Characterization of Pozzolanic Reaction and Its Effect on the C-S-H Gel in Fly Ash-cement Paste

High resolution solid-state 29Si MAS NMR,combined with XRD,SEM and FTIR were used to characterize the pozzolanic activity of FA,type of main pozzolanic reaction products,and the effect of pozzolanic reaction on the C-S-H microstructure in fly ash-cement (FC) paste.The experimental results indicate that in the hydrated FC paste with 30% dosage of FA at 3 d,FA partially participated in the pozzolanic reaction,while,at 120 d,FA largely reacts.During the hydration of FC paste at laboratory temperature,the pozzolanic reaction products are C-S-H gel rather than zeolitic gel.Moreover,after the covalent bonds of Si-O-Si,Si-O-Al and Al-O-Al in the structure of FA are broken,monosilicates Si-OH and Al-OH groups form,these chemical species can connect C-S-H dimers,thus producing more Al-free C-S-H and aluminous C-S-H than in the plain cement paste.The increased content of Al for Si substitution in the bridging tetrahedra of C-S-H may decrease the stability of C-S-H,which results in a rather obvious loss in the mechanical strength of hardened FC paste.     

Effect of pozzolanic reaction products on alkali-silica reaction

1 IntroductionThe use of fly ashto control the expansion dueto al-kali-silica reaction (ASR) is well established and a num-ber of reviews have been published recently[1-4]. Howflyash brings about this reductionin expansionis not yet un-derstood although a number of theories have been put for-ward to explain its action. For controlling mechanism,they put more emphasis onthe adsorption andresort of al-kali by supplementary cementing material (SCM) , formore acidity oxide in SCM,and the secon…     

Effects of molecular structure of polycarboxylate-type superplasticizer on the hydration properties of C3S

Effects of polycarboxylate-type superplasticizer(PC) molecular structure on the hydration heat of tricalcium silicate(C3S) paste and polymerization degree of hydration products(C-S-H gel) were researched by using TAM AIR isothermal microcalorimetry(TA) and 29Si nuclear magnetic resonance(NMR).Methoxy polyethylene glycol-methacrylates-based polycarboxylate superplasticizers with different side chain lengths and main chain lengths were employed.PC molecules with shorter main chain or longer side chains caused stronger retardation of C3S early hydration and lesser increase of C3S 3 d hydration degree.NMR measurement indicated that the incorporation of PC increased the hydration degree of C3S paste and the polymerization degree of silicon-oxygen tetrahedron of C-S-H gel.The tendency for C3S 7 d hydration degree to improve was more pronounced while PC molecules with longer main chain or shorter side chain were added.Whereas,PC molecules with longer main chains or longer side chains increased the 7 d polymerization degree of C-S-H gel.     

A Comparative Study on the Pozzolanic Activity between Nano-SiO2 and Silica Fume

The pozzolanic activity of nano-SiO2 and silica fume was comparatirely stndied by X-ray diffraction （ XRD ） , differential scanning calorimetry （DSC）, scanning electron micrascopy （SEM） and the compressive , bond and bending streugths of hardened paste and concrete were also measured. Results indicate that the compressive strength development of the paste made from Ca（OH）2 and nano-SiO2, the reaction rate of Ca（ OH）2 with nano- SiO2 and the velocity of C-S-H gel formation from Ca （ OH）2 with nano-SiO2 showed marked increases over those of Ca（ OH）2 with silica fume. Furthermore, the bond strength at the interface between aggregate and hardened cement paste, and the bending strength of concrete incorporated with 3% .NS increased more than those with SF, especially at early ages. To sum up, the pozzolanic activity of nano-SiO2 was much greater than that of silica fume. The results suggest that with a small amount of nano-SiO2, the Ca（ OH）2 crystal at the interface between hardened cement paste and aggregate at early ages may be effectively absorbed in high performance concrete.     

Effects of curing systems on properties of high volume fine mineral powder RPC and appearance of hydrates

The effects of different curing systems on the properties of high volume fine mineral powder RPC (reactive powder concrete) and the appearances of hydrates were studied. The experimental results show that dry-heating curing promotes the development of pozzolanic reactivity of fine mineral powder; due to low cement content, 0.20 water-bind ratio and high reactive fine mineral powder content, the strength of RPC increases by around 200% after steam curing and subsequent dry-heating curing. Scanning electron microscopy and energy spectrum diagram showed that: after the high volume fine mineral powder RPC with 0.16 water-bind ratio underwent steam curing and dry-heating curing, there was no significant change in the appearance of hydrates; after the RPC with 0.20 water-bind ratio, the cement content of 150 kg/m³ and more steel slag powder underwent dry-heating curing, there was a certain change in the appearance of C-S-H, the structure of gel was more compact and was uniformly distributed, and the Ca/Si of C-S-H gel decreased from 1.41 to around 1.20.     

