Heat evolution in hydrated cementitious systems admixtured with different set controlling components

Calorimetry has been used in the investigations of cementitious systems with different set controlling admixtures. The kinetics and mechanism of hydration process was thus characterized on two different cement clinkers mixed with calcium sulphate containing materials. These admixtures were collected as a residue in the fluidised bed combustion (FBC) of coals with simultaneous desulphurisation process - so-called bottom ash. Apart from anhydrite/gypsum, they were composed mainly of alumina and silica containing material of disordered structure, originating from the coal contaminations of clay character. Anhydrite/gypsum acts as set controlling admixture. The aluminosilicate component reacts with calcium ions released to the solution from the calcium silicate clinker minerals. It has been found that fluidised bed combustion wastes can be successfully used as set controlling admixture. There is no other harmful effects; those could be easily detectable by calorimetry. However the effect is dependent upon the composition of cement clinker. At low calcium aluminate content a slight acceleration of hydration process can be easily observed, particularly at higher amount of admixture. In the mixtures with high calcium aluminate clinker the heat evolved is slightly reduced in the presence of admixture. The dominating role of aluminate phase in heat evolution process within the first hours of hydration process has been thus proved. This revised version was published online in July 2006 with corrections to the Cover Date.     

Calorimetric investigations of the influence of waste aluminosilicate on the hydration of different cements

The aim of this work is to compare the influence of addition of waste aluminosilicate catalyst on the initial periods of hydration of different cements, i.e. calcium aluminate cements of different composition and Portland cement, basing on the calorimetric studies. Cement pastes containing up to 25 mass% of additive were studied, where the water/(cement+additive) ratio was 0.5. An attempt was undertaken to explain the mechanism of action of introduced aluminosilicate in the system of hydrating cement, particularly in the case of calcium aluminate cement pastes. It was found that the presence of fine-grained additive caused in all studied cases the increase of the amount of released heat in the first period after the addition of water. In the case of aluminate cements with aluminosilicate addition, a significant reduction of induction time and faster precipitation of hydration products were observed compared to the reference sample (without additive). In the experimental conditions, the additive caused the acceleration of aluminate cements hydration, and the mechanism of its action is probably complex and can encompass: nucleative action of small grains and formation of new chemical compounds.     

Isothermal and solution calorimetry to assess the effect of superplasticizers and mineral admixtures on cement hydration

The heat of hydration evolution of eight paste mixtures of various water to binder ratio and containing various pozzolanic (silica fume, fly ash) and latent hydraulic (granulated blast furnace slag) admixtures have been studied by means of isothermal calorimetry during the first 7 days of the hydration process and by means of solution calorimetry for up to 120 days. The results of early heat of hydration values obtained by both methods are comparable in case of the samples without mineral admixtures; the values obtained for samples containing fly ash and granulated blast furnace slag differ though. The results from isothermal calorimetry show an acceleration of the hydration process by the presence of the fine particles of silica fume and retarding action of other mineral admixtures and superplasticizer. The influence of the presence of mineral admixtures on higher heat development (expressed as joules per gram of cement in mixture) becomes apparent after 20 h in case of fly ash without superplasticizer and after 48 h for sample containing fly ash and superplasticizer. In case of samples containing slag and superplasticizer the delay observed was 40 h. The results obtained by solution calorimetry provide a good complement to the ones of isothermal calorimetry, as the solution calorimetry enables to study the contribution of the mineral admixtures to the hydration heat development at later ages of the hydration process, which is otherwise hard to obtain by different methods.     

Calorimetry in the studies of cement hydration

Calorimetry was applied to an investigation of the early hydration of Portland cement (PC)–calcium aluminate cement (CAC) pastes. The heat evolution measurements were related to the strength tests on small cylindrical samples and standard mortar bars. Different heat-evolution profiles were observed, depending on the calcium aluminate cement/Portland cement ratio. The significant modification of Portland cement heat evolution profile within a few hours after mixing with water was observed generally in pastes containing up to 25% CAC. On the other hand the CAC hydration acceleration effect was also obtained with the 10% and 20% addition of Portland cement. As one could expect the compressive and flexural strength development was more or less changed—reduced in the presence of larger amount of the second component in the mixture, presumably because of the internal cracks generated by expansive calcium sulfoaluminate formation.     

