Early activation and properties of slag cement

Early age activation of granulated blast-furnace slag (BFS) and blends of slag and portland cement (OPC) has been studied. Activators include sodium-hydroxide, sodium sulfate, alum (potassium aluminum sulfate), superplasticizer, and calcium aluminate cement. Heat of hydration, x-ray phase characterization, compressive strength, viscometry, pore size distribution and related characterization studies have been made. Activated BFS-cement mortars having equivalent strengths at 1 day to OPC have been prepared, which also have 28- and 90-day strengths exceeding those of the OPC. Mechanisms of activation are discussed.     

高掺量混合材复合水泥的水化性能

通过水化微量热、化学结合水测定和X射线衍射、热重-差热分析、扫描电镜等测试方法研究了3种高掺量矿渣、粉煤灰、石灰石复合水泥的水化性能,并与硅酸盐水泥的水化进行了对比。结果表明：高掺混合材复合水泥的水化放热特征与硅酸盐水泥有明显不同,早期水化反应速度低于硅酸盐水泥,但后期由于矿渣、粉煤灰的二次水化反应使其水化速度增长较快。主要的水化产物亦为水化硅酸钙凝胶、钙钒石和Ca(OH)2晶体,但Ca(OH)2含量明显低于硅酸盐水泥浆体中的Ca(OH)2含量。     

矿渣水泥水化动力学的研究

应用恒温导热量热仪对矿渣水泥和波特兰水泥的水化动力学进行了研究。实验结果表明,水泥水化在不同反应阶段具有不同的反应机理,所适用的动力学公式及动力学参数亦不同。加速期由自动催化(auto catalytic)反应控制,减速期由化学反应和扩散过程双重控制,衰减期由扩散过程控制。矿渣水泥对温度的敏感性高于波特兰水泥,原因是矿渣玻璃相具有较高的表观活化能。提高温度(热激发)对矿渣水泥的水化更为有利。在研究中采用两种活性不同的矿渣,它们的活性之差别可以从水化动力学参数K、E与N(与反应机理有关的常数)反映出来。     

Effect of calcium chloride on the volume contraction,non-evaporable water content and bound chloride content of hydrated portland cement and blast-furnace slag

The change in volume during hydration, Δv, and the water retained at 105°C at ultimate hydration, w_n^o, have been measured for cement-calcium chloride-water systems in which the cements consisted of portland cement, blastfurnace slag and mixtures of portland cement and blastfurnace slag in equal parts by mass.The results showed that the quantity of chloride bound in the solid phases increased with the initial concentration of chloride in the aqueous phase but the parameters Δv and w_n^o for a particular system were independent of the initial chloride concentration in the aqueous phase.     

Supplementary cementitious materials for mitigating degradation of kraft pulp fiber-cement composites

Kraft pulp fiber reinforced cement-based materials are being increasingly used where performance after exposure to environmental conditions must be ensured. However, significant losses in mechanical performance due to wet/dry cycling have been observed in these composites, when portland cement is the only cementitious material used in the matrix. In this research program, the effects of partial portland cement replacement with various supplementary cementitious materials were investigated. Binary, ternary, and quaternary blends of silica fume, slag, Class C fly ash, Class F fly ash, metakaolin, and diatomaceous earth/volcanic ash blends were examined for their effect on the degradation of kraft pulp fiber-cement composite mechanical properties (i.e., strength and toughness) during wet/dry cycling. After 25 wet/dry cycles, it was shown that binary composites containing 90% slag, 30% metakaolin, or greater than 30% silica fume did not exhibit any signs of degradation, as measured through mechanical testing and microscopy. Ternary blends containing 70% slag/10% metakaolin or 70% slag/10% silica fume were also effective in preventing degradation. A reduction in calcium hydroxide content and the stability of the alkali content due to supplementary cementitious material addition were shown to be primary mechanisms for improved durability.     

Mössbauer and X-ray investigations of some portland cements

The Mössbauer spectroscopic and x-ray diffraction investigations have been carried out on a variety of ordinary portland, portland pozzolanic, portland slag and sulphate resisting portland cements, using dry as well as hydrated samples. The discussion of the Mössbauer parameters shows that Fe atoms occupying distorted octahedral and tetrahedral sites in the dry cements are hydrated to form ferrite monosulphate without producing Fe(OH)₃ and its gel; hydration of the slag cement proceeds much faster than other cements; and that the composition of the iron-bearing phase in the sulphate resisting portland cement, studied in detail, is close to C₄AF.     

含硫铝酸钙硅酸盐水泥中粉煤灰活化机理

用差示扫描-热重分析扫描电镜和化学分析法研究了含硫铝酸钙粉煤灰硅酸盐水泥和含硫铝酸钙矿渣硅酸盐水泥水化过程中水化产物的种类、形状、数量和孔溶液离子浓度等方面的变化规律.借助固体高分辨核磁共振波谱技术对水泥中硅氧四面体不同聚合状态的分布,Al的不同配位状态进行分析.结果表明:含硫铝酸钙硅酸盐水泥对粉煤灰激发作用大于对矿渣的激发作用,含硫铝酸钙粉煤灰水泥水化放热量多,促进粉煤灰玻璃体中AlO2-的溶出,在较高温度粉煤灰玻璃体网络结构激活,解聚速率加快.     

