Microstructure and Composition of Hydration Products of Ordinary Portland Cement with Ground Steel-making Slag

The effect of ground steel-making slag on microstructure and composition of hydration products of ordinary Portland cement (OPC) was investigated by mercury intrusion porosimetry (MIP),X-ray diffraction (XRD) and differential thermal analysis (DTA).Results show that ground steel-making slag is a kind of high activity mineral additives and it can raise the longer-age strength of OPC mortar.The total porosity and average pore diameter of OPC paste with ground steel-making slag increase with the increase of the amount of ground steel-making slag replacing OPC at various ages,while after 28 days most pores in OPC paste with ground steel-making slag do not influence the strength because the diameter of those pores is in the rang of 20 to 50nm.The hydration mechanism of ground steel-making slag is similar to that of OPC but different from that of fly ash and blast furnace slag.The hydration products of ground steel-making slag contain quite a lot of Ca(OH) 2 in long age.

Hydration Products of Cement-silica Fume-quartz Powder Mixture under Different Curing Regimes

Composition, morphology, and structure of hydration products in hardened pastes of three kinds of blended cement（cement-silica fume, cement-quartz powder and cement-silica fume-quartz powder） hydrated under different curing regimes（standard curing, 90 ℃ steam curing, 200 ℃ and 250 ℃ autoclave curing） were investigated by X-ray diffraction and field emission scanning electron microscope equipped with EDAX system. Results showed that the main hydration products in three kinds of hardened pastes under standard curing condition are all C-S-H gels, CH, and AFt. Under 90 ℃ steam curing condition, the main hydration products of cement-silica fume and cement-silica fume-quartz powder are C-S-H gels, whereas those of cement-quartz powder are C-S-H and CH. Under 200 or 250 ℃ autoclave curing condition, no obvious crystallized CH phase is found in hardened pastes of three kinds of blended cement, and C-S-H gels are transformed into one or more crystalline phases such as tobermorite, jennite, and xonotlite. The chemical composition and morphology of these crystalline phases depend on the composition of mixture and autoclave temperature.

Influence of Cellulose Ethers on Hydration Products of Portland Cement

Cellulose ethers are widely used to mortar formulations,and it is significant to understand the interaction between cellulose ethers and cement pastes.FT-IR spectra,thermal analysis and SEM are used to investigate hydration products in the cement pastes modified by HEMC and HPMC in this article.The results show that the hydration products in modified cement pastes were finally identical with those in the unmodified cement paste,but the major hydration products,such as CH（calcium hydroxide）,ettringite and C-S-H,appeared later in the modified cement pastes than in the unmodified cement paste.The cellulose ethers decrease the outer products and increase inner products of C-S-H gels.Compared to unmodified cement pastes,no new products are found in the modified cement pastes in the present experiment.The HEMC and HPMC investigation shows almost the same influence on the hydration products of Portland cement.

Quantitative Calculation of Hydration Products for Binary Slag-Portland Cement System

The reaction models and the quantitative calculation on the volume fraction of hydration products for binary ground granulated blast-furnace slag （GGBFS） cement system are presented, in which two important factors are taken into account, i e, the reactivity of GGBFS influenced by its chemical compositions and the partial replacement of aluminum phase in calcium silicate hydrate （C-S-H） gel. A simplified treatment is further suggested towards the quantification. In particular, when the replacement level of GGBFS is lower than 70%, the ratio of calcium over silica （C/S） is set at 1.5 or at 1.2 otherwise. The validity of the proposed model is addressed in terms of the contents of calcium Portlandite and non-evaporable water.

Early Stage Hydration Mechanism of Cellulose Ether Modified Thin Layer Cement Pastes

The early stage hydration mechanism of cellulose ether modified thin layer cement pastes was studied, using brick as the matrix. Samples of 6 h, 24 h, and 3 d and 7 d hydration time were analyzed to study the hydration law on the surface of high water-absorbing matrix. Hydration products were qualitatively and semi-quantitatively analyzed using XRD, TG-DSC-DTG, FTIR and SEM. The experimental results show that there is no enough water for 2 mm thick cement pastes to hydrate, because of rapid water absorption of matrix. Trace amounts of Ca （OH）2 was detected after three days hydration. With the prolongation of hydration time, the category and concentration of hydration products do not change. Compared with 2 mm thick cement pastes, 6 mm thick cement pastes and 10 mm thick cement pastes have lower dehydration rate and water loss. The humidity field of the cement paste show different changes within the same time. 6 mm thick cement paste and 10 mm thick cement pastes have longer time and more water to hydrate. Ca（OH）2 and ettringite were detected after 6 hours hydration and the concentrations of hydration products increased from 24 hours to 7 days.