活性矿物掺合料对超高性能水泥基材料的影响

通过复掺粉煤灰和硅灰,制备一种抗压强度超过200 MPa的超高性能水泥基复合材料(UHPCC),采用扫描电镜、微区能谱分析、X射线衍射、汞压入法和差示扫描量热分析等现代测试手段,研究了活性矿物掺合料对UHPCC微观结构及性能的影响.实验结果表明,UHPCC水泥石主要以低mCa/mSi、结构致密的C-S-H凝胶和许多未水化颗粒组成;活性矿物掺合料的火山灰效应使水泥浆体与集料间界面过渡区得以改善;矿物掺合料的微集料效应使体系颗粒级配优化,致使基体内部结构致密,总孔隙率减小,孔尺寸得到细化,孔结构得以优化,材料性能得以提高.     

Effect of curing regime on polymerization of C-S-H in hardened cement pastes

The effect of two different curing regimes on the polymerization degree of C-S-H in hardened cement pastes within 28 d were investigated by measuring the chemical environments of ²⁹Si with magic angle spinning (MAS) nuclear magnetic resonance (NMR) and by analyzing the ²⁹Si NMR spectra with deconvolution technique. The experimental results indicate that, at curing regime of constant temperature of 20 °C, the polymerization of C-S-H increases and then decreases with curing age, and the Al/Si ratio increases gradually with curing age, furthermore, the two non-bridging oxygen bonds of bridging silicate tetrahedra in C-S-H structure mainly bond to H⁺. At curing regime of variable temperature, the polymerization of C-S-H firstly increases then changes slightly and subsequently decreases with the temperature from low to high and then to low, and the Al/Si ratio firstly increases then keeps invariant and subsequently slightly decreases. Moreover, the temperature decreasing is advantageous for the Ca²⁺ to be bonded to the bridging silicate tetrahedra and entering into the interlayer of C-S-H structure. The polymerization of C-S-H at curing regime of variable temperature is higher than that cured at constant temperature, but the curing regime of constant temperature is more beneficial to the substitution of Al³ for Si⁴⁺ than that of variable temperature.     

Effect of Curing Regime on Degree of Al3＋ Substituting for Si4＋ in C-S-H Gels of Hardened Portland Cement Pastes

The effect of curing regime on degree of Al3+ substituting for Si4+(Al/Si ratio) in C-S-H gels of hardened Portland cement pastes was investigated by 29Si magic angel spinning(MAS) nuclear magnetic resonance(NMR) with deconvolution technique. The curing regimes included the constant temperature(20, 40, 60 and 80 ℃) and variable temperature(simulated internal temperature of mass concrete with 60 ℃ peak). The results indicate that constant temperature of 20 ℃ is benefi cial to substitution of Al3+ for Si4+, and Al/Si ratio changes to be steady after 180 d. The increase of Al/Si ratio at 40 ℃ is less than that at 20 ℃ for 28 d. The other three regimes of high temperature increase Al/Si ratio only before 3 d, on the contrary to that from 3 to 28 d. However, the 20 ℃ curing stage from 28 to 180 d at variable temperature regime, is benefi cial to the increase of Al/Si ratio which is still lower than that at constant temperature regime of 20 ℃ for the same age. A nonlinear relation exists between the Al/Si ratio and temperature variation or mean chain length(MCL) of C-S-H gels, furthermore, the amount of Al3+ which can occupy the bridging tetrahedra sites in C-S-H structure is insuffi cient in hardened Portland cement pastes.     

Effect of corrosive solutions on C-S-H microstructure in portland cement paste with fly ash

By means of ²⁹Si and ²⁷Al magic angle spinning nuclear magnetic resonance (MAS NMR) combined with deconvolution technique, X-ray diffraction (XRD), scanning electron microscopy (SEM) as well as energy dispersive X-ray system(EDX), the effect of 5 wt% corrosive solutions (viz. 5 wt% Na₂SO₄, MgSO₄, Na2SO4+NaCl and Na₂SO₄+NaCl+Na₂CO₃) on C-S-H microstructure in Portland cement containing 30 wt% fly ash was investigated.The results show that, in MgSO₄ solution, Mg²⁺ promotes the decalcification of C-S-H by SO ₄ ^2- ,increasing silicate tetrahedra polymerization and mean chain length (MCL) of C-S-H. However, the substituting degree of Al³⁺ for Si⁴⁺ (Al[4]/Si) in the paste does not change evidently. Effect of Na²SO⁴ solution on C-S-H is not significantly influenced by NaCl solution, while the MCL and Al[4]/Si of C-S-H in fly ashcement paste slightly change. However, the decalcification of C-S-H by SO ₄ ^2- and CO ₃ ^2- attack, as well as the activation of fly ash by SO ₄ ^2- attack will increase the MCL and Al[4]/Si, which are both higher than that under Na₂SO₄ corrosion, MgSO₄ or Na₂SO₄ +NaCl coordination corrosion.     

