Probing development of microstructure of early cement paste using 1H low-field NMR

Development of microstructure of early cement paste (0–6 h) was investigated with ¹H low-field NMR. It was found that T ₂ (transverse relaxation time) distributions of fresh cement paste were bimodal and two peaks were ‘long component’ and ‘short component’. Separation degree of two peaks was a sign of exchange of water within flocculation and outside flocculation. Factors such as water cement ratio, specific surface area and dosage of superplasticizer had influences on the separation degree: the separation degree increased with the water cement ratio; the separation degree of cement paste prepared with cement with a high specific surface area was zero; dosage of superplasticizer will decrease separation degree. Results also suggested that T ₂ distribution gradually moved to the left and T ₂ of long component and initial fluidity were linearly correlated.     

Multi-level flocculation structures of fresh cement paste by confocal laser scanning microscope

Under saturation dosage of all kinds of SP, the free water amount was examined by centrifuge. The distribution of solution and flocculation microstructures in fresh cement paste was observed in three- dimensional space by confocal laser scanning microscope（CLSM）. Results indicate that SP can increase the free water amount by destroying the flocculated cement particle structure and different free water amount is released by different kinds of SP. The changes of the size of flocculation structures and the dispersion of solution were obviously detected with confocal laser scanning microscope： the size of flocculation structures was smaller and more dispersed in fresh cement paste with polycarboxylate superplasticizer, but the size of flocculation structures was bigger and cannot be dispersed uniformly in fresh cement paste with others SP. The multi- level flocculation structures theoretical model of fresh cement paste was then set up. The theory indicates that different kinds of SP with different dispersion strength will open the flocculation structures at different levels, which in turn present different water reducing rate.     

Microscopic properties and sealing performance of new gas drainage drilling sealing material

The geological condition of Chinese coal mines are complex and high gassy, which account for fifty percent to seventy percent. Because of the abundant pores and cracks around the drainage drilling hole, the gas concentration attenuates rapidly, and the effective gas drainage period is short. The traditional sealing materials of yellow mud and cement-sand grout will readily shrink after the drilling hole is sealed, the sealing length is short and the sealing quality is not satisfactory. Currently widely used polyurethane material will shrink when it comes into contact with water, and the price is also very high. In this study, taking cement as a base material, a novel composite sealing material mixed by expansion admixture, additive, and fibrin and coupling agent was developed and the sealing performance and expansion property of the material were also studied and analyzed. The FEI Quanta TM 250 environmental scanning electron microscope was used to investigate the microstructure of material. The results revealed that the new composite sealing material had a desirable expansion performance and a definite fluidity convenient for grouting. The solidified material, combining closely with the drilling wall, possessed an adequate strength and was not easy to shrink. Compared to the conventional polyurethane, the gas drainage concentration by drilling sealing exceeded 40 percent, and the sealing capacity improves 5 times, the sealing effect increases significantly.     

The hydration characteristics and expansion machanism of expansive cement at low<Emphasis Type="Italic">W/B</Emphasis> ratio

The hydration characteristics and expansion impetus of three kinds of cement paste under free-and confined-curing conditions were investigated, which were respectively mixed with three different kinds of expansive agent at low W/B ratio. The results show that the hydration products of pure cement paste and paste mixed with expansive agent are same, but the amount of hydration products, un-hydrated C₃S and C₂S are obviously different at the same hydration age. At 3 d age, the amount of CH in pure cement paste is less than that of paste mixed with expansive agent, but it is reverse when at 28 d age. The amount of AFt at 3d and 28d age in pure cement paste is less than those of paste mixed with expansive agent. Regardless of under free- or confined-curing condition, the amount of ettringite produced varies little since 3d age. The joint effect of the tumefaction of gel-ettringite due to water absorption and the expansive pressure on the pore caused by the crystalloid ettringite is the cause of the volume expansion of cement paste, and the former effect is much greater than the latter. LU Lin-nu : Born in 1972 Funded by 973 High-tech Project of China (No. 2001CB610704-2) and the Natural Science Foundation of Hubei Province(No. 2002AB075)     

Influence of elevated curing temperature on the properties of cement paste and concrete at the same hydration degree