Hydration mechanism of low quality fly ash in cement-based materials

The hydration mechanism of low quality fly ash in cement-based materials was investigated. The hydration heat of the composite cementitious materials was determined by isothermal calorimetry, and the hydration products, quantity, pore structure and morphology were measured by X-ray diffraction(XRD), thermalgravity-differential thermal analysis(TG-DTA), mercury intrusion porosimetry(MIP) and scanning electron microscopy(SEM), respectively. The results indicate that grinding could not only improve the physical properties of the low quality fly ash on particle effect, but also improve hydration properties of the cementitious system from various aspects compared with raw low quality fly ash(RLFA). At the early stage of hydration, the low quanlity fly ash acts as almost inert material; but then at the later stage, high chemical activity, especially for ground low quality fly ash(GLFA), could be observed. It can accelerate the formation of hydration products containing more chemical bonded water, resulting in higher degree of cement hydration, thus denser microstructure and more reasonable pore size distribution, but the hydration heat in total is reduced. It can also delay the induction period, but the accelerating period is shortened and there is little influence on the second exothermic peak.

Effect of Nano-TiO_2 Addition on the Hydration and Hardening Process of Sulphoaluminate Cement

The influences of nano-TiO2 on the setting time, hydration process, hydration products and morphology of sulphoaluminate cement were studied by Vicar apparatus, isothermal calorimetry, X-ray diffraction （XRD）, thermal analysis and scanning electron microscopy （SEM）. The experimental results show that the incorporation of nano-TiO2 can obviously promote the setting and hardening process of sulphoaluminate cement, and shorten the interval between the initial and final setting time, the hydration induction period of sulphoaluminate cement is significantly shortened and the acceleration period begins immediately, but the hydration exothermic rate at hydration stationary phase is not obviously impacted. The nano-TiO2 additives have influence on the formation rate and degree of crystallinity, but do not affect the type of hydration process. The structure of hydration products is compact at middle age, but their content and microstructure do not change

Rheological study of methane gas hydrates in the presence of micron-sized sand particles

Natural gas hydrates,intricate crystalline structures formed by water molecules and small gas molecules,have emerged as a significant and globally impactful clean energy resource.However,their commercial exploitation faces challenges,particularly operational disruptions caused by sand-related blockages.Understanding the rheological properties of hydrate slurry,especially in the presence of micron-sized sand particles,is imperative for ensuring the flow assurance of subsea hydrate exploitation.This study extensively investigates the rheological properties of sand-containing hydrate slurries.The findings reveal that these slurries exhibit non-Newtonian fluid characteristics,including yield stress,thixotropy,and shear-thinning behavior.Solid-like elastic features are observed in sand-containing hydrate slurries before yielding,transitioning to viscous behavior after yielding.Even with a minimal amount of sand,both static yield stress and yield strain experience substantial changes,correlating with the increase in sand concentration.The research conclusively establishes the thixotropic nature of sand-hydrate slurries,where the viscosity decay rate is directly influenced by the shear rate.These insights aim to contribute comprehensively to the development of effective flow assurance strategies,ensuring the safe and stable operation of subsea hydrate exploitation.

Analysis of Hydration Mechanism and Microstructure of Composite Cementitious Materials for Filling Mining

To obtain the compositions and microstructure of hydration products of cementitious material in different hydration ages and its growth law of filling strength, the optimal proportion of composite cementitious material was determined according to the chemical composition of cement clinker which was composed of the Portland cement 32.5R, CSA 42.5 sulphoaluminate cement and two gypsum（CS）. The characterization of composite cementitious materials in different hydration ages was conducted by NMR, XRD and SEM techniques. The mechanism of hydration was explored. It is shown that the compressive strength of the test block increases gradually with the increase of hydration age. The microstructure of composite cementitious material can be changed from Al-O octahedron into Al-O tetrahedron in the hydration process. The hydrated alkali alumi niumsilicate formed with Si-O tetrahedron and Al-O tetrahedron. The degree of polymerization of Si-O tetrahedron gradually increased, and the structural strength of cementitious materials continued to increase. The diffraction peak of clinker minerals gradually decreased with the extension of hydration age. The CaSO4 completely hydrated to produce Aft during hydration which resulted in high early strength of cementitious material. The early hydration product of composite cementitious materials was Aft with a needle bar structure. The main middle and last hydration products were CSH gel and CH gel with dense prismatic shape. The microscopic pore of composite cementitious material gradually decreased and improved the later strength of filling block. The strong support was provided for mined-out area.

