Effects of Water-cement Ratio and Hydration Heat Regulating Materials on Hydration Process of Early-age Cementitious Materials

By means of low-field nuclear magnetic resonance(LF-NMR),the transverse relaxation time(T_(2))signals of physically bound water in cement paste were monitored to indicate water content change and characterize the early-age hydration process.With the curves of the T_(2)signals and hydration time obtained,the hydration process could be divided into four typical periods using the null points of the second derivative curve,and the influences of water-cement ratio(w/c)and hydration heat regulating materials(HHRM)on hydration process were analyzed.The experimental results showed that the hydration rate of pure cement paste in accelerated period presented a positive correlation with w/c.Compared to pure cement paste,the addition of HHRM extended all four periods,and led to a much faster hydration rate in initial period as well as a slower rate in accelerated period.Finally,according to the LFNMR test results,the early-age hydration model of cementitious materials was proposed considering w/c and HHRM content.

Early-age Hydration Characteristics of Composite Binder Containing Graphite Powder

The early-age hydration characteristics of composite binder containing graphite powder(GP)with two different finenesses were investigated by determining the hydration heat,thermo gravimetric,morphology of hardened paste as well as the compressive strength of mortar.The experimental results show that:replacing 2%-6%of cement with graphite powder significantly improves the piezoresistive effect of early age mortar,can be used to monitor accidental loads caused by dropped objects,collisions,or other accident events,and thus avoids initial damage.Some GP provides additional nucleation sites that lead to a fast formation of hydration products(nucleation-site effect).However,due to the almost hydrophobic water contact angle,most of the GP causes a large number of micro-cracks in the hydrated paste(gap effect).Because of the lamellar shape and high surface energy,GP is easily balled and can not be uniformly distributed in the composite,resulting in clumping together and wrapping some of the cement particles(barrier effect).Due to nucleation-site effect,when the dosages of coarse and fine GP reached 2%and 4%,1 d strength were increased by 9.1%and 9.6%,respectively.At 3 days,as the interior damage caused by the gap effect gradually increased,and the retarding effect on cement hydration caused by barrier effect was enhanced.GP has an obvious negative effect on compressive strength.However,micro-cracks caused by fine GP are less,so its negative effect on 3 d compressive strength is lower.

Effect of Additional Surfaces on Ordinary Portland Cement Early-Age Hydration

Early-age hydration of Ordinary Portland Cement (OPC) was studied in the presence of two additional surfaces. Additional surfaces are known to accelerate the early-age hydration of OPC. Autocatalytic reaction modelling was used to determine acceleration mechanism of additional surfaces. Heat development of the hydration was measured with semi-adiabatic calorimetry and the results were modelled with an autocatalytic reaction. Autocatalytic reaction modelling was able to determine number of initially active nucleation sites in early-age hydration. OPC hydration followed autocatalytic reaction principles throughout induction period and accelerating period. Both of the added surfaces, limestone filler and calcium-silicate-hydrate (C-S-H) coated limestone filler accelerated the early-age hydration. According to autocatalytic modelling, the C-S-H coated filler increased the number of initially active nucleation sites. Pristine limestone filler accelerated the early-age hydration by providing the additional nucleation sites throughout the early-age hydration. The difference was explained with common theories of nucleation and crystal growth. Autocatalytic model and measured calorimeter curve started to significantly deviate at the inflection point, where the reaction mode changed. The reaction mode change depended on the average particle distance. Early-age hydration, modelled as autocatalytic reaction was able to improve understanding of OPC early-age hydration and quantify the number of initially active nucleation sites. Understanding and quantifying the acceleration mechanisms in early-age hydration will aid larger utilization of supplementary cementitious materials where understanding the early-age strength development is crucial.

