A Conduction Calorimeter for Measuring the Heat of Cement Hydration in the Initial Hydration Period

A new-design conduction microcalorimeter is described, which has been used to measure the heat of cement hydration evolved in the initial period of hydration. The calorimeter is 30 cm³ in volume; the heat loss coefficient is 27.270±0.015 W V^–1, the time constant is 300 s. This revised version was published online in July 2006 with corrections to the Cover Date.     

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.     

A comparison of early hydration properties of cement–steel slag binder and cement–limestone powder binder

The early hydration properties of cement–steel slag composite binder and cement–limestone powder composite binder were compared in this study by determining the hydration heat of binder within 3 days, the pore structure of paste and the compressive strength of mortar at the age of 3 days. Results show that at the curing temperature of 25 °C, the early hydration heat of the binder containing steel slag is smaller, and the early pore structure of the paste containing steel slag is coarser, but the early compressive strength of the mortar containing steel slag is higher compared with the mix containing limestone powder. Though the early reaction degree of steel slag is low, its chemical contribution to the strength of mortar cannot be neglected. At the curing temperature of 50 °C, the early hydration heat of the binder containing steel slag is larger, and the early pore structure of the paste containing steel slag is finer, and the early compressive strength of the mortar containing steel slag is even higher compared with the mix containing limestone powder. Raising curing temperature can enhance the role played by steel slag more significantly than that played by limestone powder in the hydration and hardening of the composite binder.     

Effects of the type of calorimeter and the use of plasticizers and hydrophobizers on the measured hydration heat development of FGD gypsum

Thermal phenomena at the hydration of calcium sulphate hemihydrate (CaSO₄·0.5H₂O) are investigated in the paper. Time development of hydration heat of β-calcium sulphate hemihydrate prepared from flue gas desulphurization (FGD) gypsum is determined using two different types of calorimeter, namely the differential calorimeter DIK 04 and the isothermal heat flow calorimeter KC 01, and the differences in measured data analyzed. Then, the effects of plasticizers and hydrophobizers on the hydration process of analyzed gypsum mixtures are studied.     

Comparing study on hydration properties of various cementitious systems

The hydration properties of slag sulfate cement (SSC), slag Portland cement (PSC), and ordinary Portland cement (POC) were compared in this study by determining the compressive strength of pastes, the hydration heat of binders within 72 h, the pore structure, the hydration products, and the hydration degree. The results indicated that main hydration products of PSC paste and POC paste are calcium hydroxide and C–S–H gel, while those of SSC paste are ettringite and C–S–H gel from the analyses of XRD, TG–DTA, and SEM. At the early curing age, the compressive strength depends on the clinker content in the cementitious system, while at the late curing age, which is related to the potential reactivity of slag. From hydration heat analysis, the cumulative hydration heat of PSC is lower than that of POC, but higher than that of SSC. Slag can limit chemical reaction and the delayed coagulation of gypsum, which also plays a role in the early hydration. So SSC shows the lowest heat release and slag can’t be simulated without a suitable alkaline solution. Based on MIP analysis, the porosity of POC paste is the smallest while the average pore size is the biggest. At the age of 90 days, the compressive strength of SSC can get higher development because of its relative smaller pore size than that of PSC and POC paste.     

Hydration of shrinkage-compensating binders with different compositions and water-binder ratios

The calorimetric data of blended shrinkage-compensating binders with different compositions were measured at 25°C at different water-binder ratios using an isothermal calorimeter. The hydration characteristics of shrinkage-compensating binders were evaluated and their influence on the expansive properties of blended shrinkage-compensating binders was determined. Composition and w/b ratio significantly affect the hydration rate and degree of shrinkage-compensating binders, as well as their expansive and mechanical properties. The total heat of hydration of binders decreases with w/c ratios. Its final hydration degree also decreases with w/c ratio. The ternary binders composed with Portland cement, mineral admixture and expansive agent show low hydration heat and rate of heat evolution, but their total heat of hydration increases continuously and surpasses that of binary binder in later period at low w/b ratio. This revised version was published online in August 2006 with corrections to the Cover Date.     