Heat evolution in hydrating expansive cement systems

Calorimetry was applied to follow the hydration of special cement mixtures exhibiting expansion or shrinkage compensation. The standard, common cements show generally less or more visible shrinkage on setting and hardening but mixed with and expansive agent, usually of aluminate and sulfate nature, they can exhibit the increase of volume. The calcium aluminate cement CAC 40 was ground together with special sulfate–lime sinter to produce an expansive additive to Portland cement (CEM I 42.5R). The expansive additive in the environment of hydrating cement transforms into ettringite at “right time” to give expansion before the final setting and hardening takes place. In the experiments the proportions of components of expansive mixture and basic cement were variable. The rate of hydration versus time for common cements is commonly known and reflects the moderate setting and early hardening during the first days after mixing with water (two peaks and the induction period between them). The aim of measurements presented in this study was to show the course of heat evolution curve and the heat evolved values, equivalent to the acceleration/retardation of hydration, in case of the paste with the expansive mixture, as well as the pastes produced from Portland cement and the components of expansive additives added in variable proportions. It was possible to see how the calorimetric curve and consequently the hydration process itself declines from the controlled setting/hardening. These measurements were supplied by the examples of phase composition studies by XRD.     

Thermal monitoring of flash setting in portland cement clinkers

Flash setting behavior of a Type I Portland cement clinker with and without the presence of gypsum (calcium sulphate dihydrate) used as a set regulator has been studied by using thermogravimetry and differential thermal analyzing techniques. The effect of sulphate addition in controlling the flash set is monitored over the critical initial period of hydration and its consequences on the ultimate setting properties of clinker are discussed. A correlation between degree of hydration and flash setting, caused mainly by a rapid reaction between water and the phase tricalcium aluminate present in the clinker, is also established by estimating the amount of chemically bound water and free calcium hydroxide incorporated in the hydration products formed from clinker-water and clinker-calcium sulphate-water systems. It is shown that the addition of sulphate ions effectively controls the early clinker hydration possibly by reacting with tricalcium aluminate to form ettringite that shields it from further rapid hydration.     

Calorimetric studies of β-Ca2SiO4 hydration in solutions of electrolytes

The hydration of β-Ca₂SiO₄ stabilized by thermal treatment and barium addition was studied in CaCl₂, Ca(NO₃)₂ and BaCl₂ solutions. The heat evolution kinetics was followed by calorimetry. A considerable acceleration of the hydration process was found in the presence of electrolytes. The positive influence of barium ions was confirmed. The highest total heat output during the 3-day hydration was found for samples doped with 3 mole % BaO.     

Calorimetric study of ternary binder of calcium aluminate cement,Portland-limestone cement and FGD gypsum

To use flue gas desulfurization (FGD) gypsum and limestone as supplement of cement, conduction calorimetry was applied to investigate the early hydration of ternary binder of calcium aluminate cement (CAC), Portland-limestone cement (PLC), and FGD gypsum, supplemented with the determination of setting times and X-ray diffraction (XRD) analysis. Different exothermal profiles were presented in two groups of pastes, in which one group (group A) sets the mass ratio of FGD gypsum/CAC at 0.25 and the other group (group B) sets the mass ratio of PLC/CAC at 0.25. Besides the two common exothermal peaks in cement hydration, a third exothermal peak appears in the pastes with 5–15% FGD gypsum after gypsum is depleted. It is found that not PLC but FGD gypsum plays the key role in such ternary binder where the reaction of ettringite formation dominates the hydration process. PLC accelerates the hydration of ternary binder, which mainly attributes to the nucleating effect of fine limestone particles and PC clinker. The modified hydration process and mechanism in this case is well visualized by the means of calorimetry and it helps us to optimize such design of ternary cementitious material.     

