Hydration characteristics of Portland cement paste with phosphorus slag powder incorporated and hydration kinetics was investigated with SEM, X-ray diffraction, DTA-TG and calorimeter Ⅱ80. Results showed that phospho...Hydration characteristics of Portland cement paste with phosphorus slag powder incorporated and hydration kinetics was investigated with SEM, X-ray diffraction, DTA-TG and calorimeter Ⅱ80. Results showed that phosphorus slag powder could reduce total amount of hydration products yet had little influence on the type of hydration products. The total amount of heat of hydration was decreased by 49.11% and the final setting was postponed by 2.28 h when phosphorus slag powder substituted 35% Portland cement by mass. The accelerating stage of this composite paste was controlled by catalysis, decreasing stage controlled by both catalysis and diffusion while stabilizing stage by diffusion alone. Hydration resistance and activation energy were reduced and hydration speed was accelerated.展开更多
Low field NMR technique was applied to investigate the hydration of cement pastes with different water to cement ratios or addition of superplasticizer. As a nondestructive method, this technique can be used to monito...Low field NMR technique was applied to investigate the hydration of cement pastes with different water to cement ratios or addition of superplasticizer. As a nondestructive method, this technique can be used to monitor the hydration kinetics process by following the changes of longitudinal relaxation time （T1） of water constrained in the pastes. The experimental results indicate that the T1 distributions of water in the fresh paste normally exhibite bimodal distribution, where the large peak is corresponding to the free water while the small one is contributed by the water stored in the flocculations. Time dependence of the weighted average T1 has a good agreement with the hydration process and could be divided into four stages, i e, initial period, dormant period, accelerated period and steady period. The hydration mechanism of each stage was described based on the theory of cement chemistry. In addition, the total signal intensity, which is proportional to the content of the physically bound water in the samples, decrease successively during the hydration reflecting the consumption of physically bound water by hydration reactions.展开更多
To elucidate the intrinsic reaction mechanism of cementitious materials composed of red mud and coal gangue（RGC）, the hydration kinetics of these cementitious materials at 20°C was investigated on the basis of ...To elucidate the intrinsic reaction mechanism of cementitious materials composed of red mud and coal gangue（RGC）, the hydration kinetics of these cementitious materials at 20°C was investigated on the basis of the Krstulovi？-Dabi？ model. An isothermal calorimeter was used to characterize the hydration heat evolution. The results show that the hydration of RGC is controlled by the processes of nucleation and crystal growth（NG）, interaction at phase boundaries（I）, and diffusion（D） in order, and the pozzolanic reactions of slag and compound-activated red mud-coal gangue are mainly controlled by the I process. Slag accelerates the clinker hydration during NG process, whereas the compound-activated red mud-coal gangue retards the hydration of RGC and the time required for I process increases with increasing dosage of red mud-coal gangue in RGC.展开更多
To solve the energy consumption and CO_(2) emission during cement production,the new binders must be developed as an alternative to cement.CaO/CaSO_(4)-activated slag binder is an eco-friendly and safe cementitious ma...To solve the energy consumption and CO_(2) emission during cement production,the new binders must be developed as an alternative to cement.CaO/CaSO_(4)-activated slag binder is an eco-friendly and safe cementitious material;however,its low strength during initial stages limits its applications.In this study,colloidal nanosilica(CNS)was employed as an additive to improve the strength of CaO/CaSO_(4)-activated slag binder,and the effects of CNS on the workability,hydration kinetics,hydration products(type,quantity,and polymerization degree),and binder microstructure were thoroughly investigated.A moderate CNS content,through its nucleation effect,significantly increased the hydration rate of the nucleation and crystal growth(NG),phase boundary interaction(I)and diffusion(D)processes,which generated large quantities of calcium aluminosilicate hydrate(C-A-S-H)gel in the initial hydration stage.Meanwhile,the addition of CNS improved the polymerization degree of C-A-S-H gel.This amorphous reactant well-filled the pore space between slag particles and yielded a compact microstructure,consequently enhancing the binder strength.Considering the reduction in fluidity and the increase in production cost,the CNS mass fraction was controlled as3%,and the binder reached the satisfactory strengths of 3.87,24.47,31.43,and 41.78 MPa at 1,3,7,and 28 d,respectively.展开更多
As a byproduct of water treatment,drinking water treatment aluminum sludge(DWTAS)has challenges related to imperfect treatment and disposal,which has caused potential harm to human health and the environment.In this p...As a byproduct of water treatment,drinking water treatment aluminum sludge(DWTAS)has challenges related to imperfect treatment and disposal,which has caused potential harm to human health and the environment.In this paper,heat treatment DWTAS as a supplement cementitious material was used to prepare a green cementing material.The results show that the 800℃ is considered as the optimum heat treatment temperature for DWTAS.DWTAS-800℃ is fully activated after thermal decomposition to form incompletely crystallized highly activeγ-Al_(2)O_(3) and active SiO_(2).The addition of DWTAS promoted the formation of ettringite and C-(A)-S-H gel,which could make up for the low early compressive strength of cementing materials to a certain extent.When cured for 90 days,the compressive strength of the mortar with 30% DWTAS-800℃ reached 44.86 MPa.The dynamic process was well simulated by Krstulovi′c-Dabi′c hydration kinetics model.This study provided a methodology for the fabrication of environmentally friendly and cost-effective compound cementitiousmaterials and proposed a“waste-to-resource”strategy for the sustainable management of typical solid wastes.展开更多
In recent decades,MgSO_(4)·7H_(2)O(epsomite)has attracted significant attention as a promising thermochemical-based thermal energy storage material due to its high theoretical energy density,wide availability,and...In recent decades,MgSO_(4)·7H_(2)O(epsomite)has attracted significant attention as a promising thermochemical-based thermal energy storage material due to its high theoretical energy density,wide availability,and affordability.Despite extensive research efforts,progress in achieving high-energy density has been limited,primarily due to inadequate understanding of its reaction mechanisms and unfavorable dehydration/hydration kinetics.This study systematically investigated the hydration/dehydration kinetics and cyclability of MgSO_(4)·7H_(2)O.The results reveal that the dehydration process is influenced by the heating rate,with an optimal rate of 5℃/min,resulting in a seven-step MgSO_(4)·7H_(2)O dehydration process with a dehydration heat close to the theoretical value.The reaction kinetic analysis indicated that the rate of hydration was approximately 50%lower than that of dehydration.In addition,thermal cycling tests of MgSO_(4)·7H_(2)O under the conditions of this study(small sample size)indicated good cyclability,with hydration rates increasing with increasing cycling numbers up to approximately 10 cycles where level-off occurs.These results are consistent with scanning electron microscopy analyses,which revealed the formation of cracks and channels in the salt hydrate particles,facilitating mass transfer and improved kinetics.展开更多