Influence of Polyaluminum Chloride Residue on the Strength andMicrostructure of Cement-Based Materials

In this paper,cement and dechlorinated Polyaluminum Chloride Residue(PACR)have been used to prepare a net slurry and mortar specimens.Two hydration activity indicators have been used to quantitatively analyze the dechlorinated PACR hydration activity.In particular,the effect of dechlorinated PACR content on the compressive strength of mortar has been assessed by means of compressive strength tests.Moreover,X-ray diffraction(XRD)and scanning electron microscopy(SEM)have been employed to observe the microstructure of the considered hydration products.The following results have been obtained.The 28th day activity index of the dechlorinated PACR is 75%,and therefore it meets the criterion for the use of active admixture.The increase in the content of the dechlorinated PACR tends to reduce the compressive strength of mortar specimens,however,it is beneficial to its later strength growth.When the content is not greater than 10%,the strength remains unchanged,otherwise,it decreases.The PACR does not form a new crystalline phase in the cement slurry,and the dechlorinated PACR remains active until the age of the 28th day.The inclusion of the PACR mainly deteriorates the early strength of the cement slurry,but it promotes the production of hydration products in the cement slurry after the 7th day.

Numerical study on gas production via a horizontal well from hydrate reservoirs with different slope angles in the South China Sea

It is important to study the effect of hydrate production on the physical and mechanical properties of low-permeability clayey–silty reservoirs for the largescale exploitation of hydrate reservoirs in the South China Sea.In this study,a multiphysical-field coupling model,combined with actual exploration drilling data and the mechanical experimental data of hydrate cores in the laboratory,was established to investigate the physical and mechanical properties of low-permeability reservoirs with different slope angles during 5-year hydrate production by the depressurization method via a horizontal well.The result shows that the permeability of reservoirs severely affects gas production rate,and the maximum gas production amount of a 20-m-long horizontal well can reach186.8 m3/day during the 5-year hydrate production.Reservoirs with smaller slope angles show higher gas production rates.The depressurization propagation and hydrate dissociation mainly develop along the direction parallel to the slope.Besides,the mean effective stress of reservoirs is concentrated in the near-wellbore area with the on-going hydrate production,and gradually decreases with the increase of the slope angle.Different from the effective stress distribution law,the total reservoir settlement amount first decreases and then increases with the increase of the slope angle.The maximum settlement of reservoirs with a 0°slope angle is up to 3.4 m,and the displacement in the near-wellbore area is as high as2.2 m after 5 years of hydrate production.It is concluded that the pore pressure drop region of low-permeability reservoirs in the South China Sea is limited,and various slope angles further lead to differences in effective stress and strain of reservoirs during hydrate production,resulting in severe uneven settlement of reservoirs.

Hydration of concrete containing calcium-enriched fly ash at subzero temperature

The compressive strength,hydration products and microstructure of concrete with calcium-enriched fly ash(CEFA) at different temperature were investigated.The result indicates that the hydration products age of 7 d at-15 ℃ are mainly ettringite and C-S-H,and fly ash particles remain original state.Standard curing was adapted after 7 d curing at-15 ℃.At the age of 35 d,C-S-H was found on the surface of fly ash particles.The hydration product of CEFA is mainly C-S-H gel,which can densify the microstructure of concrete.

Hydrate Prevention Strategies and the Associated Cost in the Gulf of Mexico

With the petroleum industry endeavoring to develop promising oil and gas in deeper water, gas hydrates prevention is a serious concern for oil and gas producing companies producing at conditions in the hydrate region. This paper details lessons learned from the successful field deployment of AA LDHI and proper implementation strategies used for 3 different practical fields as case studies in the Gulf of Mexico. From the 3 field experiences, the AA LDHI has been used to replace the conventional thermodynamic hydrate inhibitor due to its numerous benefits during steady state operations and transition operations where AA LDHI is injected prior to extended shut in and restart for fields producing at low water cut. However, the strategy to develop a cost effective chemical management of hydrates for fields producing at high water cut is by pumping methanol or diesel to push down the wellbore fluid below the mud line during planned and unplanned shut-ins to delay water production, it also secures the riser with non hydrate fluids. This illustrates how the AA LDHIs are used in conjunction with more conventional hydrate management approaches to reach an optimal cost effective field hydrate management solution. However, this shows that the key to overall success of hydrate prevention is a full integration of a good front end design, a comprehensive deployment and an effective down hole monitoring system.