Three different curing temperatures(20 ℃, 40 ℃, and 60 ℃) were set, so that the nonevaporable water(w_n) contents of plain cement pastes cured at these three temperatures were measured to determine the hydration degree of cement. Tests were carried out to compare the pore structure and strength of cement paste, as well as the strength and permeability of concrete under different temperature curing conditions when their cements were cured to the same hydration degree. The experimental results show that either at a relatively low hydration degree(w_n=15%) or high hydration degree(w_n=16.5%), elevated curing temperature has little influence on the hydration products of cement paste, while it has a negative influence on the pore structure and compressive strength of cement paste. However, this negative effect is weaker at high hydration degree. The large capillary pore(100 nm) volumes of cement pastes remain almost the same at high hydration degree, regardless of curing temperatures. As for the concrete, elevated curing temperature also has negative influence on its compressive strength development, at both low hydration degree and high hydration degree. And this negative effect is stronger than that on cement paste's compressive strength at the same hydration degree. On the whole, elevated curing temperature has little influence on the resistance of concrete to chloride ion penetration.     

粉煤灰与矿粉改进减水剂与水泥相容性的研究

采用萘系、聚羧酸系减水剂与粉煤灰、矿粉双掺法,进行水泥流动性的试验,测定净浆流动度损失,研究粉煤灰、矿粉对减水剂与水泥相容性影响,研究发现,粉煤灰、矿粉能有效改进萘系、聚羧酸系减水剂与水泥的相容性;而聚羧酸系减水剂与水泥的相容性比萘系减水剂好．     

结合分形理论的水泥絮凝研究

目的对水泥絮凝进行定量化研究,找出其微观结构与宏观性质的联系.方法用“激光颗粒分布测量仪”测试了不同水泥絮凝颗粒的粒度分布,分析了各絮凝颗粒的分形特征,探讨了分形维数与水泥比表面积、净浆流动度的关系.结果水泥絮凝颗粒的粒度分布具有很好的自相似性,属于典型的无规三维分形体;且分形维数越大,比表面积越大,水泥净浆流动度越小.结论用分形维数对抽象的水泥絮凝粒度分布进行定量描述是可行的,从分形维数可以推断出比表面积和净浆流动度等宏观性质的变化趋势.     

The influence of steel slag with high Al2O3 content on the initial hydration of cement

The initial hydration of steel slag with high Al₂O₃ content and its influence on the initial hydration of cement were investigated in this study. Steel slag with high Al₂O₃ content may contain much calcium aluminate mineral but very little gypsum. The steel slag hydrates much more quickly than cement in the initial hydration period, producing many flake products which have a great influence on the fluidity, initial setting time, and adsorption level of superplasticizer of paste. Replacing part of cement by steel slag with high Al₂O₃ content can change the hydration condition of calcium aluminate mineral of the cement by decreasing the gypsum to calcium aluminate mineral ratio, resulting in accelerating the hydration rate of calcium aluminate mineral in the initial hydration period. Paste containing steel slag with high Al₂O₃ content has a shorter initial setting time, higher adsorption level of superplasticizer, and greater loss in fluidity than the pure cement paste.     

Multi-scale modeling of the effective chloride ion diffusion coefficient in cement-based composite materials

N-layered spherical inclusions model was used to calculate the effective diffusion coefficient of chloride ion in cement-based materials by using multi-scale method and then to investigate the relationship between the diffusivity and the microstructure of cement-basted materials where the microstructure included the interfacial transition zone（ITZ）between the aggregates and the bulk cement pastes as well as the microstructure of the bulk cement paste itself.For the convenience of applications,the mortar and concrete were considered as a four-phase spherical model,consisting of cement continuous phase,dispersed aggregates phase,interface transition zone and their homogenized effective medium phase.A general effective medium equation was established to calculate the diffusion coefficient of the hardened cement paste by considering the microstructure.During calculation,the tortuosity（n）and constrictivity factors（D_s/D₀）of pore in the hardened pastes are n≈3.2,D_s/D₀=1.0×10^-4respectively from the test data.The calculated results using the n-layered spherical inclusions model are in good agreement with the experimental results;The effective diffusion coefficient of ITZ is 12 times that of the bulk cement for mortar and 17 times for concrete due to the difference between particle size distribution and the volume fraction of aggregates in mortar and concrete.     