Considering the complicated interactions between temperature,pressure and hydration reaction of cement,a coupled model of temperature and pressure based on hydration kinetics during deep-water well cementing was estab...Considering the complicated interactions between temperature,pressure and hydration reaction of cement,a coupled model of temperature and pressure based on hydration kinetics during deep-water well cementing was established.The differential method was used to do the coupled numerical calculation,and the calculation results were compared with experimental and field data to verify the accuracy of the model.When the interactions between temperature,pressure and hydration reaction are considered,the calculation accuracy of the model proposed is within 5.6%,which can meet the engineering requirements.A series of numerical simulation was conducted to find out the variation pattern of temperature,pressure and hydration degree during the cement curing.The research results show that cement temperature increases dramatically as a result of the heat of cement hydration.With the development of cement gel strength,the pore pressure of cement slurry decreases gradually to even lower than the formation pressure,causing gas channeling;the transient temperature and pressure have an impact on the rate of cement hydration reaction,so cement slurry in the deeper part of wellbore has a higher rate of hydration rate as a result of the high temperature and pressure.For well cementing in deep water regions,the low temperature around seabed would slow the rate of cement hydration and thus prolong the cementing cycle.展开更多
A green pregelatinized glutinous rice flour biological admixture was developed in this paper.The cement hydration process,hydration products,pore structure,and strength of mortar with different quantities of glutinous...A green pregelatinized glutinous rice flour biological admixture was developed in this paper.The cement hydration process,hydration products,pore structure,and strength of mortar with different quantities of glutinous rice flour(GRF),and the macroscopic changes in concrete cracking resistance testing were investigated.Simultaneously,a fast cracking resistance evaluation method based on graphic recognition was proposed.The results indicated that pregelatinized glutinous rice flour(T-GRF)delayed the dissolution rate of anhydrous cement during the induction period,shifting the main exothermic peak of hydration backward.The compressive strength developed slowly in 7-28 d age and returned to normal in 28-56 d.The compressive strength of T-GRF-0.6% modified mortar at 56 d age is less than 10% different from that of control group.The 3.0%T-GRF decreased the total porosity by 3%,and the average pore size decreased from 31.2 to 21.3 nm measured by MIP,indicating that T-GRF could inhibit harmful pores and densify concrete.The crack resistance coefficient of T-GRF modified concrete was obtained by image recognition method,and the GRF could decrease the length,width,and damaged area of cracks in the early age of concrete.展开更多
Curing temperature significantly affects the pozzolanic reaction kinetics of phosphorous slag(PS),thereby governing the early-age(7 d)hydration behavior of PS composite binders at 20,30,and 60℃.The Krstulovic-Dabic k...Curing temperature significantly affects the pozzolanic reaction kinetics of phosphorous slag(PS),thereby governing the early-age(7 d)hydration behavior of PS composite binders at 20,30,and 60℃.The Krstulovic-Dabic kinetic model was applied to identify three characteristic processes:nucleation and growth(NG),phase boundary interaction(I),and diffusion(D).Control mixtures containing inert quartz powder with comparable particle size distributions were prepared for comparison.Pore characteristics of hardened PS pastes at different temperatures were analyzed via mercury intrusion porosimetry,while hydration products were characterized using X-ray diffraction(XRD)and thermogravimetric analysis(TG-DTG).The experimental results indicate that the retarding effect of PS on early cement hydration outweighs its accelerating effect,attributed to the combined influence of nucleation and dilution,with retardation decreasing as temperature increases.PS exhibits early reactivity and continuously consumes calcium hydroxide through the pozzolanic reaction,as evidenced by stable phase assemblages accompanied by reduced CH content in XRD and TG-DTG analyses.At 20℃,increasing PS content maintains the NG→I→D mechanism but slows reaction rates across all stages.Elevated temperatures significantly accelerate the NG process,shifting the dominant mechanism from NG toward D.Simultaneously,enhanced PS reactivity contributes to a refined pore structure and improved compressive strength.展开更多
The feasibility of sulphoaluminate cement （SAC） utilization in support mortar was studied. Setting time and strength of as-received sulphoaluminate cement （SAC） paste were examined, hydration kinetics behavior was...The feasibility of sulphoaluminate cement （SAC） utilization in support mortar was studied. Setting time and strength of as-received sulphoaluminate cement （SAC） paste were examined, hydration kinetics behavior was determined through Isothermal Calorimeter, and hydration mechanism was investigated by X-Ray diffraction analysis （XRD） and field emission scanning electron microscopy analysis （FSEM）. Results showed that as-received SAC contained 61% of anhydrous calcium sulfate （3CA＇CaSO4） and dicalcium silicate （C2S）. The strength after 1 day or 3 days grew to 68.6% or 85.7% of that after 28 days respectively, while most of hydration heat was released within 1 day. The emergency of three exothermic peaks at acceleration stage was found and hydration kinetics model was established choosing the terminal time of the first exothermic peak at accelerating stage as the beginning of accelerating stage. XRD analysis suggested that large amount of ettringite （AFt） was produced at early age and FSEM observation revealed that ettringite （AFt） formed in sulphoaluminate cement （SAC） paste was characterized of different morphology which was proved to be caused by different ion concentrations.展开更多
Early hydration mechanism of cement-based materials with silica fume, nano-SiO2 and silica sol of different contents was investigated, and the detailed effect of these Si-rich mineral admixtures in three stages of ear...Early hydration mechanism of cement-based materials with silica fume, nano-SiO2 and silica sol of different contents was investigated, and the detailed effect of these Si-rich mineral admixtures in three stages of early hydration（NG, I, D） using kinetics model was focused. The results showed that silica fume, nano-SiO2, and silica sol have significant effect on kinetic parameters n, k1, k2 and k3, the fineness and existing form of SiO2 particles in these Si-rich mineral admixtures are two important factors to affect the hydration process and on the parameters. Through integrated use of methods of hydration heat-Krstulovic-Dabic Modelsynthetical thermal analysis, data of hydration heat were collected, hydration degree was characterized, as well as the resulting crystallization behavior of early hydration, to build a numerical relationship between parameter n and CH contents that n decreases with increasing CH, and thus, a direct connection between hydration heat release behavior and crystallization behavior has been established.展开更多
