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.     

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.     

Influence of Polyepoxysuccinic Acid on Solid Phase Products in Portland Cement Pastes

The influence of polyepoxysuccinic acid(PESA) on the solid phase products in hydrated Portland cement pastes was investigated by isothermal calorimetry, X-ray diffraction(XRD), ²⁹Si and ²⁷Al nuclear magnetic resonance(NMR). The results indicated that PESA bonds Ca²⁺ ions in pore solution to prevent portlandite formation, and also combines with Ca²⁺ ions on the surface of silicate minerals to prolong the control time of phase boundary reaction process, leading to the retardation of silicate mineral hydration. Meanwhile, the interlayer Ca²⁺ ions in Jennite-like structure bridging PESA and C-S-H gels prevent silicate tetrahedron and aluminum tetrahedron from occupying the sites of bridging silicate tetrahedron, which causes the main existence of dimer in C-S-H structure, deceases the degree of Al³⁺ substituting for Si⁴⁺ and promotes the transformation from 4-coordination aluminum to 6-coordination aluminum. Furthermore, the -Ca⁺ chelating group from reacting PESA with Ca²⁺ ions combines easily with SO₄^2- ions, resulting in transformation from ettringite, AFm to TAH(Third aluminum hydrate). However, with the higher addition of PESA, it will bridge the excess PESA by Ca²⁺ ions to form a new chelate with ladder-shaped double chains structure, which not only reduces the amount of PESA bonding Ca²⁺ ions, but also decreases its solidifying capability for SO₄^2- ions, leading to the transformation from TAH to AFm or ettringite. Meanwhile, at later hydration, the inhibition effect of PESA on cement hydration is weakened, and the transformation degree from TAH to AFm is higher than that to AFt with the addition of PESA.     

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 Al in slag blended cement paste under sulfate attack

Unilateral sulfate attack of cementitious materials containing 40% slag with different water to binder ratios was investigated. The results showed that the degradation of slag blended cement pastes was nearly from the corners of paste surface with cracking and spallings, water-to-binder(w/b) ratio made a significant sense to the damage that low w/b ratio led to little weight loss, less cracking and spalling damage and vice versa. Microstructural experimental results demonstrated that in the three different stages of sulfate attack, degradation of pastes was primarily associated with the migration behavior and bonding configuration of aluminum, in the early ages Al was mostly present in C-(A)-S-H, and thus, the damage of pastes hardly appeared while at later ones Al had been largely transferred from C-(A)-S-H into AFt, leading to expansive damage.     

赤泥-粉煤灰-矿渣碱激发胶凝材料性质的研究

以赤泥、粉煤灰、矿渣等工业废渣为主要原料制备碱激发胶凝材料,通过正交实验找出了赤泥、矿渣和粉煤灰的最佳配比。当赤泥与粉煤灰比例为3∶1、矿渣的掺量为40%、12%硅酸钠促硬剂为0.12A、减水剂为0.7%时,所制备的碱激发胶凝材料力学性能较好。用蒸压养护制度可得出性能最优的碱激发胶凝材料。赤泥-粉煤灰-矿渣碱激发胶凝材料具有一定的耐酸碱盐腐蚀性、耐高温性能和良好的抗冻性能;吸水率由高到低依次为:水泥、净浆试体、胶砂试体Ⅰ(灰砂比为2∶1)、胶砂试体Ⅱ(灰砂比为1∶1)。X-射线衍射分析表明:在碱激发胶凝材料中生成了大量的铝硅酸盐和钙硅酸盐的复合反应产物,如:莫来石(K2O.Na2O.H2O、Al6Si2O13)、托勃莫来石和C-S-H、C2-S-H凝胶产物等。该类材料不仅具有类似有机聚合物的完整岛状结构及链状结构,还能与矿物颗粒表面的[SiO4]4-和[AlO4]4-四面体通过脱烃基作用形成化学键;来源于原料中Ca(OH)2的C-S-H凝胶多生成于水泥水化的C-S-H凝胶孔隙之中,从而大大提高了结构密实度,是其获得高强度的直接原因。     

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.     

粉煤灰-矿渣基地聚物混凝土力学性能与微观结构

为考察不同配合比对地聚物混凝土性能的影响,开展了粉煤灰与矿渣比例、水玻璃模数以及水玻璃掺量(质量分数)对其宏观力学性能影响的实验研究,并从微观层次扫描电子显微镜(SEM)、能量弥散X射线分析(EDS)、X射线衍射(XRD)、傅里叶红外光谱(FT-IR)以及压汞实验(MIP)对微观结构进行研究.结果表明:养护龄期的增加,...     

