Impact of prolonged warm (85°C) moist cure on Portland cement paste

A commercial Portland cement paste was fabricated as 200-g cylinders to a water/cement weight ratio of 0.50. After 30 days cure at 20°C, cylinders were additionally cured at 20°C and 85°C, both ±2°C, in sealed, vapour-saturated systems for 8.4 years. Thereafter, cylinders were allowed to stand, still in sealed state, at 20° for 1.5 to 2.0 years. The 20°C cure mineralogy and microstructure is essentially normal: only a little unhydrated clinker persists and the matrix consists of relatively coarse, blocky Ca(OH)₂ crystals embedded in a groundmass of C-S-H together with some AFt (ettringite). However, prolonged 85°C cure significantly alters the microstructure and mineralogy. Clinker hydration progressed only slowly between 28 days and 8.4 years, with the result that 30% cement clinker persists. Subsequent prolonged storage at 20°C has apparently not allowed hydration to restart. Ca(OH)₂ is present in approximately unchanged amounts, comparing the two cures, provided allowance is made for the presence of unhydrated clinker. Paste porosity is, however, significantly increased at 85°C relative to 20° cure. The 85°C mineralogy consists of four solid hydrate phases: Ca(OH)₂, C-S-H gel, with a Ca/Si mole ratio close to 1.52, katoite (a siliceous hydrogarnet) and a hydrotalcite-like phase. The amounts of these phases are determined. The compositions of the C-S-H gel and hydrogarnet have been estimated by transmission electron microscopy and microprobe analysis. The amount and composition of the mineral phases can be recalculated to yield a bulk composition of the cement that agrees with a batch analysis.     

Morphology and microstructure of autoclaved slag-clinker pastes in presence and absence of silica sand

Morphology and microstructure of autoclaved slag-clinker and slag-clinker-sand mixtures were undertaken using scanning electron microscopy. The microstructure of autoclaved slag-clinker hydration products displayed nearly amorphous, fibrous and radial plates of CSH phase, large cubes of hydrogarnet-like hydrates (mainly as C₃ASH₄) as well as hexagonal precipitations of calcium hydroxide. The hydration of slag-clinker-sand mixture (an optimum composition) was associated with the formation of semi-crystalline low-lime tobermorite (mainly as CSH(I)) as well as fibrous and massive plates of crystalline 11Å tobermorite as the main hydration products. The strength development could also be related with the microstructure of the formed hydrates.     

Hydrothermal Treatment of a Silica Sand Complex with Lime

The feasibility of using relatively low-purity silica as the starting material for hydrothermal solidification was investigated from the consideration of effective utilization of natural resources. Hydrothermal solidification was performed at 140°–180°C for periods ranging from 2 to 40 h using a mixture of 80% silica sand (containing 67% quartz, 22% clay minerals (mica, clinochlore, and kaolinite), and 7% feldspar) and 20% Ca(OH)₂. Within the range of experimental conditions, the flexural strength of the solidified bodies increased with increased treatment temperature and treatment time, reaching values of up to 20 MPa. The flexural strength was proportional to the amount of, but independent of the type of, reaction products. Hydrogarnet and C-S-H were formed in the initial stages of the reaction; the amount of these phases tended to decrease, and 1.1 nm tobermorite formed as the reaction further progressed. These results indicated that hydrogarnet and C-S-H were precursors of 1.1 nm tobermorite.     

NaOH和Na2CO3对磷渣水化过程的影响

采用NaOH和Na2CO3作为磷渣的激发剂。通过测定磷渣的凝结时间、化学结合水和反应率,研究碱激发剂对磷渣水化程度的影响。利用X射线衍射和扫描电镜分析,研究碱激发磷渣水化产物的物相组成和微观形貌。结果表明,这两种碱激发剂均能加快磷渣的水化速率,其中NaOH对磷渣的激发效果明显优于Na2CO3。NaOH和Na2CO3对磷渣水化过程的影响主要表现为促进磷渣玻璃体溶解,生成更多的C-S-H(B)和托贝莫来石,从而形成致密的结构。     

C-S-H及C-S-H脱水相对水泥石结构改性的研究

以C-S-H及C-S-H脱水相作水泥水化物沉淀中心的品种。从理论上阐明了它们是具有较大介电常数、较小物理化学不均匀系数、高分散度的晶种物质,故具有优先吸附的界面效应及优先沉淀的结晶中心作用,可缓和原始矿物表面的高浓度的屏蔽效应及界面的近程析晶,使水化物分布均匀、结构致密,从而提高水泥石强度。C-S-H及C-S-H脱水相两者中,尤以后者作用更显著。     