Setting time and strength of sulphoaluminate rapid hardening cement （SAC） incorporated in the presence and absence of silica fume （SF） were determined. Combined with the techniques of＂ isothermal calorimeter, XRD...Setting time and strength of sulphoaluminate rapid hardening cement （SAC） incorporated in the presence and absence of silica fume （SF） were determined. Combined with the techniques of＂ isothermal calorimeter, XRD and FSEM, the hydration kinetics of the two systems and the effect mechanism of SF on SAC were investigated. The experimental results showed that SF was proved to be beneficial for SAC system, in terms of setting time and late strength gain. Evidence of accelerator effect of silica fume was found during the first 8 hours of hydration. The formation of AFt was accelerated and the microstructure of the hydration products grew denser with incorporation of SF. SF was proved to play the role of dispersion and setting control at early age and had a greater contribution to later strength due to the increment of crystal nucleation point and the pozzolanic activity. Therefore, SF can be used to not only control the hydration kinetics of SAC, but also develop the late strength and improve the microstructure.展开更多
The Shenhu Area in the South China Sea is rich in oil and gas resources and has many vertical gas chimneys,making it an excellent geological environment for hydrate accumulation.This paper examines the geological cond...The Shenhu Area in the South China Sea is rich in oil and gas resources and has many vertical gas chimneys,making it an excellent geological environment for hydrate accumulation.This paper examines the geological conditions governing these gas-chimneys.A numerical simulation method based on the partial-equilibrium reaction model of hydrate was applied to simulate the migration of methane gas and the resultant hydrate formation when the gas enters the hydrate stability zone under the seabed through gas-chimneys.The dynamics of this gaschimney hydrate accumulation were analyzed,and the influences of different factors―namely,the fluid supply time,rate,and temperature―on the formation temperature and ultimate distribution of the hydrate reservoir were evaluated.The simulation results indicate that the accumulation of hydrate via gas-chimneys is significantly affected by the temperature of the gas source,the transfer state of the methane gas,and the number of cycles of alternating gas-water invasion.Hydrate accumulation takes shape in an annular or semi-annular distribution pattern divided by fluid state as follows:a two-phase gas-water zone,a three-phase gas-water-hydrate zone,a two-phase water-hydrate zone,and a phase of water passing from the inside to the outside.Formation inclination and reservoir heterogeneity can greatly affect the distribution shape and abundance of the hydrate.A high fluid supply temperature,frequent alternating invasions of gas and water,and long-term pore-water invasion at a high rate can jointly cause a large central hydrate-free zone.In contrast,a long-term supply shutdown during the alternating gas-water invasion process,and a high gas rate with a low water rate in the gas-dominant invasion stage,foster the accumulation of hydrate in great abundance and with considerable thickness.The results of this study can help us understand the accumulation of hydrate through gas chimneys in the Shenhu Area.展开更多
Thermal energy storage(TES)solutions offer opportunities to reduce energy consumption,greenhouse gas emissions,and cost.Specifically,they can help reduce the peak load and address the intermittency of renewable energy...Thermal energy storage(TES)solutions offer opportunities to reduce energy consumption,greenhouse gas emissions,and cost.Specifically,they can help reduce the peak load and address the intermittency of renewable energy sources by time shifting the load,which are critical toward zero energy buildings.Thermochemical materials(TCMs)as a class of TES undergo a solid-gas reversible chemical reaction with water vapor to store and release energy with high storage capacities(600 kWh m^(-3))and negligible self-discharge that makes them uniquely suited as compact,stand-alone units for daily or seasonal storage.However,TCMs suffer from instabilities at the material(salt particles)and reactor level(packed beds of salt),resulting in poor multi-cycle efficiency and high-levelized cost of storage.In this study,a model is developed to predict the pulverization limit or Rcrit of various salt hydrates during thermal cycling.This is critical as it provides design rules to make mechanically stable TCM composites as well as enables the use of more energy-efficient manufacturing process(solid-state mixing)to make the composites.The model is experimentally validated on multiple TCM salt hydrates with different water content,and effect of Rcrit on hydration and dehydration kinetics is also investigated.展开更多
In this paper, the effect of adding different concentrations of kinetic inhibitors on the induction time of hydrogen sulfide hydrate formation in a reactor equipped with automatic adjustable temperature controller is ...In this paper, the effect of adding different concentrations of kinetic inhibitors on the induction time of hydrogen sulfide hydrate formation in a reactor equipped with automatic adjustable temperature controller is studied. A novel method namely ＂sudden cooling＂ is used for performing the relevant measurements, in which the induction time of H2S hydrate in the presence/absence of PVP and L-tyrosine with different concentrations （100, 500, and 1000 ppm） is determined. As a result, PVP with the concentration of 1000 ppm in aqueous solution is detected as a more suitable material for increasing the induction time of H2S hydrate formation among the investigated kinetic hydrate inhibitors.展开更多
It is necessary to understand all the prerequisites, which result in gas hydrate formation for safe design and control of a variety of processes in petroleum industry. Thermodynamic hydrate inhibitors (THIs) are norma...It is necessary to understand all the prerequisites, which result in gas hydrate formation for safe design and control of a variety of processes in petroleum industry. Thermodynamic hydrate inhibitors (THIs) are normally used to preclude gas hydrate formation by shifting hydrate stability region to lower temperatures and higher pressures. Sometimes, it is difficult to avoid hydrate formation and hydrates will form anyway. In this situation, kinetic hydrate inhibitors (KHIs) can be used to postpone formation of gas hydrates by retarding hydrate nucleation and growth rate. In this study, two kinetic parameters including natural gas hydrate formation induction time and the rate of gas consumption were experimentally investigated in the presence of monoethylene glycol (MEG), L-tyrosine, and polyvinylpyrrolidone (PVP) at various concentrations in aqueous solutions. Since hydrate formation is a stochastic phenomenon, the repeatability of each kinetic parameter was evaluated several times and the average values for the hydrate formation induction times and the rates of gas consumption are reported. The results indicate that from the view point of hydrate formation induction time, 2 wt% PVP and 20 wt% MEG aqueous solutions have the highest values and are the best choices. It is also interpreted from the results that from the view point of the rate of gas consumption, 20 wt% MEG aqueous solution yields the lowest value and is the best choice. Finally, it is concluded that the combination of PVP and MEG in an aqueous solution has a simultaneous synergistic impact on natural gas hydrate formation induction time and the rate of gas consumption. Furthermore, a semi-empirical model based on chemical kinetic theory is applied to evaluate the hydrate formation induction time data. A good agreement between the experimental and calculated hydrate formation induction time data is observed.展开更多