Calorimetric study of calcium aluminate cement blended with flue gas desulfurization gypsum

The use of by-product gypsum is an important alternative in concrete design. In present experiment, conduction calorimetry was applied to investigate the early hydration of calcium aluminate cement (CAC)/flue gas desulfurization (FGD) gypsum paste, supplemented with the determination of setting times and analysis of hydrates by X-ray diffraction (XRD). It was found that different profiles of heat evolution rate were presented depending on the CAC/FGD gypsum ratio. Two distinct exothermic peaks, associating with CAC hydration and ettringite formation respectively, appeared when the FGD gypsum content was less than 20%. Hydrate barrier mechanism was introduced to explain the difference in induction periods of the pastes with or without FGD gypsum. It is concluded that the blending of FGD gypsum accelerates the hydration of CAC for the quick formation of ettringite and generates greater hydration heat from per gram of pure CAC for the high exothermic effect of ettringite formation. The dissolution and diffusion of gypsum plays an important role of reacting controller during the hydrations of the pastes with FGD gypsum. The modified hydration process and mechanism in this case is well visualized by means of calorimetry.     

煤催化气化工艺中碱金属腐蚀刚玉质耐火材料的实验研究

针对煤催化气化反应器设计中遇到的材料问题,采用碳酸钾及催化气化工况富含碱金属气化灰渣为实验原料,进行了碱金属腐蚀刚玉质耐火材料的实验研究。着重考察了有氧空气气氛和无氧还原性气氛、反应温度、反应时间、碱金属存在形态对腐蚀行为的影响,并结合SEM-EDX、XRD、核磁Al谱等表征手段,研究了反应前后碱金属和刚玉质耐火材料的成分、物相及结构变化。结果表明,碱金属对耐火材料腐蚀行为受反应的温度、气氛、时间及碱金属存在形态等因素影响较大。分析表明,有氧空气气氛下腐蚀尤为严重的原因是,原料中存在的钾与刚玉耐火材料发生化学反应生成新的钾的铝酸盐物相,且其含量随温度升高、反应时间延长而增加。     

Calorimetry and other methods in the studies of expansive cement hydrating mixtures

In this study, the calorimeter was applied to follow the hydration of special cement mixtures exhibiting expansion or shrinkage compensation. The shrinkage-less and expansive binders were produced by mixing of Portland cement with an expansive additive produced by sintering and composed of calcium sulfoaluminate (yeelimite), calcium sulfate (anhydrite) and lime. The studies were focused on the synthesis of this aluminate??sulfate??lime additive (temperature of burning process as a parameter controlling the relative activity of components) from the materials being the by products and subsequently on the mixture proportions to ensure the hydration process resulting in non-shrinkage or expansion effect. In the experiments the proportions of expansive mixture and cementitious materials were variable. The investigations with aim to find the relationship between the volume changes and composition of initial mixtures in cement pastes and mortars (with sand) were also carried out. The phase composition and microstructure of products were characterized. The expansive additive in the environment of hydrating cement transforms into ettringite and gives an increase of volume when the plastic material transforms to the more rigid matter but before the ultimate hardening takes place. Proper, moderate setting and hardening in strongly modified mixtures is achieved when the calorimetric curve corresponding to the heat evolution on hydration is analogous to that for the basic Portland cement. The rate of heat evolution data are well compatible with the other results related to the other methods of hydration kinetics assessment (e.g. chemical shrinkage) and discussed in terms of the phase composition of hydration products.     

Principal component and cluster analyses as supporting tools for co-crystals detection

The effects of super absorbent polymer (SAP) on the early hydration evolution of Portland cement within 72 h were investigated by isothermal calorimetry, thermal analysis and X-ray diffraction analysis. The results show that the SAP definitely affects the early hydration process of Portland cement, increases the hydration heat evolution rate during the acceleration period and during the main exothermic peak, promotes the earlier appearance of the main exothermic peak, but does not affect the lengths of the initial reaction period and the induction period and the onset of the acceleration period. The SAP can accelerate cement hydration to increase the hydration degree within 72 h. But the dosage variation of SAP has minor influence on the hydration heat evolution and hydration degree. The SAP enhances the formation of Ca(OH)₂ after 12 h to keep higher content than that in the reference paste. The SAP does not affect the maximum content of ettringite, but delays the conversion of ettringite to monosulphate to remain ettringite content higher at later hydration time. Besides, no new phases are found to have formed in cement paste with SAP.     