The Early Hydration and Strength Development of High-strength Precast Concrete with Cement/Metakaolin Systems

To study the relationship between material composition, curing conditions and strength development, the study simulated high-strength precast concrete pile production, and a high-strength mortar up to 90 MPa was designed and a hot-water pool was built for concrete curing. The major point of the study was to achieve a high early strength by using cement/metakaolin systems without autoclave curing with high-pressure steam. By means of XRD and thermal analysis, the progress of the hydration of the cement pastes blended with metakaolin was characterized. The main results indicate that high strength can be obtained at early age by the use of metakaolin and thermal treatment （hot-water curing）. The improvement in strength of mortars with metakaolin can be explained by an increase in the amount of C-S-H and C-S-A-H hydrated phases and a decrease in the amount of calcium hydration（CH）. Further more, a decrease in Ca/Si ratio of the matrix was observed from the results of EDX analysis, which also leaded to an improvement of the compressive strength. These results are of great importance for the high-strength precast concrete manufacturing industry.

Early Hydration of Composite Cement with Thermal Activated Coal Gangue

Composite cement samples were prepared by mixing clinker, gypsum with burnt coal gangues which was calcined at various temperatures. The mechanical strength and Ca（OH）2 content in the cement paste were tested, and the paste composition and microstructure were analyzed by thermogravimetry-differential thermal analysis （TG-DSC）, X-ray diffraction（XRD）, scanning electronic microscopy （SEM） and pore structure analysis. Results demonstrate that the thermal activated coal gangue could accelerate the early hydration of cement clinker obviously, which promotes the gangue hydration itself. The early hydrated products of the cement are C-S-H gel, Ca（OH）2 and AFt. The cement with 30% （in mass） the gangue exhibits higher mechanical strength, and among all the cement samples the one with the gangue burnt at 700 ℃ displays the highest hydration rate, mechanical strength, the most gel pores and the lowest total porosity.

Application of the monitoring and early warning system for internal solitary waves:Take the second natural gas hydrates production test in the South China Sea as an example

Internal solitary waves(ISWs) contain great energy and have the characteristics of emergency and concealment. To avoid their damage to offshore engineering, a new generation of monitoring and early warning system for ISWs was developed using technologies of double buoys monitoring, intelligent realtime data transmission, and automatic software identification. The system was applied to the second natural gas hydrates(NGHs) production test in the Shenhu Area, South China Sea(SCS) and successfully provided the early warning of ISWs for 173 days(from October 2019 to April 2020). The abrupt changes in the thrust force of the drilling platform under the attack of ISWs were consistent with the early warning information, proving the reliability of this system. A total of 93 ISWs were detected around the drilling platform. Most of them occurred during the spring tides in October–December 2019 and April 2020, while few of them occurred in winter. As suggested by the theoretical model, the full-depth structure of ISWs was a typical current profile of mode-1, and the velocities of wave-induced currents can reach 80 cm/s and30 cm/s, respectively, in the upper ocean and near the seabed. The ISWs may be primarily generated from the interactions between the topography and semidiurnal tides in the Luzon Strait, and then propagate westward to the drilling platform. This study could serve as an important reference for the early warning of ISWs for offshore engineering construction in the future.

Physical characteristics of high concentrated gas hydrate reservoir in the Shenhu production test area,South China Sea

High concentrated and heterogeneous distribution of gas hydrates have been identified in the gas hydrate production test region in the Shenhu area,South China Sea.The gas hydrate-bearing sediments with high saturation locate at two ridges of submarine canyon with different thickness and saturations just above the bottom simulating reflection.The crossplots of gamma ray,acoustic impedance(P-impedance)and porosity at four sites show that the sediments can be divided into the upper and lower layers at different depths,indicating different geotechnical reservoir properties.Therefore,the depositional environments and physical properties at two ridges are analyzed and compared to show the different characteristics of hydrate reservoir.High porosity,high P-wave velocity,and coarse grain size indicate better reservoir quality and higher energy depositional environment for gas hydrate at Sites W18 and W19 than those at Sites W11 and W17.Our interpretation is that the base of canyon deposits at Sites W18 and W19 characterized by upward-coarsening units may be turbidity sand layers,thus significantly improving the reservoir quality with increasing gas hydrate saturation.The shelf and slope sliding deposits compose of the fine-grained sediments at Sites W11 and W17.The gas hydrate production test sites were conducted at the ridge of W11 and W17,mainly because of the thicker and larger area of gas hydrate-bearing reservoirs than those at Sites W18 and W19.All the results provide useful insights for assessing reservoir quality in the Shenhu area.

