Effect of fly ash on the kinetics of Portland cement hydration at different curing temperatures

This paper describes the effect of fly ash on the hydration kinetics of cement in low water to binder (w/b) fly ash-cement at different curing temperatures. The modified shrinking-core model was used to quantify the kinetic coefficients of the various hydration processes. The results show that the effect of fly ash on the hydration kinetics of cement depends on fly ash replacement ratios and curing temperatures. It was found that, at 20 °C and 35 °C, the fly ash retards the hydration of cement in the early period and accelerates the hydration of cement in the later period. Higher the fly ash replacement ratios lead to stronger effects. However, at 50 °C, the fly ash retards the hydration of the cement at later ages when it is used at high replacement ratios. This is because the pozzolanic reaction of the large volumes of fly ash is strongly accelerated from early in the aging, impeding the hydration of the cement.     

Hydration in high-performance cementitious systems containing vitreous calcium aluminosilicate or silica fume

The influence of a relatively new high-performance cement replacement material—vitreous calcium aluminosilicate (VCAS)—on the hydration behavior in cementitious systems, and its comparison to silica fume (SF) are presented in this paper. VCAS is shown to have no cementitious qualities, but exhibits significant pozzolanicity, which has been quantified using strength activity index and electrical conductivity change. VCAS modified pastes are found to consume more water during hydration than the corresponding SF modified pastes. Based on a normalized calcium hydroxide content defined in this paper, it is seen that the pozzolanic reaction of VCAS does not happen until 7 days while that of SF occurs as early as the first day. The degrees of hydration of the modified pastes are predicted using a model that employs the change in non-evaporable water resulting from the use of these replacement materials. VCAS modified pastes show lower later age porosities as compared to the plain and SF modified pastes. However, at equal degrees of hydration, SF modified pastes show the lowest porosity.     

Modeling the hydration of concrete incorporating fly ash or slag

Granulated slag from metal industries and fly ash from the combustion of coal are industrial by-products that have been widely used as mineral admixtures in normal and high strength concrete. Due to the reaction between calcium hydroxide and fly ash or slag, the hydration of concrete containing fly ash or slag is much more complex compared with that of Portland cement. In this paper, the production of calcium hydroxide in cement hydration and its consumption in the reaction of mineral admixtures is considered in order to develop a numerical model that simulates the hydration of concrete containing fly ash or slag. The heat evolution rates of fly ash- or slag-blended concrete is determined by the contribution of both cement hydration and the reaction of the mineral admixtures. The proposed model is verified through experimental data on concrete with different water-to-cement ratios and mineral admixture substitution ratios.     

垃圾焚烧飞灰早期胶凝活性激发研究

从城市生活垃圾焚烧飞灰在水泥混凝土材料领域中的资源化利用角度出发,采用比强度分析方法试验研究了飞灰的胶凝活性,探讨了化学激发剂对飞灰-水泥复合胶凝体系早期强度的活性激发以及相关的机理。结果表明：飞灰早期胶凝活性较低,尤其当掺量高于20％后,表现十分明显。分别掺入1％～3％的CaSO4,KAl（SO4）2,Al2（SO4）3和Na／SiO3的化学激发剂后,浆体的早期抗压强度明显提高,激发效果显著,但随龄期的延长,激发效果减弱。     

Influence of hydration on the fluidity of normal Portland cement pastes

The rheological properties of cement paste strongly influence the workability of concrete. It is known that early hydration processes alter phase composition and microstructure of cement pastes. These processes affect fluidity and setting behaviour of cement paste. While many studies tried to measure and model rheological properties of cement pastes, only a few studies assessed the influence of the hydrate morphology on the fluidity of cement pastes.Results of the present study compare the influence of long prismatic hydrates (i.e. syngenite, secondary gypsum) on the fluidity of cement pastes with the effect of other hydrates (AFm).To induce the formation of certain hydration products the cement composition was modified by addition of set regulators and alkali sulphates. Furthermore a combination of various analytical methods such as fluidity (viscometric) testing and microstructural analysis (phase quantification by XRD-Rietveld analysis, investigation by Environmental SEM, BET analysis etc.) was performed. Results are implemented into a fundamental discussion on the influence of various hydration products on the fluidity of the paste.     