In oil and gas field, the application of kinetic hydrate inhibitors （KHIs） independently has remained problematic in high subcooling and high water-cut situation. One feasible method to resolve this problem is the c...In oil and gas field, the application of kinetic hydrate inhibitors （KHIs） independently has remained problematic in high subcooling and high water-cut situation. One feasible method to resolve this problem is the combined use of KHIs and some synergists, which would enhance KHIs’ inhibitory effect on both hydrate nucleation and hydrate crystal growth. In this study, a novel kind of KHI copolymer poly（N-vinyl-2-pyrrolidone-co-2-vinyl pyridine）s （HGs） is used in conjunction with TBAB to show its high performance on hydrate inhibition. The performance of HGs with different monomer ratios in structure II tetrahydrofuran （THF） hydrate is investigated using kinetic hydrate inhibitor evaluation apparatus by step-cooling method and isothermal cooling method. With the combined gas hydrate inhibitor at the concentration of 1.0 wt%, the induction time of 19 wt% THF solution could be prolonged to 8.5 h at a high subcooling of 6℃. Finally, the mechanism of HGs inhibiting the formation of gas hydrate is proposed.展开更多
Natural gas hydrate inhibitor has been serving the oil and gas industry for many years. The development and search for new inhibitors remain the focus of research. In this study, the solution polymerization method was...Natural gas hydrate inhibitor has been serving the oil and gas industry for many years. The development and search for new inhibitors remain the focus of research. In this study, the solution polymerization method was employed to prepare poly(N-vinyl caprolactam-co-butyl methacrylate)(P(VCap-BMA)), as a new kinetic hydrate inhibitor(KHI). The inhibition properties of P(VCap-BMA) were investigated by tetrahydrofuran(THF) hydrate testing and natural gas hydrate forming and compared with the commercial KHIs. The experiment showed that PVCap performed better than copolymer P(VCap-BMA). However,low doses of methanol or ethylene glycol are compounded with KHIs. The compounding inhibitors show a synergistic inhibitory effect. More interesting is the P(VCap-BMA)-methanol system has a better inhibitory effect than the PVCap-methanol system. 1% P(VCap-BMA) + 5% methanol presented the best inhibiting performance at subcooling 10.3 °C, the induction time of natural gas hydrate was 445 min.Finally, the interaction between water and several dimeric inhibitors compared by natural bond orbital(NBO) analyses and density functional theory(DFT) indicated that inhibitor molecules were able to form the hydrogen bond with the water molecules, which result in gas hydrate inhibition. These exciting properties make the P(VCap-BMA) compound hydrate inhibitor promising candidates for numerous applications in the petrochemical industry.展开更多
Low dosage kinetic hydrate inhibitors(KHIs)are a kind of alternative chemical additives to prevent gas hydrate formation in oil&gas production wells and transportation pipelines.In this work,a series of KHIs were ...Low dosage kinetic hydrate inhibitors(KHIs)are a kind of alternative chemical additives to prevent gas hydrate formation in oil&gas production wells and transportation pipelines.In this work,a series of KHIs were experimentally synthesized with N-vinyl caprolactam(N-VCap)and vinyl ether including vinyl ether,vinyl n-butyl ether,vinyl isobutyl ether,triethylene glycol divinyl ether,with the mole ratio ranging from 9:1 to 5:5.The inhibition performance of new-synthesized KHIs on the formation process of methane hydrate were examined and compared with that of commercial N-vinyl caprolactam PVCap.Several ethylenediamine reagents were used as synergists and tested to improve the inhibition capacity of new-synthesized KHIs.The experimental results demonstrate that the introduction of ether groups on PVCap improves the performance of hydrate inhibitors.PVCap-VNBE(N-VCap:vinyl n-butyl ether=5:5)shows the best inhibition performance for methane hydrate,which could extend the TVO to 1251 min under 6 K subcooling.N,N'-dimethylethylenediamine shows the best synergistic effect for PVCap-VNBE(5:5),and extends the TVO by 2.75 times at 7 K subcooling.Additionally,the relationship between hydrate inhibition performance and interfacial tension of newly-synthesized KHIs under high pressure were studied.It shows that the lower interfacial tension of KHIs would result in longer onset time,exhibiting better inhibition performance.展开更多
The hydration of cement compounds gives hydrated compounds, which allow linking together, the different particles and aggregate of cement, and gives the concrete the required qualities. The dynamics of hydration react...The hydration of cement compounds gives hydrated compounds, which allow linking together, the different particles and aggregate of cement, and gives the concrete the required qualities. The dynamics of hydration reactions will depend on many factors, such as the fineness of cement, the ratio w/c during hydration, temperature, mixing technique, and the presence of additives in blended cement, as pozzolan, tuff and slag from blast furnaces. We studied the thermal and kinetic reactions of Portland cement hydration, and its variants with different additions using a differential scanning calorimetric analysis. The parameters from these models of curves allow us to evaluate the enthalpies, and the degree of progression of this blended cement, and finally determine their activation energies. We can say that the hydration of Portland cement is due to a series of reactions as （ C3S,C2S,C3A and C4AF reactions with water） and each of them, has its own kinetic, the experimental measurement of the heat of hydration, allows us to represent the overall kinetics of these reactions values of activation energy, they are therefore apparent and global energy. In our experiments, significant differences in these physicochemical parameters were observed, depending on the additive used.展开更多
基金Funded by the National Natural Science Foundation of China (No. 50539010)China Central Special Non-profit Research Funds for Institutes (Nos.200901066 and YWF090)
文摘Hydration characteristics of Portland cement paste with phosphorus slag powder incorporated and hydration kinetics was investigated with SEM, X-ray diffraction, DTA-TG and calorimeter Ⅱ80. Results showed that phosphorus slag powder could reduce total amount of hydration products yet had little influence on the type of hydration products. The total amount of heat of hydration was decreased by 49.11% and the final setting was postponed by 2.28 h when phosphorus slag powder substituted 35% Portland cement by mass. The accelerating stage of this composite paste was controlled by catalysis, decreasing stage controlled by both catalysis and diffusion while stabilizing stage by diffusion alone. Hydration resistance and activation energy were reduced and hydration speed was accelerated.