Hydration Heat Evolution of Cement and Its Relation With Setting Time

In order to veritably measure the first peak of hydration heat evolution that has been illustrated important in indicating cement behavior in early hydration, an improved way of water addition into cement in isothermally calorimetric experiment is put forward. The experimental results indicated that: the magnitude of first peak of heat evolution varies from sample to sample, correlation between heat evolution during first peak of heat evolution and initial (as well as final) setting time is unsatisfactory when samples are not classified; while groups of sample classified based on strength grade represent satisfactory correlations, which indicating the existence of close relation between hydration heat evolution in much earlier hydration age and setting property of cement in rather later age. Importance of first peak in hydration heat evolution for understanding cement setting property and reasons for sample classification are also discussed in this paper.

Hydration Heat Effect of Cement Pastes Modified with Hydroxypropyl Methyl Cellulose Ether and Expanded Perlite

Hydration heat effect of cement pastes and mechanism of hydroxypropyl methyl cellulose ether （HPMC） and expanded perlite in cement pastes were studied by means of hydration exothermic rate, hydration heat amount, FTIR and TG-DTG. The results show that HPMC can significantly delay the hydration induction period and acceleration period of cement pastes. As mixing amount increased, hydration induction period of cement pastes enlarged and accelerated period gradually went back. At the same time, the amount of hydration heat gradually decreased. Expanded perlite had worse delay effects and less change of hydration heat amount of cement pastes than HPMC. HPMC changed the structure of C-S-H during cement hydration. The more amount of HPMC, the more obvious effect. However, EXP had little influence on the structure of C-S-H. At the same age, the content of Ca （OH）2 in cement pastes gradually decreased as the mixing amount increase of HPMC and expanded perlite, and had better delay effect than that single-doped with HPMC or expanded perlite when HPMC and expanded nerlite were both dooed in cement pastes.

Temperature distributions in concrete box girders due to heat of concrete hydration

Based on heat transfer theory,a two-dimensional complex exponential function was used to compute heat of concrete hydration.A concrete box girder consisting of a single box with two cells used on Harbin Songpu Bridge was measured on site.The two coefficients in the complex exponential function were determined to best fit the field measured data.ABAQUS program was used to simulate the heat transfer and determine the temperature distribution in the concrete box girders during concrete setting.The calculated temperature distribution in the box girders were compared with the field measured data and good agreement was observed.The temperature distribution and gradient in the entire box section,webs and bottom slab were analyzed using the measured and calculated results during the course of concrete hydration.

Reaction Rate Characteristics of SrBr2 Hydration System for Chemical Heat Pump Cooling Mode

Here, we propose a chemical heat pump chiller with a SrBr2 hydration reaction system for utilization of waste heat. The SrBr2 hydration reaction could recover waste heat in low temperatures ranging from 373 K to 353 K, and the system showed good potential in terms of the high cooling thermal-storage density. Previous studies have given little information on the reaction characteristics of the SrBr2 hydration reaction. In this paper, we developed a measuring method for the hydration reaction equilibrium and reaction rate based on the volumetric method. We analyzed the hydration reaction rate with an unreacted-core shell model. In the experiments, the SrBr2 equilibrium temperature observed was equal to the theoretical equilibrium temperature obtained from thermodynamic databases. In addition, the hysteresis gap between the hydration and dehydration values was 2.0 K. Thus, the hysteresis effect was negligible for the chemical heat pump cooling operation. The reaction fraction of the SrBr2 hydration reached 0.7 within 20 s. By analyzing the hydration reaction rate with the unreacted-core shell model, the activation energy value was calculated to be56.6 kJ/mol. The calculation results showed good agreement with those of the experiment as the reaction fraction reached 0.7.

Preparation and Mechanism Research of Hydrationheat-inhibiting Materials with Microcapsule Sustained-releasing Technology

Hydration-heat-inhibiting materials(HIM)with polysaccharide as core material was prepared using microcapsule sustained-releasing technology,through a centrifugal spray granulation process after melting together.The preparation process parameters of HIM were selected by the semi-adiabatic temperature rise test of cement paste.TAM air microcalorimeter was used to investigate the regulation performance of HIM on the hydration of cement.The influence of HIM on the microstructure of cement was investigated by XRD,SEM,and TG-DSC.The results showed that the most suitable wall material for HIM was polyethylene wax,the optimum polyethylene wax/polysaccharide mass ratio was 1,and the most effective particle size was 0.16-0.30 mm.Polysaccharide coated by polyethylene wax released slowly,and the peak heat release rate of cement could be reduced by 55.2%after continuous regulaion.The regulation period continued to 120 h.HIM mainly decreased the C3S reaction rate,which resulted in a 39.2%peak value reduction of hydration heat release rate.However,HIM had little regulation on C3A.The hydration heat release process of cement-based materials can be designed by adjusting the dosage of HIM.