Characterization of yield stress development of cement paste by electrical resistivity

Yield stress development of cement paste is potentially governed by percolation of 3-dimensional links formed by hydration products on the surface of the particles. It rises steadily at a gradual rate before a sudden increase in rate of growth. In this study, a method was proposed to predict the yield stress development based on the diameter of spread(D) of mini slump cone test and gradient from electrical resistivity measurement(K_m). To evaluate the significance of(D) and(K_m) in terms of yield stress, they were quantitatively compared to the initial yield stress(τ_0) and rate of yield stress growth(K) obtained from a rheometer. A mathematical relationship between the yield stress of cement paste, diameter of spread and electrical resistivity characteristic gradient was developed. The equation developed can be used as an alternative method to estimate yield stress of cement paste.     

Effect of magnesium on the C-S-H nanostructure evolution and aluminate phases transition in cement-slag blend

The microstructural study was conducted on cement and cement-slag pastes immersed in different concentrations of Mg(NO_3)_2 solutions utilizing ~(29)Si, ~(27)Al NMR spectroscopy and XRD techniques. The results show that the hydration of both the cement and cement-slag pastes is delayed when the pastes are cured in Mg(NO_3)_2 solutions as compared to the pastes cured in water. Moreover, Mg~(2+) ions also exhibit an decalcifying and dealuminizing effect on the C-A-S-H in cement and cement-slag pastes, and thereby decrease Ca/Si and Al[4]/Si ratios of the C-A-S-H. The dealuminization of C-A-S-H is mitigated for cement-slag paste as compared to pure cement paste. The depolymerized calcium and aluminum ions from C-A-S-H gel mainly enter the pore solution to maintain the pH value and form Al~[6] in TAH, respectively. On the other hand, Mg~(2+) ions exert an impact on the intra-transition between Al~[6] species, from AFm and hydrogarnet to hydrotalcite-like phase. NO_3~-ions are interstratified in the layered Mg-Al structure and formed nitrated hydrotalcite-like phase(Mg_(1-x)Al_x(OH)_2(NO_3)_x·nH_2O). Results from both ~(27)Al NMR and XRD data show that ettringite seems not to react with Mg~(2+) ions.     

Early age hydration of cement paste monitored with ultrasonic velocity and numerical simulation

Early age hydration of cement paste was investigated by monitoring the ultrasonic propagation velocity and simulated with the numerical model CEMHYD3D. The ultrasonic velocity of the P-wave was recorded during the first 24 hours of the hydration process and its evolution was analyzed. It is shown that the UPV method is an effective, accurate and non-destructive method for monitoring the early age hydration process of cement paste. The early age hydration process can be classified as four periods, which are the dormant period, acceleration period, deceleration period and stabilization period. Higher w/c ratios result in lower UPV, and delay initial setting time due to the decreased solid volume. The change of UPV is clearly related to the hydration degree of cement particles.     

Effect of polycarboxylate-type superplasticizer on the paste fluidity based on the water film thickness of flocs

The excess water film theory and the properties of flocs are integrated to examine the effect of the polycarboxylate-type superplasticizer on the paste fluidity.The theory states that excess water can surround the flocs rather than the particles and that the cell consists of a floc and a superficial water film.Experiments on limestone powder pastes were conducted to verify the theory.The superplasticizer dosage(sp%)and the water–powder ratio by volume(Vw/Vp)were systematically varied.A sedimentation balance method was used to measure the size distribution of the flocs in the limestone powder pastes.The water film thickness(WFT)of flocs was then calculated and shown to determine the paste fluidity.Based on this WFT of flocs,the effect of the sp on the paste fluidity was determined and then compared with the effect of water.     

Influence of CG With High Content of Metallic Particles as a Cement Admixture on Cement Strength

1　IntroductionCopperresidueisanindustrialby productdis chargedbycopperrefineries ,butitusuallycontainssomeusefulmetals .Forexamplecopperresiduecontains 4 %to5 %copper ,1.0 1g tgold ,2 4g tsilverand 4 2 %magne tite ,alltheseexceedthecontentforacomprehensiveutili zation .Inordertoextracttheseusefulmetals ,thecoolingtechnologyofremovingresidueisintroducedbyslowlycooling (4 8h)sothatsomemetallicionsgrow .Afteronemoreflotationforcopperandmagneticbyextractionofiron ,thedischargedresidueiscalledcopp…     

Effect of competitive adsorption between sodium tripolyphosphate and naphthalene superplasticizer on fluidity of cement paste