The influence of water removal techniques on the composition and microstructure of hardened cement pastes

The removal of water from hardened cement paste for analysis or to arrest ongoing hydration has been reported to affect the composition of hydrated phases and microstructure. The effect that arresting the hydration of hardened cement paste by replacing the pore water with acetone before drying, and by removing the water by freeze, vacuum and oven drying has on the hardened cement paste has been investigated. Two pastes were studied, a cemented iron hydroxide floc where a high proportion of ordinary Portland cement (OPC) had been replaced by pulverised fuel ash, and a pure hydrated OPC. The results showed that none of the water removal techniques caused any major deterioration in the composition and microstructure of the hardened cement pastes studied, but the pores appeared better preserved after arresting hydration using acetone quenching. Freeze drying appeared to cause more cracking of the microstructure than the other water removal techniques.     

Alkali binding in hydrated Portland cement paste

The alkali-binding capacity of C-S-H in hydrated Portland cement pastes is addressed in this study. The amount of bound alkalis in C-S-H is computed based on the alkali partition theories firstly proposed by Taylor (1987) and later further developed by Brouwers and Van Eijk (2003). Experimental data reported in literatures concerning thirteen different recipes are analyzed and used as references. A three-dimensional computer-based cement hydration model (CEMHYD3D) is used to simulate the hydration of Portland cement pastes. These model predictions are used as inputs for deriving the alkali-binding capacity of the hydration product C-S-H in hydrated Portland cement pastes. It is found that the relation of Na⁺ between the moles bound in C-S-H and its concentration in the pore solution is linear, while the binding of K⁺ in C-S-H complies with the Freundlich isotherm. New models are proposed for determining the alkali-binding capacities of C-S-H in hydrated Portland cement paste. An updated method for predicting the alkali concentrations in the pore solution of hydrated Portland cement pastes is developed. It is also used to investigate the effects of various factors (such as the water to cement ratio, clinker composition and alkali types) on the alkali concentrations.     

Properties and hydration of blended cements with calcareous diatomite

In this paper the effect of diatomite addition on blended cement properties and hydration was studied. Calcareous diatomaceous rocks of Zakynthos Island, Ionian Sea, containing mainly CaCO₃ and amorphous silica of biogenic origin with the form of opal-A were used. Cement mortars and pastes, with 0%, 10%, 20% and 35% replacement of cement with the specific diatomite, were examined. Strength development, water demand and setting time were determined in all samples. In addition, XRD, SEM and weight loss at 350 °C were applied in order to study the hydration products and the hydration rate in the cement-diatomite pastes. Blended cements, having up to 10% diatomite content, develop the same compressive strength, as the corresponding Portland cement, while the presence of diatomite leads to an increase of the paste water demand. Diatomite is characterized as natural pozzolana, as it satisfies the requirements of EN 197 1 concerning the active silica content. The pozzolanic nature of the diatomite results to the formation of higher amounts of hydrated products, specifically at the age of 28 days.     

煤矸石对硅酸盐水泥水化历程的影响

从强度、反应程度、孔溶液碱度和SEM等方面,研究了煤矸石作为水泥辅助胶凝材料的水化情况,并与Ⅱ级粉煤灰进行比较。试验结果表明:煤矸石发生火山灰反应时间比粉煤灰早,且发生火山灰反应所需的碱度值比粉煤灰低;掺煤矸石水泥水化样的早期抗压强度比粉煤灰水泥水化样低,但7d到28d强度增长速率明显大于相同掺量的粉煤灰水泥,相同28d抗压强度的条件下,煤矸石掺量比粉煤灰的掺量高10%。     

Effect of treatment temperature on the early hydration characteristics of superplasticized silica fume blended cement pastes