Coupled Effects of Heat and Moisture of Early-Age Concrete

In order to analyze the coupled influence of temperature and humidity on early-age concrete(including cement and copper tailings),a mathematical model is introduced on the basis of the Krstulovic-Dabic hydration reaction kinetic equations.In such a framework,the influence of hydration-released heat and water consumption are also taken into account.The results provided by such a model are verified by means of experiments and related sensor measurements.The research results show that this model can adequately predict the internal temperature and the humidity temporal evolution laws.

Experimental Evaluation of the Heat Output/Input and Coefficient of Performance Characteristics of a Chemical Heat Pump in the Periodic Operation of CaCl₂Hydration

We herein evaluate the use of a chemical heat pump (CHP) for upgrading waste heat. CaCl2 was used in the system of CHP. We evaluated the heat storage and heat releasing of CHP, and confirmed the practicality from the experimental results. The reactor module employed was an aluminum plate-tube heat exchanger with corrugated fins, and the CaCl2 powder was in the form of a packed bed. Heat storage operation and heat dissipation operation are performed at the same time and supplied to the heat demand destination. At this time, an environmental heat source can be used during the heat radiation operation, and the heat output can release more heat than the heat input during heat storage. The heat discharging and charging characteristics of the reactor module were evaluated experimentally. The coefficient of performance (COP) was calculated for the heat upgrading cycle, and the heat output in the system was determined. A COP of 1.42 and output of 650 W/L, based on the heat exchanger volume, were obtained using a 600 s change time for the heat pump.

Effects of Citric Acid on Hydration Process and Mechanical Properties of Thermal Decomposed Magnesium Oxychloride Cement

In order to make full use of salt lake magnesium resources and improve the strength of the thermal decomposed magnesium oxychloride cement （TDMOC）, the effects of citric acid on the hydration process and mechanical properties of TDMOC was studied. The hydration heat release at initial 24 h and strengths at 3, 7, and 28 days of TDMOC specimens were conducted. The hydration products and paste microstructure were analyzed by XRD, FT-IR and SEM, respectively. The results showed that citric acid can not only reduce the 24 h hydration heat release and delay the occurring time of second peak of TDMOC, but also produce more 5Mg（OH）z.MgC12.SH20 and less Mg（OH）2 in hydration process of TDMOC. More perfect and slender crystals were observed in the microstructure of the TDMOC pastes with citric acid. The results demonstrated that citric acid as an additive of TDMOC can decrease the hydration heat release and increase the compressive strength and flexural strength of TDMOC. The possible mechanism for the strength enhancement was discussed.

Heat flow pattern,base of methane hydrates stability zones and BSRs in Shenhu Area,northern South China Sea

Using the collected 433 heat flow values, we estimated the bases of methane hydrate stability zone （BHSZ）, in northern South China Sea （NSCS）. Through comparing BHSZs with the depths of bottom simulating reflectors （BSRs）, in Shenhu Area （SA）, we found that there are big differences between them. In the north of SA, where the water depth is shallow, many slumps developed and the sedimentation rate is high, it appears great negative difference （as large as -192%）. However, to the southeast of SA, where the water depth is deeper, sedimentation rate is relatively low and uplift basement topography exists, it changes to positive difference （as large as ＋45%）. The differences change so great, which haven＇t been observed in other places of the world. After considering the errors from the process of heat flow measurement, the BSR depth, the relationship of thermal conductivity with the sediments depth, and the fluid flow activities, we conclude that the difference should be not caused by these errors. Such big disagreement may be due to the misunderstanding of BSR. The deviant ＂BSRs＂ could represent the paleo-BSRs or just gas-bearing sediment layers, such as unconformities or the specific strata where have different permeability, which are not hydraterelated BSRs.