The adsorption amount, ζ-potential of cement particles and fluidity of cement paste were tested to research the competitive adsorption between naphthalene superplasticizer(FDN) and STPP. The experimental results showed that the presence of STPP could significantly improve the fluidity of cement paste and reduce the fluidity loss with FDN. There existed a competitive adsorption between STPP and FDN. STPP and calcium ions formed complexes; they preferentially adsorbed onto surface of cement particles and preempt adsorption points of FDN; and it reduced adsorption amount of FDN. In the absence of STPP, saturation adsorption amount of FDN was 5.93 mg/g; but when the dosage of STPP was 0.1%, it reduced to 4.3 mg/g(about 72.5%). The adsorption amount of FDN was reduced by STPP, but ζ-potential of cement particles enhanced and fluidity of cement paste increased because of strong negative charge effect of the complexes. Adsorption of the complexes would delay Ca2+ into liquid and inhibit formation of active adsorption points. Then, content of FDN in liquid increased with the addition of STPP and ζ-potential of cement particles became stable. In this way, fluidity loss of cement paste reduced.     

The Hydration of Blended Cement at Low W/B Ratio

1　IntroductionThehydrationandhardeningprocessesofordinarycementhavebeenstudiedintensively[1-3 ] .Partlyreplac ingcementwithflyash ,slag ,orotheractivemineralad mixturecannotonlymodifythecementstrengthgrade ,re ducethehydrationheatofcement ,butalsomelioratethestructureofhardencementpaste[4] .Applyingexpansiveagentinordinaryconcretecancombinethebearingandwaterprooffunctionsofabuilding ,anditcanalsoreducetheshrinkageandpreventthecrackingofconcrete[5,6] .However ,thehydrationprocessofcementmixedw…     

Dominant factors on the early hydration of metakaolin-cement paste

The dominant factors during early hydration process of cement paste containing 10% metakaolin replacement (MK10) and 10% kaolin replacement (K10) are investigated in comparison to neat cement paste (NCP), and X-ray Diffraction (XRD) analysis is employed to identify the crystalline phases of all specimens. Thermogravimetric (TG) and Differential Scanning Calorimetry (DSC) are used to identify the phase constituents. The amount of acid-insoluble residue (AIR) of all specimens is used to evaluate the unreacted materials. The results indicate that, after the first day, MK act as nuclei for the formation of C-S-H during hydration of C₃S and C₂S, densifying the microstructure of cement paste. Its contribution is mainly due to the fine nature of the MK. From 3 days to 7 days, more and more MK reacts with CH to form C-S-H, making the microstructure denser. The strength contribution is mainly due to the chemical activity of MK.     

Influence of MgO/MgCl2 molar ratio on phase stability of magnesium oxychloride cement

Formation, solution and phase change of hydration products in MgO-MgCl₂-H₂O system was studied with thermodynamics method, and resistance to water immersion and phase change of magnesium oxychloride cement with different MgO/MgCl₂ molar ratio was experimented. The results show that pH value of immersion solution of cement paste has a remarkable influence on phase stability of hydration products. A higher pH value leads to a lower solubility and a better phase stability of hydration products. When the solution pH value is higher than 10.37, the precipitation of much Mg(OH)₂ crystal induces a worse phase stability of hydration products. With the increasing MgO/MgCl₂ molar ratio (lower than 6), the more amount of MgO in the hydration products enhances the alkalinity of solution and the phase stability is improved. However, when the MgO/MgCl₂ molar ratio is higher than 6 and the excessive MgO exsits in the hydration products, the cement paste may be damaged by the excessive crystallization stress of a great deal of Mg(OH)₂ formation. Funded by the National Natural Science Foundation of China(No. 50078019)     

The effect of elevated temperature on bond performance of alkali-activated GGBFS paste

The main reaction products were investigated by analysis of microstructure of alkali-activated ground granulated blast furnace slag (GGBFS) paste. An experimental research was performed on bond performance of alkali-activated GGBFS paste as a construction adhesive after exposure to 20–500 °C. Through XRD analysis, a few calcium silicate hydrate, hydrotalcite and tetracalcium aluminate hydrate were determined as end products, and they were filled and packed each other at room temperature. In addition, akermanite dramatically increased at 800 °C and above. The two key parameters, the ultimate load P _u.T and effective bond length L _e, were determined using test data of carbon fiber-reinforced polymer (CFRP)-to-concrete bonded joints at elevated temperature. The experimental results indicate that the ultimate load P _u.T remains relatively stable initially and then decreases with increasing temperature. The effective bond length L _e increases with increasing temperature except at 300 °C. The proposed temperature-dependent effective bond length formula is shown to closely represent the test data.     

Hydration mechanism of sulphoaluminate cement

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.