In this investigation, two mixes were used: ordinary Portland cement (OPC) and a blended cement prepared with the partial substitution of OPC by 10 mass% silica fume (SF). The setting and hardening characteristics were monitored by the aid of electrical conductivity as a function of curing time. The shear stress and electrical conductivity were studied at different temperatures, namely, 20, 35, 45 and 55 °C. As the temperature increases, the shear stresses decrease with the increase of shear rate. The height of electrical conductivity peaks of superplasticized cement pastes increases due to the increase of the paste fluidity. In the presence of 1.0% polycarboxylate (PC), the electrical conductivity of cement pastes decreases from 1 to 28 days. PC retards the hydration of cement pastes. The presence of PC extended the setting times of cement pastes at 35 °C than at 20 °C due to the increase in the adsorption capacity at this temperature. PC extends the dormant stage of the hydration process and delays the onset of the accelerating stage, without affecting its rate.     

Effects of three Turkish fly ashes on the heat of hydration of PC-FA pastes

Effects of the type and amount of fly ash substitution on the heat of hydration of portland cement-fly ash pastes were investigated. Three Turkish fly ashes were used. One of them was a high-calcium and the other two were low-calcium fly ashes. The specimens contained 0, 10, 20, and 40% fly ash by weight of portland cement. The tests were carried out as described in ASTM C 186 however one separate set of specimens were first subjected to an early external temperature of 67±2°C for six hours followed by the standard temperature until time of test. The results revealed that the low-calcium fly ashes, regardless of their type, reduce the heat evolution when used for partial cement replacement. The high-calcium fly ash, on the other hand, does not produce significant changes in the heat of hydration.     

垃圾焚烧飞灰胶凝活性和水泥对其固化效果的研究

垃圾焚烧飞灰是生活垃圾焚烧后烟气除尘器收下的物质,其主要成分属CaO-SiO_2-Al_2O_3-Fe_2O体系,与目前常用的高炉矿渣、粉煤灰等辅助性胶凝材料非常接近,因其中含有能被水浸出的重金属物质而被认为是危险废物,必须对之进行稳定及固化处理。通过试验研究了掺入垃圾焚烧飞灰的硬化水泥浆体的力学性能和水化机理,考察了水泥固化垃圾焚烧飞灰的效果,探讨了垃圾焚烧飞灰作为辅助性胶凝材料利用的可行性。研究表明:垃圾焚烧飞灰的水化反应活性较低,它的掺入在一定程度上延缓了水泥的水化过程,虽然其水化过程可以形成适量的钙矾石,对强度发展有利,但掺量较大时会显著降低水泥强度;采用水泥稳定及固化垃圾焚烧飞灰的效果良好,垃圾焚烧飞灰中重金属可以通过包容、替代或吸收等形式固化进水化产物结构中。     

粉煤灰水泥基材料的水化产物

用热重仪-差示扫描量热仪、扫描电子显微镜、透射电子显微镜、X射线能量散射、高分辩电子显微镜、压汞仪,测定了粉煤灰水泥基材料水化产物的形貌特征、微观结构、化学组成及水泥石的孔结构,讨论了水化产物性质及水泥石孔结构随粉煤灰掺量的变化规律。结果表明：粉煤灰的大量掺加,可以改善凝胶的化学组成。水化后期,粉煤灰与Ca(OH)2及由熟料水化生成的高n(Ca)／n(Si)的水化硅酸钙(C—S—H)凝胶发生二次水化反应,生成低n(Ca)／n(Si)的C—S—H凝胶,此种凝胶的固碱能力强,可减少碱-集料反应的危害性。同时,二次水化产物能够填充那些对水泥石强度和耐久性极为不利的孔隙空洞,使水泥石的结构更加致密,优化水泥石的孔结构,对提高水泥基材料的耐久性作用极大,为进一步提高工业废渣利用的技术水平奠定了基础。     

Influence of nucleation seeding on the hydration kinetics and compressive strength of alkali activated slag paste

Addition of pure calcium silicate hydrate (C–S–H) to alkali-activated slag (AAS) paste resulted in an earlier and larger hydration rate peak measured with isothermal calorimetry and a much higher compressive strength after 1 d of curing. This is attributed to a nucleation seeding effect, as was previously established for Portland cement and tricalcium silicate pastes. The acceleration of AAS hydration by seeding indicates that the early hydration rate is controlled by nucleation and growth. For the experiments reported here, the effect of C–S–H seed on the strength development of AAS paste between 1 d and 14 d of curing depended strongly on the curing method. With sealed curing the strength continued to increase, but with underwater curing the strength decreased due to cracking. This cracking is attributed to differential stresses arising from chemical and autogenous shrinkage. Similar experiments were also performed on Portland cement paste.     