Hydration Characteristics of Sodium Sulfate Slag Cement System

The hydration characteristics by thermal analysis (DTA) were determined, and an isothermal calorimeter (IC) was used to study the pastes. The experimental results indicate: (1) The main hydration products of SSC are C-S-H (I) gel with a low Ca/Si ratio, crystalline Thomsonite-type and AFt-type phases containing certain alkali cations; (2) No phases of the AFm-type and high alkaline Ca (OH)(2) in SSC system could benefit the hydrated cements to improve its strength and durability; (3) Crystalline Thomsonite-type and AFt-type phases containing Na+ will greatly reduce free alkali and alleviate the harmness of alkali aggregate reaction (AAR) in SSC system; (4) Similar to ordinary Portland cement (OPC), the hydration process of SSC could be classified into five stage: initial, induction, acceleration, deceleration and decay; (5) Regardless of the activator used, the apparent activation energy is higher with the increased slag in cement system, and the rising temperature could promote the hydration of SSC.

Hydration Kinetics of Municipal Solid Wastes Incineration(MSWI) Fly Ash-Cement

Hydration heat behavior and kinetics of blended cement containing up to 20% MSWI fly ash were investigated based on its hydration heat evolution rate measured by isothermal calorimeter. Kinetics parameters, N and K, and hydration degree, Ca(OH)2 content, were also calculated and analyzed. According to the experimental results, the induction period was elongated, the second heat evolution peak was in advance, and the third hydration heat peak could be detected due to MSWI fly ash pozzolanic reaction. The hydration reaction rate was controlled by nucleation kinetics in the acceleration period and then by diffusion in the decay period, but in the deceleration period, the hydration experienced a dual controlling reaction of autocatalytic chemical reaction and diffusion. The hydration rate of blended cement was faster. Ca(OH)2 content increased before 14 days.

Effect of Phosphorus and Fluorine on Hydration Process of Tricalcium Silicate and Tricalcium Aluminate

By means of hydration heat, XRD and SEM, effect of phosphorus and fluorine （P205 and F-） in phosphorous slag on hydration process of tricalcium silicate （C3S） and tricalcium aluminate （C3A） was explored. The results indicated that the early hydration exothermic rate of C3S and C3A was obviously lowered by P205 and F- in phosphorous slag, the second peak occurring time of C3A was delayed by 0.9 h, the exothermal output of C3S was reduced by 25.04% and the time of accelerating stage was postponed by 0.86 h. The early hydration degree of C3S and C3A was also decreased. Due to the influence of P205 and F, more pores and thinner crystals can be observed in the microstructure of hardened paste and the chance of cracks was reduced.

Measurements of Hydrate Equilibrium Conditions for CH4, CO2, and CH4＋C2H6＋C3H8 in Various Systems by Step-heating Method

Phase equilibrium conditions of gas hydrate in several systems were measured by the step-heating method using the cylindrical transparent sapphire cell device.The experimental data for pure CH4 or CO2+deionized water systems showed good agreement with those in the literatures.This kind of method was then applied to CH4/CO2+sodium dodecyl sulfate(SDS)aqueous solution,CH4/CO2+SDS aqueous solution+silica sand,and(CH4+C2H6+C3H8)gas mixture+SDS aqueous solution systems,where SDS was added to increase the hydrate formation rate without evident influence on the equilibrium conditions.The feasibility and reliability of the step-heating method,especially for porous media systems and gas mixtures systems were determined.The experimental data for CO2+silica sand data shows that the equilibrium pressure will change significantly when the particle size of silica sand is less than 96μm.The formation equilibrium pressure was also measured by the reformation of hydrate.