Application of calorimetry as a main tool in evaluation of the effect of carbonate additives on cement hydration

Calorimetry was applied to follow the hydration in the Portland cement–dolomite–limestone mixtures. In the experiments the limestone additive of various fineness (standard component of various common cements), as well as the dolomite additive (not a standard component) were used. The rate of hydration versus time for common cements reflects the proper setting and early hardening during the first days after mixing with water (two or three peaks and the induction period between them). The aim of measurements presented in this work was to show the course of heat evolution curve and the heat evolved values, equivalent to the acceleration/retardation of hydration, in case of the pastes produced from Portland cement and the carbonate additives mixed in variable proportions, as well as to verify the results by other methods. The rate of heat evolution accompanying cement paste hydration, total heat evolved, conductivity of hydrating suspension and rheological (flow) properties versus time are modified by the fine grained carbonate additives. This is due to the hypothetical nucleating effect of limestone and dolomite.     

Electroless Ni-plating on PTFE fine particles

A Ni electroless plating process was used with polytetrafluoroethylene (PTFE) fine particles (25–500 μm). Using nonionic hydrocarbon surfactant, PTFE particles were dispersed in the plating bath. The PTFE hydrophobicity was sufficiently high that Ni was deposited partly on the PTFE surface in the initial step. The Ni-PTFE particles were formed into the Ni-PTFE plate by heat treatment at 350 °C after pressing. The Ni-PTFE plate had electrical conductivity and gas permeability, which were influenced by the pore distribution in the plate. Pores with 1 μm diameter might be especially important to impart high gas permeability to the Ni-PTFE plate.     

Investigation of early hydration of high aluminate cement-based binder at different ambient temperatures

The effect of spent FCC catalyst on early hydration (up to 48?h) of high aluminate cement (Al₂O₃ >70%) at different ambient temperatures (10, 20, and 30?°C) was investigated. Cement pastes with constant ratio of water/binder?=?0.35 (binder?=?cement?+?addition) and containing 0, 5, 10, and 15% mass of addition as replacement of cement were studied. The hydration kinetics was determined by calorimetric measurements and the structure of hardened binders after 2?days of curing at an appropriate temperature was also investigated using X-ray, SEM, and thermal analysis methods. Due to the fact that hydration of aluminate cements is highly sensitive to temperature conditions as well as certain changes of temperature are inevitable in practice, the evaluation of the impact of the waste catalyst addition in such conditions is justified. On the basis of obtained results, it was stated that the temperature determines the early hydration of high aluminate cement and decides about the influence of waste aluminosilicate. The introduction of the discussed addition has a big impact on the kinetics of cement hydration closely related to the curing temperature. The presence of spent catalyst accelerates the hydration at the temperatures of 20 and 30?°C, but at the temperature of 10?°C this waste aluminosilicate acts as a retarding agent. The effect of the addition on the microstructure of hardened binders after 48?h of hydration is rather insignificant, especially at 20?°C, compared to the influence of the temperature on hydration. At the temperature of 10?°C, a formation of low amount of C₂AH₈ can be observed because of the presence of spent catalyst, while at the temperature of 30?°C the introduction of the mineral addition prevents the hydrogarnet formation.     