Hydration of Portland cement with alkanolamines by thermal analysis

Four types of alkanolamines (i.e., traditional alkanolamines represented by TEA and TIPA and new alkanolamines represented by DEIPA and EDIPA) were added to Portland cement as chemical additives, and their effects on the cement properties and hydration process were investigated. An isothermal calorimeter was used to track the hydration heat flow of the cement pastes with or without alkanolamines. Thermogravimetric analyses were performed to measure the degree of hydration over the course of 28 days. In addition, X-ray diffraction, MIP analysis and SEM were used as auxiliary tests. The results indicated that alkanolamines improved the compressive strength of the cement mortars. It was found that TEA increased the rate of the second hydration of C₃A, and TIPA accelerated the hydration of C₄AF. DEIPA and EDIPA promoted the hydration of both the aluminum and ferrite phases as well as catalyzed the conversion of AFt to the AFm phase. By contrast, the new alkanolamines represented by DEIPA and EDIPA expressed more superior properties.     

Influence of Submicron Fibrillated Cellulose Fibers from Cotton on Hydration and Microstructure of Portland Cement Paste

This paper reports the influence of submicron hydrophilic fibers on the hydration and microstructure of Portland cement paste. Submicron fibrillated cellulose (SMC) fibers was prepared by the acid hydrolysis of cotton fibers in H₂SO₄ solution (55% v/v) for 1.5 h at a temperature of 50 °C. The SMC fibers were added into cement with a dosage of 0.03 wt.%, and the effect of SMC on the hydration and microstructure of cement paste was investigated by calorimeter analysis, XRD, FT-IR, DSC-TG, and SEM. Microcrystalline cellulose (MCC) fibers were used as the contrast admixture with the same dosage in this study. The results show that the addition of SMC fibers can accelerate the cement hydration rate during the first 20 h of the hydration process and improve the hydration process of cement paste in later stages. These results are because the scale of SMC fibers more closely matches the size of the C-S-H gel compared to MCC fibers, given that the primary role of the SMC is to provide potential heterogeneous nucleation sites for the hydration products, which is conducive to an accelerated and continuous hydration reaction. Furthermore, the induction and bridging effects of the SMC fibers make the cement paste microstructure more homogeneous and compact.     

A comparative study on cement hydration and microstructure of cement paste incorporating aminosulfonate–phenol–salicylic acid–formaldehyde and aminosulfonate–phenol–formaldehyde polymer

In this article, the water-soluble aminosulfonate–phenol–salicylic acid–formaldehyde (AH) polymer and aminosulfonate–phenol–formaldehyde polymer (AS) were incorporated into cement paste, and the effect of AH polymer on cement hydration and microstructure of cement paste was compared with AS polymer by means of isothermal calorimetry, X-ray diffraction, thermal analysis, mercury intrusion porosimetry, and scanning electron microscopy. The test results showed that the incorporation of AH and AS polymers into cement paste retards the rate of hydration reaction and reduces the amount of hydration products at early stages of hydration. The use of AH and AS polymers into cement paste also improves pore structure of cement paste. The pore size distribution of cement paste shifts toward smaller pore size scope. A smaller particle size of hydration product can be found in cement paste with AH and AS polymers. The cement paste with AH and AS polymers has a higher pore volume and total porosity. The surface morphologies of cement paste with AH and AS polymers are looser and more homogeneous than blank cement paste. Moreover, at the same dosage of polymer, the effect of AH polymer on the cement hydration and microstructure of cement paste was more significant than that of AS polymer.     

Influence of mechanical grinding on pozzolanic characteristics of circulating fluidized bed fly ash (CFA) and resulting consequences on hydration and hardening properties of blended cement

This paper investigates the influence of mechanical grinding on pozzolanic characteristics of circulating fluidized bed fly ash (CFA) from the dissolution characteristics, paste strength, hydration heat and reaction degree. Further, the hydration and hardening properties of blended cement containing different ground CFA are also compared and analyzed from hydration heat, non-evaporable water content, hydration products, pore structure, setting time and mortar strength. The results show that the ground CFA has a relatively higher dissolution rate of Al₂O₃ and SiO₂ under the alkaline environment compared with that of raw CFA, and the pozzolanic reaction activity of ground CFA is gradually improved with the increase of grinding time. At the grinding time of 60 min, the pozzolanic reaction degree of CFA paste is improved from 6.32% (raw CFA) to 13.71% at 7 days and from 13.65 to 28.44% at 28 days, respectively. The relationships of pozzolanic reaction degree and grinding time of CFA also conform to a quadratic function. For ground CFA after a long-time grinding such as 60 min, the hydration heat and non-evaporable water content of blended cement containing CFA are significantly improved. Owing to relatively smaller particle size and higher activity of ground CFA, the blended cement paste has more hydration products, narrower pore size distribution and lower porosity. For macroscopic properties, with increase in grinding time of CFA, the setting time and strength of blended cement are gradually shortened and improved, respectively.     