基金Funded by the Major State Basic Research Development Program of China(‘973’ Program) (No. 2009CB623105)
文摘Low field NMR technique was applied to investigate the hydration of cement pastes with different water to cement ratios or addition of superplasticizer. As a nondestructive method, this technique can be used to monitor the hydration kinetics process by following the changes of longitudinal relaxation time （T1） of water constrained in the pastes. The experimental results indicate that the T1 distributions of water in the fresh paste normally exhibite bimodal distribution, where the large peak is corresponding to the free water while the small one is contributed by the water stored in the flocculations. Time dependence of the weighted average T1 has a good agreement with the hydration process and could be divided into four stages, i e, initial period, dormant period, accelerated period and steady period. The hydration mechanism of each stage was described based on the theory of cement chemistry. In addition, the total signal intensity, which is proportional to the content of the physically bound water in the samples, decrease successively during the hydration reflecting the consumption of physically bound water by hydration reactions.
基金financially supported by the National Natural Science Foundation of China(Nos.51302012 and 51234008)the China Postdoctoral Science Foundation(No.2016M590046)
文摘To elucidate the intrinsic reaction mechanism of cementitious materials composed of red mud and coal gangue（RGC）, the hydration kinetics of these cementitious materials at 20°C was investigated on the basis of the Krstulovi？-Dabi？ model. An isothermal calorimeter was used to characterize the hydration heat evolution. The results show that the hydration of RGC is controlled by the processes of nucleation and crystal growth（NG）, interaction at phase boundaries（I）, and diffusion（D） in order, and the pozzolanic reactions of slag and compound-activated red mud-coal gangue are mainly controlled by the I process. Slag accelerates the clinker hydration during NG process, whereas the compound-activated red mud-coal gangue retards the hydration of RGC and the time required for I process increases with increasing dosage of red mud-coal gangue in RGC.
基金supported by Natural Science Foundation of Shandong Province(No.ZR2019BEE075)Scientific Research Foundation of Shandong University of Science and Technology for Recruited Talents(No.2019RCJJ007)+1 种基金Young Science and Technology Innovation Program of Shandong Province(No.2020KJD001)Youth Science and Technology Talent Growth Program of Guizhou Province(No.KY[2018]466).
文摘To solve the energy consumption and CO_(2) emission during cement production,the new binders must be developed as an alternative to cement.CaO/CaSO_(4)-activated slag binder is an eco-friendly and safe cementitious material;however,its low strength during initial stages limits its applications.In this study,colloidal nanosilica(CNS)was employed as an additive to improve the strength of CaO/CaSO_(4)-activated slag binder,and the effects of CNS on the workability,hydration kinetics,hydration products(type,quantity,and polymerization degree),and binder microstructure were thoroughly investigated.A moderate CNS content,through its nucleation effect,significantly increased the hydration rate of the nucleation and crystal growth(NG),phase boundary interaction(I)and diffusion(D)processes,which generated large quantities of calcium aluminosilicate hydrate(C-A-S-H)gel in the initial hydration stage.Meanwhile,the addition of CNS improved the polymerization degree of C-A-S-H gel.This amorphous reactant well-filled the pore space between slag particles and yielded a compact microstructure,consequently enhancing the binder strength.Considering the reduction in fluidity and the increase in production cost,the CNS mass fraction was controlled as3%,and the binder reached the satisfactory strengths of 3.87,24.47,31.43,and 41.78 MPa at 1,3,7,and 28 d,respectively.
基金This work is supported by the National Key Research and Development Program of China(No.2022YFC3203203)the Outstanding Youth Science Foundation of Shaanxi Province(No.2023-JC-JQ-36)the National Natural Science Foundation of China(No.52300121).
文摘As a byproduct of water treatment,drinking water treatment aluminum sludge(DWTAS)has challenges related to imperfect treatment and disposal,which has caused potential harm to human health and the environment.In this paper,heat treatment DWTAS as a supplement cementitious material was used to prepare a green cementing material.The results show that the 800℃ is considered as the optimum heat treatment temperature for DWTAS.DWTAS-800℃ is fully activated after thermal decomposition to form incompletely crystallized highly activeγ-Al_(2)O_(3) and active SiO_(2).The addition of DWTAS promoted the formation of ettringite and C-(A)-S-H gel,which could make up for the low early compressive strength of cementing materials to a certain extent.When cured for 90 days,the compressive strength of the mortar with 30% DWTAS-800℃ reached 44.86 MPa.The dynamic process was well simulated by Krstulovi′c-Dabi′c hydration kinetics model.This study provided a methodology for the fabrication of environmentally friendly and cost-effective compound cementitiousmaterials and proposed a“waste-to-resource”strategy for the sustainable management of typical solid wastes.