Heat calculation and numerical simulation in steam mining of permafrost gas hydrate

Steam mining method was injecting hot steam into the borehole to heat the hydrate strata at the same time of depressurization mining,which could promote further decomposition and expand mining areas of gas hydrate. Steam heat calculation would provide the basis for the design of heating device and the choice of the field test parameters. There were piping heat loss in the process of mining. The heat transfer of steam flowing in the pipe was steady,so the heat loss could be obtained easily by formula calculation. The power of stratum heating should be determined by numerical simulation for the process of heating was dynamic and the equations were usually nonlinear. The selected mining conditions were 500-millimeter mining radius,10 centigrade mining temperature and 180 centigrade steam temperature. Heat loss and best heating power,obtained by formula calculation and numerical simulation,were 21. 35 W/m and 20 kW.

Influence of Comb-Polymer Structure on C₃S Phase Hydration

The cement hydration delay is due to comb-polymers (PCP), used as dispersant agent during the preparation of the cement paste. In order to evaluate the role of the PCP structure on hydration, the comb-polymer is separated in two main parts: the backbone (PAA) and the dispersing chain. A linear polymer made up of PEO, Mw = 1000, with a carboxylic head suitable to link the inorganic surface, was synthesized to simulate the effect of the dispersing-side chain. The hydration delay of C-S-H formation induced by comb-polymer on CEM I and C3S phase was analyzed by conduction calorimetry and the morphology of the crystalline structure in growth by SEM, specially studying the relation between structure and hydration time. The results show that the hydration delay is mainly ascribable to the comb-shaped structure as a whole, where PEO chain, as from considerations on energy, might assume conformations able to modify the salt concentration near the cement surface. The different hydration rates are tentatively related to the crystal growth and the surface texture observed by SEM.

Gas chromatographic thermodynamics on hydration processes of magnesium chloride with low water

The dehydration and hydration processes of magnesium chloride hydrates were studied by means of frontal chromatography analysis, calorimetry, thermogravimetry and chemical analysis. The mathematical imitation for the adsorption isotherms of MgCl 2·4H 2O and MgCl 2·2H 2O at different temperatures indicates that Boltzmann Function is the ideal equation to describe those adsorption isotherms. Its adsorption heat is -13.06 kJ/mol and -16.11 kJ/mol, respectively. The adsorption equilibrium constants are also given. From the data obtained, there is a thermodynamical possibility to use partial dehydrated magnesium chloride hydrates as an absorbance to clean water vapor contained in bischophite dehydration equipment and let the protection gas HCl recycle in the fluid bed reaction system.

Experimental investigation on the effective thermal conductivities of different hydrate-bearing sediments

The natural gas hydrate has been regarded as an important future green energy.Significant progress on the hydrate exploitation has been made,but some challenges are still remaining.In order to enhance the hydrate exploitation efficiency,a significant understanding of the effective thermal conductivity(ETC)of the hydrate-bearing sediment has become essential,since it directly controls the heat and mass transfer behaviors,and thereby determines the stability of hydrate reservoir and production rate.In this study,the effective thermal conductivities of various hydrate-bearing sediments were in-situ measured and studied.The impacts of temperature,particle size and type of sediment were investigated.The effective thermal conductivities of the quartz sand sediments before and after hydrate formation were in-situ measured.The results show the weak negative correlation of effective thermal conductivity of the quartz sand sediment on the temperature before and after the hydrate formation.The effective thermal conductivity of the hydrate-bearing sediment decreases with the increase of particle size of the sediment.The dominant effect of the type of porous medium on the characteristics of the effective thermal conductivity of hydrate-bearing sediment was highlighted.The results indicate that both the effective thermal conductivities of hydrate-bearing quartz sand sediment and hydrate-bearing silicon carbide sediment are weakly negatively correlated with temperature,but the effective thermal conductivity of hydrate-bearing clay sediment is weakly positively dependent on the temperature.In addition,the values of the effective thermal conductivities of various hydrate-bearing sediments are in the order of hydrate-bearing silicon carbide sediment>hydrate-bearing quartz sand sediment>hydrate-bearing clay sediment.These findings could suggest that the intrinsic thermal conductivity of porous medium could control the characteristics of effective thermal conductivity of hydrate-bearing sediment.