Humidity controlled calorimetric investigation of the hydration of MgSO4 hydrates

The isothermal heat of hydration of MgSO₄ hydrates was studied by humidity controlled calorimetry. Two hydrates, starkeyite (MgSO₄·4H₂O) and a mixture of MgSO₄ hydrates with summary 1.3 mol H₂O were investigated. The solid-gas reactions were initiated at 30°C and 85% relative humidity. The heat of hydration was determined in a circulation cell in the calorimeter C80 (Setaram). The crystal phases formed after the hydration process were analyzed by thermogravimetry (TG) and X-ray powder diffraction (XRD). Starkeyite reacted with the water vapour to the thermodynamic stable epsomite and the MgSO₄ hydrate mixture with 1.3 mol water to hexahydrite. The hydration heats of starkeyite and the mixture were determined to be −169±3 and −257±5 kJmol⁻¹, respectively.     

Influence of chromate reducers on cement hydration

Present research compared the effect of chromate reducers such as ferrous sulphate heptahydrate (FeSO₄·7H₂O) and stannous sulphate dihydrate (SnCl₂·2H₂O) on the hydration of cement paste, using water?cement ratio of 0.5 and sealed in plastic bags without curing for 28 days. Uncured hydration properties of cement paste are investigated in detail by thermogravimetric analysis (TGA) and verified with the use of scanning electron microscopy (SEM) and X-ray powder diffractometry (XRD). This research concluded that the cement paste with 0.1% additives showed better hydration in the uncured condition than the control.

     

Modeling hydration properties and temperature developments of early-age concrete pavement using calorimetry tests

This research aims to evaluate the calorimetry tests for characterizing cement hydration properties and predicting temperature developments of the early-age Portland cement concrete pavement (PCCP). Analytical models are studied to simulate hydration properties, using the measured heat evolution data from both the isothermal and semi-adiabatic tests. HIPERPAV III^® engineering software with these analytical models embedded is used to predict temperature developments of the early-age PCCP. Results show that the maximum hydration time parameter τ corresponds to the maximum activation energy E_a. Semi-adiabatic tests result in a lower hydration shape parameter β yet a higher hydration time parameter τ than isothermal tests. As results, the simulated degree of hydration based on semi-adiabatic tests is higher at the early hours, but lower at later hours compared to that based on isothermal tests. This effect is also reflected from the simulated temperature developments of the early-age PCCP. Three engineering projects in this research show that predicted temperatures of the PCCP using hydration parameters determined from semi-adiabatic tests better match actual measurements than that from isothermal tests.     

Studies of cementitious systems with new generation by-products from fluidised bed combustion

The rate of heat evolution as well as total heat output are strongly affected by other components of hydrating mixture, apart from neat portland cement, such as slag, fly ash and other industrial by-products; among them the wastes from fluidised bed combustion (FBC) has been taken into account recently. In this study the calorimeter was applied to follow the early hydration of cements produced with these materials. They interact with cement paste in a few ways: as set controlling agent and as active pozzolanic admixtures. Thus the rate of heat evolution/hydration is modified, depending on the composition of clinker and percentage of waste in the mixture. After the series of measurements for clinker-waste mixture hydrated systems also some ‘model’ mixtures were investigated to separate the effects from particular waste components. This revised version was published online in July 2006 with corrections to the Cover Date.     

Dynamic mechanical thermoanalysis of layered calcium silicate hydrates

Dynamic mechanical thermoanalysis (DMTA) was conducted on compacted specimens of calcium silicate hydrates (C-S-H), 1.4 nm tobermorite, jennite, and compacted hydrated Portland cement paste powders, as well as hardened cement paste. The synthetic silicates are key elements for compositional models of the hydrated calcium silicates present in cement paste. The study focuses on the nanostructural effects due to the removal of water from the 11 % RH condition. The DMTA results (E′ and tan? versus temperature curves) in the 25–110 °C range mimicked those of DMA (E′ and tan? versus mass loss curves) conducted at room temperature for C-S-H and cement paste. In addition, the DMTA curves for 1.4 nm tobermorite and jennite in the temperature range 110–300 °C were sensitive to phase changes including the transition of 1.4 nm tobermorite to 1.1 nm tobermorite and other forms, as well as the transition of jennite to metajennite. The DMTA curves of a 50/50 mixture of 1.4 nm tobermorite and jennite exhibit similarities and differences to that of hydrated cement paste that are influenced by porosity and the amorphous nature of C-S-H in the cement paste. The study provides useful data for evaluating Taylor’s concept of a possible tobermorite-jennite model for the C-S-H present in hydrated cement paste.     