Resource utilization of slag from desulphurization and slag skimming: A comprehensive recycling process of all components

In order to make the slag from desulphurization and slag skimming (SDSS) to be comprehensively recycled and utilized, a combined process of beneficiation and building materials preparation was proposed to recover iron from SDSS, meanwhile to apply the remaining slag tailings as cement admixture. From this process, three iron-rich products were recovered in stages by clean gravity - magnetic separation, slag tailings were left. Slag powder was prepared by ultrafine grinding of slag tailings. The stability, setting time and cement mortar strength of the slag tailings cements (STC) which were mixed with Portland cement and slag powder were studied respectively. The results showed that a proper overall performance still could be obtained at the slag powder content of 30%. Chemical composition analysis, X-ray diffraction (XRD) analysis, metallographic microscope and scanning electron microscope (SEM) analysis were employed to assess the characteristics of the SDSS and the products obtained from the whole process. The results indicated that the three iron-rich products could be used as a raw material for steelmaking and ironmaking and the relatively large amount of calcium silicate (C₂S) and tricalcium silicate (C₃S) in the slag tailings make the addition of slag powder into the Portland cement feasible.     

The chloride permeability of persulphated phosphogypsum-slag cement concrete

The chloride permeability and microstructure of persulphated phosphogypsum-slag cement concrete (PPSCC), the Portland slag cement concrete (PSCC) and ordinary Portland cement concrete (OPCC) were investigated comparatively. Some test methods were used to evaluate the chloride permeability and explain the relationship between the permeability and microstructure of concrete. The results show that the resistance to chloride penetration in PPSCC is significantly better than that in OPCC, the reasons are as follows: 1) the slag in PPSCC is activated by clinker (alkali activation) and phosphogypsum (sulfate activation), forming more low Ca/Si C-S-H gel and gel pores below 10 nm than OPCC, improving the resistance to chloride penetration; 2) the hydration products of PPSCC have a much stronger binding capacity for chloride ions; and 3) in the same mix proportion, PPSCC has a better workability without large crystals calcium hydroxide in the hydration products, the interfacial transition zone (ITZ) is smoother and denser, which can cut off the communicating pores between the pastes and aggregates.     

Synthesis Mechanism and Material Characterization of C<Subscript>4</Subscript>AF Obtained by the Self-propagating Combustion Reaction Method

To investigate the influence of preparation process on the properties of synthesized C₄AF, the powder was prepared via the self-propagating combustion reaction (SPCR) method using urea as fuel and metal nitrates as cation precursors. Synthesis mechanism of the SPCR method, calculation and adjusting principles of urea dosage were detailedly introduced. Material characterization of synthesized C₄AF was performed with the aid of X-ray diffractometry, Fourier transform infrared spectrometry, scanning electron microscopy, energy-dispersive X-ray spectroscopy, ²⁷Al nuclear magnetic resonance and isothermal microcalorimetric technique. Remaining content of transition phase of calcium carbonate in synthesized C₄AF was determined by quantitative analysis of X-ray diffractometry. It was found that there was no difference in the hydration behavior of C₄AF synthesized by the SPCR method and the traditional solid-state reaction (SSR) method. C3AH6 and amorphous iron (III) hydroxide (Fe(OH)₃) would be formed during the hydration of C4AF while CH not. Crystallite size of synthesized C₄AF was 16.1 Å and the apparent activation energy was 36.2 kJ/mol. Coordinated condition of Al in C₄AF can be detected by ²⁷Al NMR technique, but the peaks were broadened and the intensities were relatively low, supporting the use of ²⁷Al NMR for the quantitative analysis of C₃A in Portland cements.     

Effect of water soluble PVA on the microstructure characteristics of C-S-H formed in Na<Subscript>2</Subscript>SiO<Subscript>3</Subscript>-Ca(NO<Subscript>3</Subscript>)<Subscript>2</Subscript> solution system

The structure characteristics of hydrated calcium silicate synthesized by solution reaction method with the existing of water soluble polymer polyvinyl alcohol(PVA)are investigated.Using Na 2 SO 3 and Ca(NO 3 ) 2 as the main raw materials,in the condition of 2%(in weight)addition of PVA and the water to solid ratio of 20,hydrated calcium silicate samples(Ca/Si=1.0 and 1.5)were prepared with 60℃water bath.IR,BET,XRD and SEM methods were used to study the microstructure of the hydration products.The results s...     

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.     

NMR research on cement clinker and its structures in early age hydration

Clinker has long been regarded as a critical factor for cement hydration and solidification.α-C2S and β-C2S in 2CaO·SiO2(C2S) phase and C3S Monoclinic 1(C3S M1) and C3S Monoclinic 3 (C3S M3) in 3CaO·SiO2 (C3S) phase were clearly recorded in the 29Si MAS NMR spectra.The content of C3S phase in the clinker deduced from the fine peak analysis coincides with the phase quantification analysis calculated by the Taylor-Bogue method based on XRF,which also accords to the statistical data in industrial production.NM...     