In situ time-resolved X-ray diffraction of tobermorite formation in autoclaved aerated concrete: Influence of silica source reactivity and Al addition

The hydrothermal formation of tobermorite during the processing of autoclaved aerated concrete was investigated by in situ X-ray diffraction (XRD) analysis. High-energy X-rays from a synchrotron radiation source in combination with a newly developed autoclave cell and a photon-counting pixel array detector were used.To investigate the effects of the silica source, reactive quartz from chert and less-reactive quartz from quartz sand were used as starting materials. The effect of Al addition on tobermorite formation was also studied. In all cases, C-S-H, hydroxylellestadite and katoite were clearly observed as intermediates.Acceleration of tobermorite formation by Al addition was clearly observed. However, Al addition did not affect the dissolution rate of quartz. Two pathways, via C-S-H and katoite, were also observed in the Al-containing system. These results suggest that the structure of initially formed C-S-H is important for the subsequent tobermorite formation reactions.     

Hydrothermal products of the C3MS2-C12A7-MgO system

The autoclave products of reduced steel-slag of an electronic furnace mainly containing C₃MS₂ phase were detected. The hydrothermal products of this slag included calcio-chondrodite, brucite, and hydrogarnet phases. When suitable (CaO + MgO)/SiO₂ molar ratios were chosen, C₃MS₂ can react with SiO₂ to produce calcium silicate hydrates tobermorite, xonotlite, gyrolite, and truscottite phases with different saturated water vapor pressures. The phase brucite was present along with tobermorite, whereas phases Mg-xonotlite, Mg-gyrolite, and Mg-truscottite can rarely coexist with brucite. Hydrogarnet phase disappeared when Mg-truscottite was formed.     

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.     

压蒸条件下花岗岩石粉对UHPC性能的影响

研究了在压蒸条件下花岗岩石粉取代石英粉掺量对超高性能混凝土力学性能(3d、180 d抗压/抗折强度)和微观结构(水化产物、C-S-H凝胶平均分子链长)的影响,并探明两者之间的关系.XRD、SEM-EDS、29Si NMR测试结果表明:3 d、180 d胶凝浆体水化产物主要为低钙硅比、本征强度较高的tobermorite晶体.随着花岗岩石粉取代率增加,混凝土抗压/抗折强度先增加后减小,当取代率为50％时,其180 d抗压强度≥190 MPa、抗折强度≥40MPa;且随着取代率的增加,C-S-H凝胶平均分子链长降低、Al[4]/Si增加;在相同取代率时,平均分子链长为180d＞3d,Al[4]/Si为180 d＜3 d.高温和高压条件下,C-S-H凝胶平均分子链长不是混凝土性能的单一影响因素,混凝土抗压强度与C-S-H凝胶平均分子链长不直接相关.     

硅钙基固废原料配比及蒸养条件对硅酸钙板力学性能的影响

研究协同利用硅钙渣、粉煤灰、水泥和脱硫石膏制备硅酸钙板时,原料配比、蒸养条件对硅酸钙板力学性能、水化产物的影响,并利用XRD、IR和SEM表征了原料的协同水化历程和水化产物的微观结构和表面形貌.试验结果表明:最佳原料配比为硅钙渣60%、粉煤灰24%、水泥10%和脱硫石膏6%;最佳蒸压养护条件为蒸养温度180℃,恒温蒸养时间8 h,硅酸钙板抗折强度满足国家标准强度的D1.3的Ⅱ级要求;随着蒸养温度升高,原料水化依次生成C-S-H凝胶、托贝莫来石和针状硬硅钙石,大量托贝莫来石和硬硅钙石的生成使得硅酸钙板的强度得以提升.     

