si ratio of the C-S-H, but to a lesser extent. Using the methods described in Part I of this paper, the results of the experimental methods were tested for mutual consistency, and volume percents of phases, porosities, and related quantities were calculated.     

偏硅酸钠激发胶凝材料性能及微观结构

以粉煤灰、矿渣为原料,研究了偏硅酸纳激发胶凝材料的力学性能及工作性能,通过XRD和SEM对水化产物进行表征,并采用量热试验对水化历程进行分析.结果表明:对于粉煤灰-矿渣体系,采用偏硅酸钠作激发剂时,碱当量为8％时,砂浆抗压强度最高;随着激发剂掺量的增加,砂浆流动度增加,凝结时间缩短,砂浆收缩率降低;体系主要水化产物为C-S-H凝胶,且随着碱当量的提高,粉煤灰和矿渣的反应程度变大,水化产物中凝胶的量增加.     

水泥-粉煤灰-矿粉-偏高岭土四元胶凝材料氯离子固化机理研究

本文在水泥、粉煤灰和矿粉组成的三元胶凝材料基础上掺入第四元矿物掺合料偏高岭土,利用X射线衍射(XRD)和热重分析(TGA/DTG)定性分析了四元胶凝材料水化产物与氯离子固化能力的关系,并在此基础上利用TGA/DTG和Rietveld外标法定量分析不同形态氯离子固化量。研究表明,掺入偏高岭土能够增加体系早期水化反应速率,促进粉煤灰和矿粉早龄期水化,增加了四元胶凝材料水化AFm相(单硫型水化硫铝酸钙)和C-S-H凝胶含量。同时也增加了体系中铝钙摩尔比,使得单硫型硫铝酸钙(Ms)在碳酸盐存在的条件下更加倾向于转化为半碳型碳铝酸钙(Hc)。氯离子等温吸附结果表明,AFm相含量与氯离子固化能力呈正相关。Rietveld外标法结果表明,掺入偏高岭土后四元体系的氯离子化学固化能力提高,物理吸附能力降低,与三元体系相比,氯离子化学固化量提高了94.16%,物理吸附量降低了7.62%,TGA/DTG定量结果表明Rietveld定量分析具有可行性。     

Self-cementitious properties of fly ashes from CFBC boilers co-firing coal and high-sulphur petroleum coke

Self-cementitious properties of fly ash from circulating fluidized bed combustion boiler co-firing coal and high-sulphur petroleum coke (CPFA) were investigated. CPFA was self-cementitious which was affected by its fineness and chemical compositions, especially the contents of SO₃ and free lime (f-CaO). Higher contents of SO₃ and f-CaO were beneficial to self-cementitious strength; the self-cementitious strength increases with a decrease of its 45 μm sieve residue. The expansive ratio of CPFA hardened paste was high because of generation of ettringite (AFt), which was influenced by its water to binder ratio (W/A), curing style and grinding of the ash. The paste cured in water had the highest expansive ratio, and grinding of CPFA was beneficial to its volume stability. The hydration products of CPFA detected by X-ray diffraction (XRD) and scanning electron microscopy (SEM) were portlandite, gypsum, AFt and hydrated calcium silicate (C-S-H).     

掺固硫渣的水泥浆体中钙矾石的定量分析研究

选用1：3乙二醇-甲醇溶剂以相当高的选择性从掺固硫渣的水泥水化浆体中萃取钙矾石并采用返滴定法测定其含量，研究表明：水化早期（一般指7d之前）水泥浆体中，钙矾石含量随龄期的增长而增加，而在水化后期，钙矾石含量随期的增长有所减少且趋于平缓。     

Studies on blended cement with a large amount of fly ash

The influence of the contents of the clinker, activators and fly ash on the properties of blended cement with high fly ash content was studied. Experimental data from X-ray diffraction and pore size distribution indicated that the main hydration product of the fly ash blended cement was C-S-H gel, ettringite and a small amount of Ca(OH)₂. The volume porosity of the pores with diameter bigger than 0.1 μm was lower than that of the micro pores and gel pores with diameter lower than 0.05 μm. The amount of chemical combined water has increased with the curing age duration, while the content of Ca(OH)₂ has reduced after 7 days.