文摘In recent decades,MgSO_(4)·7H_(2)O(epsomite)has attracted significant attention as a promising thermochemical-based thermal energy storage material due to its high theoretical energy density,wide availability,and affordability.Despite extensive research efforts,progress in achieving high-energy density has been limited,primarily due to inadequate understanding of its reaction mechanisms and unfavorable dehydration/hydration kinetics.This study systematically investigated the hydration/dehydration kinetics and cyclability of MgSO_(4)·7H_(2)O.The results reveal that the dehydration process is influenced by the heating rate,with an optimal rate of 5℃/min,resulting in a seven-step MgSO_(4)·7H_(2)O dehydration process with a dehydration heat close to the theoretical value.The reaction kinetic analysis indicated that the rate of hydration was approximately 50%lower than that of dehydration.In addition,thermal cycling tests of MgSO_(4)·7H_(2)O under the conditions of this study(small sample size)indicated good cyclability,with hydration rates increasing with increasing cycling numbers up to approximately 10 cycles where level-off occurs.These results are consistent with scanning electron microscopy analyses,which revealed the formation of cracks and channels in the salt hydrate particles,facilitating mass transfer and improved kinetics.
基金Supported by the National Natural Science Foundation of China(U1762216)China National Science and Technology Major Project(2016ZX05028-001-03)
文摘Considering the complicated interactions between temperature,pressure and hydration reaction of cement,a coupled model of temperature and pressure based on hydration kinetics during deep-water well cementing was established.The differential method was used to do the coupled numerical calculation,and the calculation results were compared with experimental and field data to verify the accuracy of the model.When the interactions between temperature,pressure and hydration reaction are considered,the calculation accuracy of the model proposed is within 5.6%,which can meet the engineering requirements.A series of numerical simulation was conducted to find out the variation pattern of temperature,pressure and hydration degree during the cement curing.The research results show that cement temperature increases dramatically as a result of the heat of cement hydration.With the development of cement gel strength,the pore pressure of cement slurry decreases gradually to even lower than the formation pressure,causing gas channeling;the transient temperature and pressure have an impact on the rate of cement hydration reaction,so cement slurry in the deeper part of wellbore has a higher rate of hydration rate as a result of the high temperature and pressure.For well cementing in deep water regions,the low temperature around seabed would slow the rate of cement hydration and thus prolong the cementing cycle.
基金Funded by Hainan Provincial Natural Science Foundation(No.522QN279)State Key Laboratory of High Performance Civil Engineering Materials(No.2023CEM004)。
文摘A green pregelatinized glutinous rice flour biological admixture was developed in this paper.The cement hydration process,hydration products,pore structure,and strength of mortar with different quantities of glutinous rice flour(GRF),and the macroscopic changes in concrete cracking resistance testing were investigated.Simultaneously,a fast cracking resistance evaluation method based on graphic recognition was proposed.The results indicated that pregelatinized glutinous rice flour(T-GRF)delayed the dissolution rate of anhydrous cement during the induction period,shifting the main exothermic peak of hydration backward.The compressive strength developed slowly in 7-28 d age and returned to normal in 28-56 d.The compressive strength of T-GRF-0.6% modified mortar at 56 d age is less than 10% different from that of control group.The 3.0%T-GRF decreased the total porosity by 3%,and the average pore size decreased from 31.2 to 21.3 nm measured by MIP,indicating that T-GRF could inhibit harmful pores and densify concrete.The crack resistance coefficient of T-GRF modified concrete was obtained by image recognition method,and the GRF could decrease the length,width,and damaged area of cracks in the early age of concrete.
基金Funded by the Sichuan Province Science and Technology Support Program(No.2025YFNZH0022)the Chengdu Municipal Science and Technology Program(No.2025-YF11-00003-HZ)。
文摘Curing temperature significantly affects the pozzolanic reaction kinetics of phosphorous slag(PS),thereby governing the early-age(7 d)hydration behavior of PS composite binders at 20,30,and 60℃.The Krstulovic-Dabic kinetic model was applied to identify three characteristic processes:nucleation and growth(NG),phase boundary interaction(I),and diffusion(D).Control mixtures containing inert quartz powder with comparable particle size distributions were prepared for comparison.Pore characteristics of hardened PS pastes at different temperatures were analyzed via mercury intrusion porosimetry,while hydration products were characterized using X-ray diffraction(XRD)and thermogravimetric analysis(TG-DTG).The experimental results indicate that the retarding effect of PS on early cement hydration outweighs its accelerating effect,attributed to the combined influence of nucleation and dilution,with retardation decreasing as temperature increases.PS exhibits early reactivity and continuously consumes calcium hydroxide through the pozzolanic reaction,as evidenced by stable phase assemblages accompanied by reduced CH content in XRD and TG-DTG analyses.At 20℃,increasing PS content maintains the NG→I→D mechanism but slows reaction rates across all stages.Elevated temperatures significantly accelerate the NG process,shifting the dominant mechanism from NG toward D.Simultaneously,enhanced PS reactivity contributes to a refined pore structure and improved compressive strength.
基金Funded by the National Natural Science Foundation of China(Nos.51379163 and 51109170)the National Key Research Program(973 Program)(No.2013CB035901)
文摘The feasibility of sulphoaluminate cement （SAC） utilization in support mortar was studied. Setting time and strength of as-received sulphoaluminate cement （SAC） paste were examined, hydration kinetics behavior was determined through Isothermal Calorimeter, and hydration mechanism was investigated by X-Ray diffraction analysis （XRD） and field emission scanning electron microscopy analysis （FSEM）. Results showed that as-received SAC contained 61% of anhydrous calcium sulfate （3CA＇CaSO4） and dicalcium silicate （C2S）. The strength after 1 day or 3 days grew to 68.6% or 85.7% of that after 28 days respectively, while most of hydration heat was released within 1 day. The emergency of three exothermic peaks at acceleration stage was found and hydration kinetics model was established choosing the terminal time of the first exothermic peak at accelerating stage as the beginning of accelerating stage. XRD analysis suggested that large amount of ettringite （AFt） was produced at early age and FSEM observation revealed that ettringite （AFt） formed in sulphoaluminate cement （SAC） paste was characterized of different morphology which was proved to be caused by different ion concentrations.