Investigation of blended cement hydration by isothermal calorimetry and thermal analysis

Hydration of portland cement pastes containing three types of mineral additive; fly ash, ground-granulated slag, and silica fume was investigated using differential thermal analysis, thermogravimetric analysis (DTA/TGA) and isothermal calorimetry. It was shown that the chemically bound water obtained using DTA/TGA was proportional to heat of hydration and could be used as a measure of hydration. The weight loss due to Ca(OH)₂ decomposition of hydration products by DTA/TGA could be used to quantify the pozzolan reaction. A new method based on the composition of a hydrating cement was proposed and used to determine the degree of hydration of blended cements and the degree of pozzolan reaction. The results obtained suggested that the reactions of blended cements were slower than portland cement, and that silica fume reacted earlier than fly ash and slag.     

Estimation of the degree of hydration of blended cement pastes by a scanning electron microscope point-counting procedure

A scanning electron microscope (SEM) point-counting technique was employed to study the hydration of plain portland and blended cement pastes containing fly ash or slag. For plain portland cement pastes, the results for the degree of cement hydration obtained by the SEM point-counting technique were consistent with the results from the traditional loss-on-ignition (LOI) of nonevaporable water-content measurements; agreement was within ±10%. The standard deviation in the determination of the degree of cement hydration via point counting ranged from ±1.5% to ±1.8% (one operator, one sample). For the blended cement pastes, it is the first time that the degree of hydration of cement in blended systems has been studied directly. The standard deviation for the degree of hydration of cement in the blended cement pastes ranged from ±1.4% to ±2.2%. Additionally, the degrees of reaction of the mineral admixtures (MAs) were also measured. The standard deviation for the degree of fly ash reaction was ±4.6% to ±5.0% and ±3.6% to ±4.3% for slag. All of the analyses suggest that the SEM point-counting technique can be a reliable and effective analysis tool for use in studies of the hydration of blended cement pastes.     

Stoichiometry of Slag Hydration with Calcium Hydroxide

The stoichiometry of the reaction between ground granulated blast furnace slag (GGBFS) having an empirical formula of C_7.88S_7.39M₃A and calcium hydroxide (CH) was investigated. Scanning electron microscopy (SEM) was used to determine the slag consumption as well as the Ca/Si ratio in calcium silicate hydrate gel (C-S-H) products. A tentative stoichiometric ratio of 2.6 mol of CH consumed per mole of slag reacted was determined using two methods. By combining consumption data determined separately for slag and CH a molar stoichiometry of 2.79 was found. Similarly, by directly determining the Ca/Si ratio in the C-S-H gel product, a range for the molar stoichiometry between 1.65 and 3.42 was found. Finally, a comparison of the stoichiometry of the slag/CH reaction was made with slag/portland cement hydration. The basic features of both appear similar. In the C-S-H gel around slag grains, a calcium-to-silica ratio of 1.3 to 1.4 was found for both slag/CH and slag/cement systems.     

高强度碱矿渣水泥

本文研制了低水灰比高强度碱矿渣水泥。抗压强度高达350MPa以上。分析了工艺条件对水泥性能的影响以及强度与水化程度,孔隙率、孔分布的关系。比较了碱矿渣水泥和波特兰水泥的界面性能和耐蚀性。并对碱矿渣水泥的水化产物进行了x-射线衍射分析、红外光谱分析、差热分析、扫描电镜观察及能谱分析。     

Aluminum Incorporation in the C–S–H Phase of White Portland Cement–Metakaolin Blends Studied by 27Al and 29Si MAS NMR Spectroscopy

The composition and structure of the calcium‐silicate‐hydrate (C–S–H) phases formed by hydration of white portland cement–metakaolin (MK) blends have been investigated using ²⁷Al and ²⁹Si MAS NMR. This includes blends with 0, 5, 10, 15, 20, 25, 30 wt% MK, following their hydration from 1 d to 1 yr. ²⁹Si MAS NMR reveals that the average Al/Si ratio for the C–S–H phases, formed by hydration of the portland cement–MK blends, increases almost linearly with the MK content but is invariant with the hydration time for a given MK content. Correspondingly, the average aluminosilicate chain lengths of the C–S–H increase with increasing MK content, reflecting the formation of a C–S–H with a lower Ca/Si ratio. The increase in Al/Si ratio with increasing MK content is supported by ²⁷Al MAS NMR which also allows detection of strätlingite and fivefold coordinated aluminum, assigned to AlO₅ sites in the interlayer of the C–S–H structure. Strätlingite is observed after prolonged hydration for MK substitution levels above 10 wt% MK. This is at a somewhat lower replacement level than expected from thermodynamic considerations which predict the formation of strätlingite for MK contents above 15 wt% after prolonged hydration for the actual portland cement–MK blends. The increase in fivefold coordinated Al with increasing MK content suggests that these sites may contribute to the charge balance of the charge deficit associated with the incorporation of Al³⁺ ions in the silicate chains of the C–S–H structure.     