The effect of admixtures on length change anomalies due to slow cooling and warming of hardened cement paste

Studies are reported on the effect of several admixtures (fly ash, water-reducing agents, mineral powder and an air-entraining agent) on the length-change anomalies present when hardened cement paste undergoes a slow cooling-warming cycle over the range 70°F to 0°F (20°C to ?18°C). Porosity, as expressed by the hydration parameters, appears to be the most important parameter influencing dimensional stability during freezing of saturated pastes, regardless of the presence of admixtures.     

Thermal behavior of cement matrix with high-volume mineral admixtures at early hydration age

Thermal cracks that usually occur in mass concrete are closely related to the thermal behavior of cement matrix, such as heat liberation, temperature rise and thermal shrinkage. Cement pastes added with large-volume mineral admixtures that are usually used for thermal controlling were cast into well-sealed plastic cylinder and covered by heat insulation materials to simulate the pseudo-adiabatic condition of mass concrete. The deformation and temperature rise of cement specimens under the heat insulation condition have been examined at early hydration age. Results show that with addition of fly ash, coal gangue and blast furnace slag the heat liberation and peak temperature of cement paste decrease, while its total shrinkage increases.There is no shrinkage but expansion of the pastes during the temperature rise process, which may be ascribed to the complete compensation of the shrinkage by thermal dilation of the pastes. The thermal dilation coefficient (TDC) of cement paste changes drastically with the hydration duration, and it is also related to the addition of mineral admixtures.     

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.     

Very High Volume Fly Ash Cements. Early Age Hydration Study Using Na2SO4 as an Activator

The early age ambient temperature hydration of a hybrid cement formulation containing very high volumes of coal fly ash (~80% by dry mass) and activated by Na₂SO₄ is presented. The Na₂SO₄ salt acts as a safe and convenient in situ source of alkali to activate fly ash glassy phases without undesirable effects on cement clinker hydration. Comparison to a reference paste with gypsum instead of sodium sulfate revealed that Na₂SO₄ reduced setting times, shortened the induction period, and increased early alite hydration and compressive strength development, but also restricted ettringite formation. When replacing the active fly ash component for milled sand of a similar particle size, the Na₂SO₄‐activated pastes set even quicker, no ettringite was observed, and early strengths were considerably reduced. Possible reaction mechanisms in the hybrid pastes are discussed.     

Influence of the cementitious paste composition on the E-modulus and heat of hydration evolutions

E-modulus and heat of hydration are features of cement-based materials that follow a rapid rate of change at early ages. This paper analyses the influence of the composition of cementitious pastes on these features by using two methods: (i) a novel technique for continuously monitoring the E-modulus of cement-based materials, based on evaluating the first resonant frequency of a composite beam containing the material under testing, and (ii) an isothermal calorimeter to determine the released heat of hydration. Seventeen mixes are tested, encompassing pastes with five w/c ratios, as well as different contents of limestone filler, fly ash, silica fume and metakaolin. The results permit the comparison of the E-modulus and heat of hydration sensitivities to mix composition changes, and to check possible relations between these features. This work also helps to establish the technique (i) as a non-destructive method for monitoring the E-modulus evolution in cement-based materials since casting.     

MXene和纳米SiO2对粉煤灰水泥水化性能的影响

本文利用差热分析、X射线衍射、扫描电镜等手段研究了纳米Si O_2和MXene对粉煤灰水泥水化性能的影响。结果表明,单掺纳米Si O_2能够促进粉煤灰水泥早期水化,提高水化开始时的放热速率,并使粉煤灰水泥浆体更加密实;而单掺MXene、复掺纳米Si O_2和MXene对粉煤灰水泥后期水化的促进作用比较明显,能够促进水泥中期强度增长。