基金Funded by the National Key Research Program(973 Program)(No.2015CB655101)the National Natural Science Foundation of China(No.51379163)
文摘Early hydration mechanism of cement-based materials with silica fume, nano-SiO2 and silica sol of different contents was investigated, and the detailed effect of these Si-rich mineral admixtures in three stages of early hydration（NG, I, D） using kinetics model was focused. The results showed that silica fume, nano-SiO2, and silica sol have significant effect on kinetic parameters n, k1, k2 and k3, the fineness and existing form of SiO2 particles in these Si-rich mineral admixtures are two important factors to affect the hydration process and on the parameters. Through integrated use of methods of hydration heat-Krstulovic-Dabic Modelsynthetical thermal analysis, data of hydration heat were collected, hydration degree was characterized, as well as the resulting crystallization behavior of early hydration, to build a numerical relationship between parameter n and CH contents that n decreases with increasing CH, and thus, a direct connection between hydration heat release behavior and crystallization behavior has been established.
基金Funded by the National Natural Science Foundation of China(Nos.51379163 and 51372184)the National Key Research Program(973 Program)(No.2013CB035901)
文摘Setting time and strength of sulphoaluminate rapid hardening cement （SAC） incorporated in the presence and absence of silica fume （SF） were determined. Combined with the techniques of＂ isothermal calorimeter, XRD and FSEM, the hydration kinetics of the two systems and the effect mechanism of SF on SAC were investigated. The experimental results showed that SF was proved to be beneficial for SAC system, in terms of setting time and late strength gain. Evidence of accelerator effect of silica fume was found during the first 8 hours of hydration. The formation of AFt was accelerated and the microstructure of the hydration products grew denser with incorporation of SF. SF was proved to play the role of dispersion and setting control at early age and had a greater contribution to later strength due to the increment of crystal nucleation point and the pozzolanic activity. Therefore, SF can be used to not only control the hydration kinetics of SAC, but also develop the late strength and improve the microstructure.
基金supported by the Guangzhou Marine Geological Survey,China Geological Survey,Guangzhou,China(No.2022C-24-216)financed by the General Project of the Shandong Natural Science Foundation,China(No.ZR2020ME090).
文摘The Shenhu Area in the South China Sea is rich in oil and gas resources and has many vertical gas chimneys,making it an excellent geological environment for hydrate accumulation.This paper examines the geological conditions governing these gas-chimneys.A numerical simulation method based on the partial-equilibrium reaction model of hydrate was applied to simulate the migration of methane gas and the resultant hydrate formation when the gas enters the hydrate stability zone under the seabed through gas-chimneys.The dynamics of this gaschimney hydrate accumulation were analyzed,and the influences of different factors―namely,the fluid supply time,rate,and temperature―on the formation temperature and ultimate distribution of the hydrate reservoir were evaluated.The simulation results indicate that the accumulation of hydrate via gas-chimneys is significantly affected by the temperature of the gas source,the transfer state of the methane gas,and the number of cycles of alternating gas-water invasion.Hydrate accumulation takes shape in an annular or semi-annular distribution pattern divided by fluid state as follows:a two-phase gas-water zone,a three-phase gas-water-hydrate zone,a two-phase water-hydrate zone,and a phase of water passing from the inside to the outside.Formation inclination and reservoir heterogeneity can greatly affect the distribution shape and abundance of the hydrate.A high fluid supply temperature,frequent alternating invasions of gas and water,and long-term pore-water invasion at a high rate can jointly cause a large central hydrate-free zone.In contrast,a long-term supply shutdown during the alternating gas-water invasion process,and a high gas rate with a low water rate in the gas-dominant invasion stage,foster the accumulation of hydrate in great abundance and with considerable thickness.The results of this study can help us understand the accumulation of hydrate through gas chimneys in the Shenhu Area.
基金supported by the Energy Efficiency and Renewable Energy,Building Technologies Program,of the US Department of Energy,under contract no.DE-AC02-05CH11231the support on the DSC/TGA 3+supported by the Office of Science,Office of Basic Energy Sciences,of the U.S.Department of Energy under Contract No.DE-AC02-05CH11231
文摘Thermal energy storage(TES)solutions offer opportunities to reduce energy consumption,greenhouse gas emissions,and cost.Specifically,they can help reduce the peak load and address the intermittency of renewable energy sources by time shifting the load,which are critical toward zero energy buildings.Thermochemical materials(TCMs)as a class of TES undergo a solid-gas reversible chemical reaction with water vapor to store and release energy with high storage capacities(600 kWh m^(-3))and negligible self-discharge that makes them uniquely suited as compact,stand-alone units for daily or seasonal storage.However,TCMs suffer from instabilities at the material(salt particles)and reactor level(packed beds of salt),resulting in poor multi-cycle efficiency and high-levelized cost of storage.In this study,a model is developed to predict the pulverization limit or Rcrit of various salt hydrates during thermal cycling.This is critical as it provides design rules to make mechanically stable TCM composites as well as enables the use of more energy-efficient manufacturing process(solid-state mixing)to make the composites.The model is experimentally validated on multiple TCM salt hydrates with different water content,and effect of Rcrit on hydration and dehydration kinetics is also investigated.
文摘In this paper, the effect of adding different concentrations of kinetic inhibitors on the induction time of hydrogen sulfide hydrate formation in a reactor equipped with automatic adjustable temperature controller is studied. A novel method namely ＂sudden cooling＂ is used for performing the relevant measurements, in which the induction time of H2S hydrate in the presence/absence of PVP and L-tyrosine with different concentrations （100, 500, and 1000 ppm） is determined. As a result, PVP with the concentration of 1000 ppm in aqueous solution is detected as a more suitable material for increasing the induction time of H2S hydrate formation among the investigated kinetic hydrate inhibitors.