INVESTIGATIONS ON THE INTERFACIAL ZONE BETWEEN AGGREGATE AND PORTLAND SLAG CEMENT PASTE

The composition and structure of the interfacial zone be-tween aggregate and portland slag cement paste as well as the orienta-tion coefficient of portlandite(I_CH) have been studied by means ofXRD and SEM. The results show that the main components in the in-terfacial zone are C-S-H gel, portlandite and AFt as well as unhy-drated clinder particles. Compared with portland cement, there aremore C-S-H gel and less portlandite in the zone and the portlanditecrystallizes badly with lower I_CH in a narrower region. Afer adding5.0% silica fume to the cement, the orientation of portlandite in thezone disappears; afer 90d, the bond strength between # 425 portlandslag cement paste and aggregate approximately attains that between #525 portland ciment paste and aggregate.     

Morphology difference between the alkali activated cement and portland cement paste on multi-scale

The features of alkali activated slag（AAS） and portland cement （PC） were observed on multi-scale,the crack and fracture sections were observed with naked eyes,and SEM and AFM were used to study the structure morphology differences between PC and AAS on micrometer to nano meter scale.The experimental results indicated that the AAS paste had soil like fracture texture and it was composed of mainly C-S-H gel but lacks of crystals,and it had a very strong tendency to shrink and crack.AAS paste is much denser and more homogeneous than PC,and on the nano scale C-S-H nano particle in the AAS paste is much smaller and packs much denser than PC paste.     

Durability and micro-structure of reactive powder concrete

Durability of traditional reactive powder concrete (RPC) with rich cement and high volume of fly-ash reactive powder concrete (FRPC) were studied. The X-diffraction and scanning electron microscope (SEM) measurement was imployed to analyze the microstructure. The results show that both types of RPC have higher compressive strength, less volume shrinkage ratio and better carbonation-, chloride-, freezing-resistances than the conventional concrete. The results of X-diffraction indicate that they basically have C-S-H as the main composition without Ca(OH)₂ crystal and ettringite. SEM results show that hydration products of FRPC is mainly III-C-S-H which is piled up closely like densely arranged stone body and it has very compacted structure, in addition, Ca/Si ratio of C-S-H gel is lower than 1.5.     

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 °C displays the highest hydration rate, mechanical strength, the most gel pores and the lowest total porosity.     

Pozzolanic Activity of Burned Coal Gangue and Its Effects on Structure of Cement Mortar

The pozzolanic activity of coal gangue burned at different burning temperatures was investigated. The burned coal gangue was mixed with portland cement in different proportions （ 20% - 60% ）. The pozzolanic activity of coal gangue burned and the hydration products were examined, the compressive strengths of the pastes of the mixtures were tested, and the mechanism of the reaction was discussed. The experimental results slum, that the coal gangue burned at 750 ℃ has the optimum pozzolanic activity, and the burned coal ganguc with SiO2 and Al2 O3 is in an active form. When the coal gangue burned at 750℃ is mixed into portland cement, the content of calcium hydroxide in paste is significantly reduced, while the contents of hydrated calcium silk.ate and hydrated calcium aluminate are increased accordingly, hence resulting in the improvement of the microstructure of mortar. The compressive strength of cement paste decreases with increasing the content of burncd coal gangue. The decease in strength is small in the range of 20% - 30% coal gangue substitution and significant in 30%- 60% substitution.     

Effect of curing regime on the distribution of Al3+ coordination in hardened cement pastes

The effect of curing regime on the distribution of Al³⁺ coordination in hardened cement pastes within 28 d were investigated by ²⁹Si and ²⁷Al magic angle spinning (MAS) nuclear magnetic resonance(NMR) with deconvolution technique. The results indicate that the tetrahedral coordination Al³⁺ incorporated in C-S-H structure mainly originate from the Al³⁺ incorporated in the alite and belite phases in the Portland cement. The curing regime of constant temperature of 20 °C is beneficial to the octahedral coordination Al³⁺ transforming to tetrahedral coordination Al³⁺ incorporated in C-S-H structure. However, at curing regime of variable temperature, the temperature rising process is more advantageous to the transformation from ettringite to monosulphate, substitution of Al³⁺ for Si⁴⁺ in the C-S-H structure and the formation of the third aluminate hydrate (TAH) than that at constant temperature of 20 °C. The high temperature of 60 °C in the holding temperature process promotes the decomposition of ettringite, and enhances the consumption of the Al³⁺ incorporated in C-S-H phases and the Al³⁺ in TAH for the monosulphate forming. The temperature decreasing promotes the transformation from monosulphate to ettringite, and increases the consumption of the Al³⁺ incorporated in C-S-H phases, and then increases the quantity of the TAH.     