Pore Structure Damage in Blended Cements Caused by Mercury Intrusion

Hydrated blast furnace slag and fly-ash cement blends have been shown to be very impermeable. Porosity measurements of these materials by methanol and helium pycnometry have been less than the values obtained by Hg intrusion to 410 MPa. Results of the three techniques for hydrated portland cement were the same. A technique was used in which mercury could be removed by distillation after Hg intrusion, and intrusion was then repeated. This was performed on several cements and cement blends. Pore-size distribution for the hydrated cement changed marginally but both blended materials changed markedly, displaying a coarser pore distribution. It was concluded that the latter bodies are composed of relatively large, but discontinuous pores, into which Hg enters by breaking through the pore structure.     

改性磷石膏对石膏矿渣水泥水化过程的影响研究

采用质量分数为5％～25％的改性磷石膏、15％的硅酸盐水泥熟料、60％～80％的矿渣混合磨细制成石膏矿渣水泥,研究了改性磷石膏掺量对石膏矿渣水泥浆体的抗压强度、水化热、孔溶液pH值及水化产物的影响情况.结果表明,掺入改性磷石膏使得石膏矿渣水泥的3 d、7 d抗压强度降低,其掺量为10％、15％时,水泥的28 d、90 d抗压强度超过普通硅酸盐水泥.在3 d至90 d龄期内,水泥孔溶液pH值随龄期增长而逐渐增大.在相同龄期时,随着改性磷石膏掺量的增大,水泥孔溶液pH值减小,水化放热峰出现时间延缓.微观分析表明,掺入改性磷石膏后,28 d龄期时的水泥水化产物主要为钙矾石和C-S-H凝胶,水化产物的生成量在改性磷石膏掺量为15％时最多.     

A note on early hydration of cement

In this note it is shown that the hydration of portland cement and of blastfurnace slag cement can be traced using the flotation of cement from mortars and concretes. The various stages of the hydration reaction, i.e. initiation, induction period, formation of an initial gel structure and the final hardening process can be detected clearly.     

Study on high-strength composite portland cement with a larger amount of industrial wastes

It is one of important measures for the sustainable development of cement industry to utilize industrial wastes. High-strength composite portland cement with a large amount of granulated blast furnace slag (GBFS), fly ash and limestone was prepared by separate grinding method, optimizing gypsum and using activators. The total amounts of blending materials are between 45% and 65% and the strength grades of cements reach 525 or even 625 according to Chinese national standard for composite portland cement. Besides setting time and strength, the hydration heat, drying shrinkage and sulfate resistance were also determined.     

水泥熟料中氧化镁的水化和膨胀性能

采用ＸＲＤ,ＤＳＣ等方法研究了熟料中氧化镁的水化及其膨胀性能,结果表明,料中氧化镁是一种制造膨胀型水泥的好材料,但它的缺陷在于水化及膨胀十分缓慢,利用钙矾石在早期产生膨胀的性能对熟料中氧化镁的延缓性能膨胀加以改进。可以为制造微膨胀型中热水泥和低热矿渣水泥提供依据。     

温度对碱-磷渣水泥水化的影响

本文研究了两种碱-磷渣水泥(用NaOH作为碱性激发剂的MO及用Na_2O·SiO_2作为碱性激发剂的M_1)在不同温度下的水化放热速率及强度发展情况。实验结果表明,M1水泥对温度的敏感性高于M0水泥,原因是这两种水泥的表现水化活化能不一样,M0水泥的为38.89KJ/mol,而M1水泥的为64.62KJ/mol。     

矿物掺合料对水泥耐酸性的影响及配比设计

以硅粉、粉煤灰和矿渣为矿物掺和料,采用XRD和SEM研究了矿物掺和料对水泥水化产物、水泥石结构和形貌的影响,探讨了酸溶液对水泥的腐蚀机理,并对矿物掺和料配比进行优化设计,以提高水泥的耐酸性.研究结果表明:掺加矿物掺和料有利于改善水泥石孔结构,降低水泥碱度,当硅粉、粉煤灰和矿渣以占水泥质量5%,10%和15%的配比掺入时,水泥的耐酸性最好.     

Supersulphated cement from blastfurnace slag and chemical gypsum available in the Netherlands and neighbouring countries

The present report covers research into the mechanical strength development and the surface hardness of supersulphated cement from blastfurnace slag, chemical gypsum and portland clinker. The tests were carried out on sand/cement mortar as well as on concrete. A comparison was made with a type of supersulphated cement which was in the market until recently, and with portland and blastfurnace cement. A review has been made of the effects of the hardening temperature, the relative humidity, the degree of grinding of the cement, the use of a water-reducing additive, and treatment with a curing compound. The conclusion is drawn that one of the cements produced, consisting of 83% m/m Dutch blastfurnace slag, 15% m/m fluorogypsum (anhydrite) and 2% m/m portland clinker ground to the relatively high specific surface of 500 m²/kg, is not inferior to blastfurnace cement as regards the properties examined.