Studies of conversion progress of calcium aluminate cement hydrates by thermal analysis method

This article presents the investigations of the progress of conversion process of calcium aluminate hydrates formed during hydration of calcium aluminate cement at various temperature conditions occurring over time by thermal analysis method. Moreover, the differences of microstructure were also confirmed by SEM/EDS studies and X-ray diffraction analysis. On the basis of the obtained results, it is concluded that thermal analysis method is a very attractive and useful way to identify the structure of hydrated calcium aluminate cement matrix and allows estimating the degree of the conversion at different times of various process conditions. The conversion process of metastable calcium aluminate hydrates into stable hydrogarnet and gibbsite is strictly temperature dependent and could be completed at different times. Acceleration of the conversion is caused not only by the increasing external temperature of storage, but also the temperature inside the sample is very important. The self-heating, which could be strong in large sample, and occurring during first few hours of hydration of calcium aluminate cement, initiates the transformation.     

Influence of Sn on the hydration of tricalcium aluminate, Ca3Al2O6

Tricalcium aluminate (Ca₃Al₂O₆, C₃A) containing 0?C5% of Sn was synthesized by solid-state method, and the products were characterized by XRD technique. Differential thermo-analytical technique (DTA) along with X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM) were applied to study the hydration behaviour of different C₃A samples with and without the presence of gypsum. Results indicate that C₃A can accommodate small amount of Sn in its structure and remaining amount forms SnO₂. Hydration studies of the synthesized C₃A shows that the additions of 0.5 and 1% Sn increase and 2% Sn decrease the reactivity of C₃A at the initial period (<3?h) of hydration. Increasing additions of Sn also increase the amounts of amorphous phases and hexagonal calcium aluminate hydrates in the cement pastes. The stabilities of these hydration products also increase with increasing content of Sn in C₃A at the experimental conditions. The presence of Sn significantly changes the hydration of C₃A and gypsum solid mixture at the initial period of hydration by enhancing the formation of more amounts of AFt and AFm phases. However, at the later stage of hydration (on or after 3?days), the hydration products in C₃A and gypsum pastes with and without the presence of Sn are almost similar.     

Liquid-phase hydration process of cyclohexene with zeolites

The liquid-phase hydration process of cyclohexene into cyclohexanol with zeolite is described. The characteristic of this industrial process is that fine particles of zeolite are used in a slurry system, which offers high productivity and a simple separation system. In this process, the hydrophobic property and shape selectivity of ZSM-5 are fully utilized so as to realize an economical industrial process.     

Study on optimization of hydration process of blended cement

To optimize the hydration process of blended cement, cement clinker and supplementary cementitious materials (SCMs) were ground and classified into several fractions. Early hydration process of each cementitious materials fraction was investigated by isothermal calorimeter. The results show fine cement clinker fractions show very high hydration rate, which leads to high water requirement, while fine SCMs fractions present relatively high hydration (or pozzolanic reaction) rate. Cement clinker fractions in the range of 8–24 μm show proper hydration rate in early ages and continue to hydrate rapidly afterward. Coarse cement clinker fractions largely play “filling effect” and make little contribution to the properties of blended cement regardless of their hydration activity (or pozzolanic activity). The hydration process of blended cement can be optimized by arranging high activity SCMs, cement clinker, and low activity SCMs in fine, middle, and coarse fractions, respectively, which not only results in reduced water requirement, high packing density, and homogeneous, dense microstructure, but also in high early and late mechanical properties.     

Thermodynamics of the silver-silver ion electrode and thermodynamic solubility product constants of silver halides and pseudo-halides in urea-water mixtures

The hydration kinetics of tricalcium aluminate, C₃A, with gypsum or anhydrite at 1:3 mole ratio were studied using hydration periods of 5 min up to 7 days. These studies were assessed with the aid of differential thermal analysis, thermogravimetric analysis and X-ray diffractometry as well as chemical analysis.The results revealed that hydration periods of up to 7 days of tricalcium aluminate with gypsum in paste form and in suspension, forms ettringite with unhydrated components of C₃A and gypsum. On the other hand, the only hydration product of the slurry of C₃A with anhydrite is ettringite after 7 days of hydration. The kinetics of hydration were studied by the quantitative determination of ettringite from the TG analysis. The results also illustrate that the rate of ettringite formation is slower in the presence of gypsum than in the presence of anhydrite and also that hydration of the slurry gives more ettringite than the hydration of the paste.