Effect of Calcium Silicate Hydrate Seeds on Hydration and Mechanical Properties of Cement

C-S-H series are synthesized at different temperatures and ages by pozzolanic reaction.The change of particle size distribution,phase composition,morphology and nanostructure of C-S-H with temperatures and ages,and the effects of C-S-H seeds and seeds parameters on the hydration behavior and mechanical properties development of cement were investigated by DLS,XRD,SEM,²⁹Si NMR,TAM-air isothermal calorimeter and mechanical properties test.The results show that the particle size,crystallinity,basal spacing and Q²/Q¹ ratio of C-S-H increases with the increase of synthesis temperature and age.The addition of synthesized C-S-H seeds to cement pastes results in the strong acceleration effect on cement hydration and significant improvement of the early strength of cement paste and mortar.The 1 day-C-S-H seeds synthesized at room temperature can increase the strength of cement paste by about 30 MPa at 12 h.The effect does not show a very regular change with the increase of the temperature and age of seeds synthesis.Considering the effect of C-S-H seeds on the hydration and mechanical properties of cement,and economy and short cycle of seeds synthesis,the C-S-H seeds synthesized at room temperature for 1 day or 55 ℃ water bath for 12 hours is recommended..     

Nanoindentation characteristics of calcium hydroxide-metakaolin blended with sodium hydroxide solutions

In order to determine the active mechanism of metakaolin (MK) as partial replacement of cement in concrete from the nanoscale structure perspective, nanoindentation characteristics of calcium hydroxide (CH)-MK blended with 5 M sodium hydroxide (NaOH) solutions simulating the condition of MK in concrete has been studied. The results indicate that three distinct phases are found by the nanoindentation and BSE tests, such as HD C-S-H gel, LD C-S-H gel and the reaction products with the network structure, the residual unreacted MK and CH, respectively. The volume fraction of HD C-S-H gel is about 96% of all reaction product phases. This means that the use of MK in concrete can increase the volume fraction of HD C-S-H gel and thus will improve the properties of concrete.     

合成C-S-H凝胶对水泥石-集料界面区的影响

研究了利用硅质材料和钙质材料经常温常压下水热反应制得的合成C-S-H疑胶对水泥石-集料界面区结构和性能的影响,发现这种合成凝胶对界面区的结构和性能有独特的改善作用。本文还探讨了合成C-S-H凝胶对界面区的作用机理。     

偏高岭土对水泥净浆火山灰效应强度贡献率的影响

根据蒲心诚教授提出的偏高岭土火山灰效应定量分析方法,进行了偏高岭土对水泥净浆(以下简称净浆)火山灰效应强度贡献率(以下简称强度贡献率)的影响研究.结果表明:随着偏高岭土掺量的增加,其净浆强度贡献率增加;随着养护龄期的增加,其净浆强度贡献率呈现先减少后增加的趋势,且7,d时出现最低值;3、28,d时小粒径偏高岭土(2.5和3.75,μm)的净浆强度贡献率明显高于7,d时的值,这说明偏高岭土火山灰效应主要是发生在早期(3,d)和后期(28,d);而大粒径偏高岭土和补充激发剂则有利于提高其中期(7,d)净浆强度.     

Binding materials of dehydrated phases of waste hardened cement paste and pozzolanic admixture

Fly ash (FA) and ground granulated blast-furnace slag (GGBFS) were added to improve the performances of regenerated binding materials (RBM) which refer to dehydrated phases with rebinding ability of waste hardened cement paste. Flowability tests, compressive strength tests, SEM, TG-DSC, and non-evaporable water content tests were employed to study the performances of the combined binding materials and the interactions between RBM, FA, and GGBFS. Results show that adding FA or GGBFS can improve the workability of RBM paste, and GGBFS has positive effects on strength of RBM. Pozzolanic reactions happen between RBM, FA, and GGBFS. And the activation effect of RBM to FA and GGBFS is superior to that of P.O grade-32.5 cement, especially at earlier ages, because of the high reactive f-CaO existing in RBM. On the advantages of the synergetic effects of RBM and pozzolanic admixtures such as FA and GGBFS, new combined binding materials can be prepared by blending them together. Funded by the National Science Foundation of China(No. 50508034)