Lateral bearing characteristics of subsea wellhead assembly in the hydrate trial production engineering

Conductor and suction anchor are the key equipment providing bearing capacity in the field of deep-water drilling or offshore engineering,which have the advantages of high operation efficiency and short construction period.In order to drill a horizontal well in the shallow hydrate reservoir in the deep water,the suction anchor wellhead assembly is employed to undertake the main vertical bearing capacity in the second round of hydrate trial production project,so as to reduce the conductor running depth and heighten the kick-off point position.However,the deformation law of the deep-water suction anchor wellhead assembly under the moving load of the riser is not clear,and it is necessary to understand the lateral bearing characteristics to guide the design of its structural scheme.Based on 3D solid finite element method,the solid finite element model of the suction anchor wellhead assembly is established.In the model,the seabed soil is divided into seven layers,the contact between the wellhead assembly and the soil is simulated,and the vertical load and bending moment are applied to the wellhead node to simulate the riser movement when working in the deep water.The lateral bearing stability of conventional wellhead assembly and suction anchor wellhead assembly under the influence of wellhead load is discussed.The analysis results show that the bending moment is the main factor affecting the lateral deformation of the wellhead string;the anti-bending performance from increasing the outer conductor diameter is better than that from increasing the conductor wall thickness;for the subsea wellhead,the suction anchor obviously improves the lateral bearing capacity and reduces the lateral deformation.The conduct of the suction anchor wellhead assembly still needs to be lowered to a certain depth that below the maximum disturbed depth to ensure the lateral bearing stability,Thus,a method for the minimum conductor running depth for the suction anchor wellhead assembly is developed.The field implementations show that compared with the first round of hydrate trial production project,the conductor running depth is increased by 9.42 m,and there is no risk of wellhead overturning during the trial production.The method for determining the minimum conductor running depth in this paper is feasible and will still play an important role in the subsequent hydrate exploration and development.

Preparation and Performance Research of Cement-based Grouting Materials with High Early Strength and Expansion

Main performance of the cement grouting materials made up by Portland cement（PC） and sulphoaluminate cement（SAC） was investigated in this program, a kind of expanding agent（EA） which was mainly constituted by metakaolin and alunite was utilized for the compensation of the shrinkage, the hydration products and micro structure of the grouting materials were researched by X-ray diffraction（XRD） and scanning electron microscopy（SEM）. The results showed that a high expansion rate of the grouting materials could be reached as the expanding agent mixed in 6% of PC mass; the addition of SAC in the S2（PC：SAC：EA=34：6：2.25） brought a further improvement of the expansion rate of the grouting materials, the analysis of XRD and SEM showed that due to the reaction of expanding agent and SAC in the grouting materials, more ettringite crystal was generated, which resulted in a higher early strength, the addition of SAC played an expansion and strength reinforcement role in the grouting materials.

Effect of Curing Temperature on Tunnel Fire Insulation of Aerogel Cement Paste Coatings

To further strengthen the protective effect of aerogel cement paste (ACP) coating on self-compacting concrete (SCC) in tunnel fire under the optimal mix proportion,the effect of curing temperature (from 5 to 80 ℃,based on site construction curing temperature and surrounding rock temperature) on fire insulation of ACP was investigated.The mechanical properties,thermal conductivity and porosity of ACP were tested.The microstructure of ACP was characterized by means of SEM,XRD and TG/DTG.The results reveal that 50 ℃ is the optimal curing temperature for ACP with good mechanical properties and fire insulation.Relatively high curing temperature can facilitate hydration and pozzolanic reactions,contributing to the generation of more stable substances (such as C-S-H gels,tobermorite and thenardite,etc).ACP under excessive low curing temperature brings inhomogeneous microstructure with coarse pores,leading to producing wider and longer microcracks when it is exposed to tunnel fire.The microcracks make the heat convection and thermal radiation more significant and thus accelerate the damage of ACP under fire.In case of the less than 7% difference of thermal conductivity,dense microstructure and stable substances are more conducive to strengthening fire insulation of ACP.In practical engineering applications,the thickness of protective layer of ACP can be further optimized when ACP is cured under about 50 ℃.