Characterization by Multinuclear High-Resolution NMR of Hydration Products in Activated Blast-Furnace Slag Pastes

The effect of activators on the hydration of granulated blast-furnace slag (gbfs) was studied through compressive strength measurements, ²⁹Si, ²⁷Al, and ²³Na high-resolution nuclear magnetic resonance, and X-ray diffraction. Four different activations containing sodium hydroxide, sodium silicate, and/or calcium hydroxide (CH) were considered, at fixed amounts of alkali: 5% Na₂O, 5% Na₂O-2.5% CH, 5% Na₂O-7.5% SiO₂, and 5% Na₂O-2.5% CH-7.5% SiO₂. Silicate-activated gbfs cements have greater compressive strength than Portland cements over the whole period of study (1 yr). Also, silicate-free activated gbfs cements have poorer mechanical strength than silicate-activated cements. In fact, substantial structural differences were observed between hydration products in both kinds of activations. In silicate-activated pastes there exists an intimate mixture of C-S-H layers and AFm-like arrangements containing Al in octahedral sites bonded to the silicate layers, originated either from phase intergrowths or from a high density of Ca-Al incorporation in the interlayer spaces of C-S-H. In pastes obtained from silicate-free activation of gbfs there is a better chemical and structural definition among C-S-H and calcium aluminate hydrate domains (AFm and hydrogarnet).     

粉煤灰对水泥中重金属存在形式的影响

本文对添加不同含量的粉煤灰后，熟料水化过程中重金属元素（Cr、Mn、Cu、Pb、Zn）存在形式及其浸出毒性进行了实验和探讨。随着粉煤灰掺入量由0%提升至10%，水化产物形貌中微细孔增多，重金属元素在C-S-H中富集程度增加，熟料重金属元素浸出毒性呈现不同程度下降趋势，最大下降幅度达到56.1%，主要因为微细孔对重金属有较好的吸附作用，且重金属元素在水化产物周围的富集程度增加，有助于重金属离子以较为稳定的形态固化在水化产物中。     

Phase Evolution during Autoclaving Process of Aerated Concrete

The reactions were investigated that occur when lime, cement, and quartz sand are mixed together and molded, then treated at 180°C under saturated steam pressures to produce autoclaved aerated concrete. The hydrothermal treatment of mixtures gives Ca-rich C-S-H with varying Ca/Si ratios as an initial product, which reacts further with silica dissolved from quartz to form 1.1-nm tobermorite with increase of curing time. During autoclaving, the composition of C-S-H and tobermorite as a binder continues to change until after 8 h, when the Ca/(Al + Si) ratio becomes constant at 0.8. As the reaction proceeds, the number of micropores increases, and the strength also increases due to the binder effect of the tobermorite. However, the total pore volume does not change, remaining constant values.     

垃圾焚烧飞灰煅烧阿利尼特水泥熟料的形成过程及其水化性能研究

以城市垃圾焚烧飞灰(以下简称焚烧飞灰)为主要原料,在实验室电炉里成功研制了阿利尼特水泥熟料。本文主要研究水泥熟料煅烧形成过程及其水化性能,分析了阿利尼特水泥的适宜石膏掺量、水化放热特征、水化产物及其显微结构。研究结果表明:利用垃圾焚烧飞灰为主要原料可以成功烧制阿利尼特水泥熟料,煅烧过程中首先出现C2S、C12A7和C2S·CaCl2,随后与MgO和CaCl2反应生成阿利尼特;掺加5%二水石膏可以促进阿利尼特水泥水化,较普通硅酸盐水泥更快,阿利尼特水泥可以作为一种早强快硬型水泥使用;阿利尼特水泥主要水化产物除含有硅酸盐水泥中常见的CSH凝胶、棒状AFt和Ca(OH)2晶体外,还含有C3A·CaCl·210H2O晶体。     

含碱砂对压蒸水化硅酸钙及其制品强度的影响

研究了以碱长石代替部份标准砂配料条件下碱含量对压蒸制品强度的影响。用XRD、DTA、SAXS等方法研究了蒸压产物中的C-S-H凝胶含量、雪硅钙石晶体含量及压蒸制品的相组成;用SEM-EDAX研究了雪硅钙石的形貌和成份。实验结果表明,C-S-H凝胶含量,雪硅钙石晶体含量、大小、形貌、压蒸产物种类以及晶体生长空间等都是影响压蒸制品强度的重要因素,而所有这些因素都与碱含量有关,碱可固溶于雪硅钙石晶体中。     

Densification of C-S-H is mainly driven by available precipitation space,as quantified through an analytical cement hydration model based on NMR data

NMR relaxometry (Muller et al., 2012, 2013) quantifies the mass fractions of differently bound water in cement paste, as functions of hydration degree and water-to-cement ratio. We here reduce these findings to a single explanation: the density of C-S-H gel is solely governed by the specific precipitation space, across three “hydration regimes”: In regime I, solid C-S-H platelets (without gel porosity) precipitate on clinker surfaces. In regime II, C-S-H starts to include gel porosity. The forming gel densifies linearly with decreasing precipitation space. Thereby, regime III starts once the C-S-H gel has completely filled the capillary porosity. These findings allow for developing an analytical hydration model. It provides expressions for C-S-H gel densification and for the evolution of the volume fractions of clinker, of solid hydrates, as well as of the gel and capillary porosities, as functions of the water-to-cement ratio and the hydration degree; consistently representing published experimental data.     