纳滤膜分离浓缩煤化工高盐废水

利用NF-HF和NF-HS纳滤膜对煤化工废水二级反渗透浓水进行处理,重点考察其对Cl与SO42-的分离效果、结垢离子的截留率以及膜抗污染性能,并采用STRO(卷式高压反渗透膜)对纳滤产水进行浓缩处理.实验结果表明,与NF-HS相比,NF-HF具有更优的Cl-/SO42-分离效果及钙、镁、硅离子截留效果和抗污染性能;NF...     

Dehydration Characteristics of C-S-H with Ca/Si Ratio 1.0 Prepared Via Precipitation

Calcium silicate hydrate(C-S-H) with Ca/Si ratio 1.0 was prepared via precipitation in solution and heated at various temperatures to investigate its dehydration behavior. The dehydration, structural collapse and recrystallization characteristics of C-S-H and its microstructural change during heating process were investigated by XRD, SEM, Raman and TG-DSC techniques. C-S-H gradually lost non-evaporable water upon heating, about 50% and 80% non-evaporable water was removed below 200 and 400 ℃, respectively, and the rest was removed up to about 1 000 ℃. At 400 ℃, dehydrated C-S-H exhibited the increasing disordering of calcium/silicon environment and the decreasing symmetrical bending vibration of Si-O-Si of Q~2 silicate chains. At 650 ℃ non-bridging oxygen atoms(O_(non)) attached to silicon were almost removed, and significant structural change occurred, and at 815 ℃ C-S-H dehydrated to wollastonite.     

Preparation and microstructure characterization of poly-sialate-disiloxo type of geopolymeric cement

In order to investigate the influence of three key molar ratios (n(SiO₂)/n(Al₂O₃), n(K₂O)/n(Al₂O₃) and n(H₂O)/n(K₂O)), a total of nine potassium poly-sialate-disiloxo (K-PSDS) geopolymeric cement matrices were designed according to orthogonal design principle. Subsequently, XRD, ESEM-EDXA and MAS-NMR techniques were employed to further characterize the microstructure of the most fully reacted geopolymeric cement matrix. The experimental results show that n(K₂O)/n(Al₂O₃) has the most significant effect on compressive strength amongst the three ratios. The highest compressive strength (20.1 MPa) can be achieved when n(SiO₂)/n(Al₂O₃)=6.5, n(K₂O)/n(Al₂O₃)=0.8 and n(H₂O)/n(K₂O)=10.0. The FTIR spectra of nine PSDS geopolymeric cement matrices also indicate that geopolymeric cement matrix with the highest strength is the most fully reacted one and possesses the largest amount of geopolymeric cement products. The microscopic analysis reveals that PSDS geopolymeric cement matrix possesses structural characteristics similar to gel substances in having a wide range of Si endowments, but predominantly the framework molecular chains of Si partially replaced by 4-coordinated Al tetrahedral.     

Effect of barium oxide on the formation and coexistence of tricalcium silicate and calcium sulphoaluminate

Formation and coexistence of tricalcium silicate (C₃S) and calcium sulphoaluminate (C₄A₃ ) minerals in Portland cement clinker containing calcium sulphoaluminate were investigated. The f-CaO content, mineral composite and formation of mineral in the clinker were analyzed respectively by chemical analysis, differential scanning calorimetry(DSC) and X-ray diffraction. The results show that, adding a suitable amount of BaO can improve the burnability of raw meal and promote the f-CaO absorption. Tricalcium silicate and calcium sulphoaluminate minerals can form and coexist in clinkers at 1 234–1 317 °C by the addition of BaO to the raw meal. A suitable amount of BaO expanded the coexistence temperature of two minerals by 58 °. Funded by the National Basic Research Program of China (No. 2009CB623100), National Eleven Five-Year Scientific and Technical Support Plans (No. 2006BAF02A24), the Natural Science Fund for Colleges and Universities in Jiangsu Province(No. 08KJB430006), the Open Fund for the Key Laboratory of Inorganical and Composite Materials in Jiangsu Province(No. wjjqfhxc1200801) and the Innovation Fund of Doctoral Dissertation of Nanjing University of Technology (No. BSCX200705)     

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.     

钛石膏作水泥缓凝剂研究

介绍了钛石膏中的杂质组成与形态,以及用钛石膏作水泥缓凝剂时,杂质对水泥性能的影响.研究结果表明,钛石膏中杂质主要为Fe(OH)3、FeSO4和Al(OH)3.杂质对水泥性能影响不大,不经预处理作水泥缓凝剂,其性能与采用天然石膏的水泥相当.