Quantitative analysis of phase transition of heated Portland cement paste

This paper studies Portland cement paste heated up to different temperatures ranging from 105 to 1,000 °C by X-ray diffraction. The heated cement paste samples are kept isothermal in furnace for 6 h and cooled down to 100 °C. Then the samples are picked out and grinded into fine powders. 10 % Corundum is blended with cement paste powders as an internal standard. Quantitative phase analysis of cement paste samples is performed by Rietveld method. With the addition of a crystalline standard, the mass fractions of all crystalline phases as well as amorphous calcium silicate hydrate (C–S–H) are determined. The Rietveld analysis results are compared with independent measurements of the same material by thermal analysis (TG/DSC). The phase transition of Portland cement paste is discussed. An empirical relationship between the dehydration degree of C–S–H and the crystallization degree of C–S–H is derived.     

Influence of superplasticizers on the course of Portland cement hydration

A multicell isoperibolic — semiadiabatic calorimeter was used for the measurement of temperature and the determination of the hydration heat evolution at earlier period of cement pastes setting and hardening. The measurements were aimed at the determination of the effect of superplasticizers (SPs) on the course of the Portland cement hydration. Commercial polycarboxylate SP was added to the mixtures and the heat effect was measured. With the increasing content of SP, the hydration temperature increased up to a certain value and then decreased. In case of a sufficient amount of water in the mixture to achieve complete hydration of cement, samples with the highest values of the maximum hydration temperature reached the highest values of the released total heat. If there is not a sufficient amount of water to achieve complete hydration, the samples with the highest values of the maximum hydration temperature reach the lowest values of the released total heat.     

Application of isothermal and isoperibolic calorimetry to assess the effect of zinc on cement hydration

The amount of zinc in the clinker or in the secondary raw materials has been increasing in recent years. Zinc can get to Portland cement from solid waste or tires which are widely used as a fuel for burning in a rotary kiln. The aim of this work was to determine the effect of zinc on Portland cement hydration. This effect was studied by isothermal and isoperibolic calorimetry. Both calorimetry methods are suitable for measurements during the first days of hydration. Isoperibolic calorimetry monitors hydration process in real-life conditions, while isothermal calorimetry does it at a defined chosen temperature. Zinc was added to the cement in the form of two soluble salts of Zn(NO₃)₂, ZnCl₂ and a poorly soluble compound ZnO. The concentration of zinc added was chosen as 0.05, 0.1, 0.5 and 1 mass%. The results show that increasing amounts of zinc ions in cement pastes lead to hydration retardation and reduce both the maximum temperature and the maximum heat flow due to the retarding effect of zinc. The newly formed compounds during hydration were identified by X-ray diffraction method.     

The study of hydrothermal processes by the differential thermal analysis method

A DTA apparatus has been developed which can operate up to pressures of 500 atm and temperatures of 500°C. A coated thermocouple (thermocoax) is used for the measurement of temperature differences. Thermograms for the dehydration of gypsum, hydration of cement paste and hydrothermal synthesis of calcium silicates hydrates are shown to demonstrate the capability of the apparatus.     

Thermokinetic analysis of the hydration process of calcium phosphate cement

A microcalorimeter (Setaram c-80) was used to study the thermokinetics of the hydration process of calcium phosphate cement (CPC), a biocompatible biomaterial used in bone repair. The hydration enthalpy was determined to be 35.8 J g^–1 at 37.0°C when up to 80 mg CPC was dissolved in 2 mL of citric buffer. In the present study, parameters related to time constants of the calorimeter were obtained by fitting the recorded thermal curves with the function θ=Ae^–?t(1– e^–?2t). The real thermogenetic curves were then retrieved with Tian function and the transformation rate of the hydration process of CPC was found to follow the equation α=1–[1–(0.0075t)³]³. The microstructures of the hydrated CPC were examined by scanning electron microscopy. The nano-scale flake microstructures are due to crystallization of calcium phosphate and they could contribute to the good biocompatibility and high bioactivity.