文摘It is necessary to understand all the prerequisites, which result in gas hydrate formation for safe design and control of a variety of processes in petroleum industry. Thermodynamic hydrate inhibitors (THIs) are normally used to preclude gas hydrate formation by shifting hydrate stability region to lower temperatures and higher pressures. Sometimes, it is difficult to avoid hydrate formation and hydrates will form anyway. In this situation, kinetic hydrate inhibitors (KHIs) can be used to postpone formation of gas hydrates by retarding hydrate nucleation and growth rate. In this study, two kinetic parameters including natural gas hydrate formation induction time and the rate of gas consumption were experimentally investigated in the presence of monoethylene glycol (MEG), L-tyrosine, and polyvinylpyrrolidone (PVP) at various concentrations in aqueous solutions. Since hydrate formation is a stochastic phenomenon, the repeatability of each kinetic parameter was evaluated several times and the average values for the hydrate formation induction times and the rates of gas consumption are reported. The results indicate that from the view point of hydrate formation induction time, 2 wt% PVP and 20 wt% MEG aqueous solutions have the highest values and are the best choices. It is also interpreted from the results that from the view point of the rate of gas consumption, 20 wt% MEG aqueous solution yields the lowest value and is the best choice. Finally, it is concluded that the combination of PVP and MEG in an aqueous solution has a simultaneous synergistic impact on natural gas hydrate formation induction time and the rate of gas consumption. Furthermore, a semi-empirical model based on chemical kinetic theory is applied to evaluate the hydrate formation induction time data. A good agreement between the experimental and calculated hydrate formation induction time data is observed.
基金supported by the National Basic Research Program of China ("973" Program) (Grant No. 2009CB219504-03)the National Natural Science Foundation of China (Grant No 51106054)the Colleges and Universities High-level Talents Program of Guangdong
文摘In oil and gas field, the application of kinetic hydrate inhibitors （KHIs） independently has remained problematic in high subcooling and high water-cut situation. One feasible method to resolve this problem is the combined use of KHIs and some synergists, which would enhance KHIs’ inhibitory effect on both hydrate nucleation and hydrate crystal growth. In this study, a novel kind of KHI copolymer poly（N-vinyl-2-pyrrolidone-co-2-vinyl pyridine）s （HGs） is used in conjunction with TBAB to show its high performance on hydrate inhibition. The performance of HGs with different monomer ratios in structure II tetrahydrofuran （THF） hydrate is investigated using kinetic hydrate inhibitor evaluation apparatus by step-cooling method and isothermal cooling method. With the combined gas hydrate inhibitor at the concentration of 1.0 wt%, the induction time of 19 wt% THF solution could be prolonged to 8.5 h at a high subcooling of 6℃. Finally, the mechanism of HGs inhibiting the formation of gas hydrate is proposed.
基金supported by the Key Science and Technology Program of Shaanxi Province (2014K10-03)。
文摘Natural gas hydrate inhibitor has been serving the oil and gas industry for many years. The development and search for new inhibitors remain the focus of research. In this study, the solution polymerization method was employed to prepare poly(N-vinyl caprolactam-co-butyl methacrylate)(P(VCap-BMA)), as a new kinetic hydrate inhibitor(KHI). The inhibition properties of P(VCap-BMA) were investigated by tetrahydrofuran(THF) hydrate testing and natural gas hydrate forming and compared with the commercial KHIs. The experiment showed that PVCap performed better than copolymer P(VCap-BMA). However,low doses of methanol or ethylene glycol are compounded with KHIs. The compounding inhibitors show a synergistic inhibitory effect. More interesting is the P(VCap-BMA)-methanol system has a better inhibitory effect than the PVCap-methanol system. 1% P(VCap-BMA) + 5% methanol presented the best inhibiting performance at subcooling 10.3 °C, the induction time of natural gas hydrate was 445 min.Finally, the interaction between water and several dimeric inhibitors compared by natural bond orbital(NBO) analyses and density functional theory(DFT) indicated that inhibitor molecules were able to form the hydrogen bond with the water molecules, which result in gas hydrate inhibition. These exciting properties make the P(VCap-BMA) compound hydrate inhibitor promising candidates for numerous applications in the petrochemical industry.
基金supported by the National Natural Science Foundation of China(Grant No.22127812,22278433,U20B6005,22178379)Hainan Province Science and Technology Special Fund(Grant NO.ZDKJ2021026)。
文摘Low dosage kinetic hydrate inhibitors(KHIs)are a kind of alternative chemical additives to prevent gas hydrate formation in oil&gas production wells and transportation pipelines.In this work,a series of KHIs were experimentally synthesized with N-vinyl caprolactam(N-VCap)and vinyl ether including vinyl ether,vinyl n-butyl ether,vinyl isobutyl ether,triethylene glycol divinyl ether,with the mole ratio ranging from 9:1 to 5:5.The inhibition performance of new-synthesized KHIs on the formation process of methane hydrate were examined and compared with that of commercial N-vinyl caprolactam PVCap.Several ethylenediamine reagents were used as synergists and tested to improve the inhibition capacity of new-synthesized KHIs.The experimental results demonstrate that the introduction of ether groups on PVCap improves the performance of hydrate inhibitors.PVCap-VNBE(N-VCap:vinyl n-butyl ether=5:5)shows the best inhibition performance for methane hydrate,which could extend the TVO to 1251 min under 6 K subcooling.N,N'-dimethylethylenediamine shows the best synergistic effect for PVCap-VNBE(5:5),and extends the TVO by 2.75 times at 7 K subcooling.Additionally,the relationship between hydrate inhibition performance and interfacial tension of newly-synthesized KHIs under high pressure were studied.It shows that the lower interfacial tension of KHIs would result in longer onset time,exhibiting better inhibition performance.
文摘The hydration of cement compounds gives hydrated compounds, which allow linking together, the different particles and aggregate of cement, and gives the concrete the required qualities. The dynamics of hydration reactions will depend on many factors, such as the fineness of cement, the ratio w/c during hydration, temperature, mixing technique, and the presence of additives in blended cement, as pozzolan, tuff and slag from blast furnaces. We studied the thermal and kinetic reactions of Portland cement hydration, and its variants with different additions using a differential scanning calorimetric analysis. The parameters from these models of curves allow us to evaluate the enthalpies, and the degree of progression of this blended cement, and finally determine their activation energies. We can say that the hydration of Portland cement is due to a series of reactions as （ C3S,C2S,C3A and C4AF reactions with water） and each of them, has its own kinetic, the experimental measurement of the heat of hydration, allows us to represent the overall kinetics of these reactions values of activation energy, they are therefore apparent and global energy. In our experiments, significant differences in these physicochemical parameters were observed, depending on the additive used.