Composition and structure of C-S-H in white Portland cement-20% metakaolin pastes hydrated at 25 °C

The microstructure and composition of water- and alkali-activated hardened pastes of white Portland cement-20% metakaolin blends have been studied using solid-state NMR spectroscopy and analytical TEM. The results show that after hydration for 1 day nearly half the cement had reacted in the water-activated paste but very little, if any, of the metakaolin; by 28 days two-thirds of the cement had reacted and most of the metakaolin. In contrast, whilst alkali-activation again led to about half the cement reacting by 1 day, about a quarter of the metakaolin had also reacted; and whilst most of the metakaolin had again reacted by 28 days, there had been no further reaction of the cement. The high degree of reaction of the MK in both pastes at 28 days resulted in long-chain highly aluminous C-S-H, with most of the bridging sites occupied by Al³⁺ rather than Si⁴⁺. The data for the C-S-H in the water-activated paste are consistent with both the tobermorite/jennite (T/J) and tobermorite/calcium hydroxide (T/CH) models for the nanostructure of C-S-H - although very little J- or CH-like structure is needed to account for the observed compositions - whilst those for the alkali-activated paste can only be accounted for on the T/CH viewpoint.     

The hydration of Portland cement,C3S and C2S in the presence of a calcium complexing admixture (EDTA)

The effect of EDTA, a calcium chelating agent, on the early hydration of Portland cement, C₃Sand β-C₂S has been studied by solution analysis and electron microscopy. EDTA is a retarded of cement hydration. Under normal conditions of hydration, the silica levels in solution are very low (<0.05 M) but in the presence of EDTA an initial flush of silica appears in the bulk aqueous phase. On continued hydration, following the saturation of EDTA with calcium, the appearance of ‘free’ calcium causes precipitation of C-S-H gel from the bulk solution and changes in microstructure of the colloidal gel around clinker particles in C₃S and β-C₂S pastes are observed. The action of EDTA as a retarding admixture is explained in terms of the membrane model of cement hydration.     

Micromechanical multiscale fracture model for compressive strength of blended cement pastes

The evolution of compressive strength belongs to the most fundamental properties of cement paste. Driven by an increasing demand for clinker substitution, the paper presents a new four-level micromechanical model for the prediction of compressive strength of blended cement pastes. The model assumes that the paste compressive strength is governed by apparent tensile strength of the C-S-H globule. The multiscale model takes into account the volume fractions of relevant chemical phases and encompasses a spatial gradient of C-S-H between individual grains. The presence of capillary pores, the C-S-H spatial gradient, clinker minerals, SCMs, other hydration products, and air further decrease compressive strength. Calibration on 95 experimental compressive strength values shows that the apparent tensile strength of the C-S-H globule yields approx. 320 MPa. Sensitivity analysis reveals that the “C-S-H/space” ratio, followed by entrapped or entrained air and the spatial gradient of C-S-H, have the largest influence on compressive strength.     

Influence of character of clinker on the early hydration process and rheological property of cement paste

Influence of characteristics of alite and interstitial phase in five Japanese clinkers on early hydration of cement and rheological properties of fresh cement paste was investigated. The yield value of fresh cement paste increased rapidly at first due to the formation of ettringite, later due to the formation of C-S-H until it reached setting. The setting time was strongly influenced by alite intense hydration, which started when Ca(OH)₂ saturation ratio in the liquid phase approached a maximum value. That position mainly was dependent upon the free CaO content in clinker and was partially dependent upon water soluble alkali content in clinker and hydraulic reactivity of alite itself. Changing the burning degree of clinker and the hydraulic modulus of raw mix, and intergrinding of clinker with quick lime are practical ways to reduce slump loss and to set an optimum setting time for concrete. All of these methods are related to free lime content for which optimum amounts are varied with burning degree of clinker and quick lime.