Study of alinite cement hydration by impedance spectroscopy

Two types of alinite cements, Mg-alinite and Zn-alinite, were synthesized using the reagent grade chemicals. Their hydration behavior was compared with ordinary Portland cement (OPC) using impedance spectroscopy (IS) and ²⁹Si nuclear magnetic resonance (NMR) spectroscopy. The bulk resistance in the IS spectra and the intensity ratio of the hydrous (Q₁ and Q₂) to anhydrous (Q₀) phases in the NMR spectra were estimated as the extent of hydration. The results obtained from both techniques were consistent each other. Mg-alinite had a comparable hydration rate to OPC and Zn-alinite exhibited faster hydration kinetics than Mg-alinite.     

Synthesis and Hydration Characteristics of Alinite Cement

A chlorine-bearing alinite cement was synthesized using reagent-grade chemicals, and the phase evolution and hydration behavior of the alinite clinker were examined. The effects of the MgO content on alinite formation and hydration also were investigated. Alinite began to appear at 1000°C from β-C₂S, C₁₁A₇CaCl₂, and unreacted raw materials, and an almost single-phase alinite was obtained at 1300°C. The alinite phase also was produced without MgO addition. However, CaO, β-C₂S, and C₁₁A₇CaCl₂ phases were present. Alinite cements hydrated rapidly after a short incubation period, and the hydration products were C-S-H gels, Ca(OH)₂, and a Fridel's saltlike phase. The local environmental changes of silicon and aluminum during the formation and hydration of alinite were determined using magic-angle-spinning nuclear magnetic resonance spectroscopy. The Cl⁻-ion exsolution from the alinite paste during hydration was measured using ion chromatography.     

垃圾焚烧飞灰煅烧阿利尼特水泥熟料的形成过程及其水化性能研究

以城市垃圾焚烧飞灰(以下简称焚烧飞灰)为主要原料,在实验室电炉里成功研制了阿利尼特水泥熟料。本文主要研究水泥熟料煅烧形成过程及其水化性能,分析了阿利尼特水泥的适宜石膏掺量、水化放热特征、水化产物及其显微结构。研究结果表明:利用垃圾焚烧飞灰为主要原料可以成功烧制阿利尼特水泥熟料,煅烧过程中首先出现C2S、C12A7和C2S·CaCl2,随后与MgO和CaCl2反应生成阿利尼特;掺加5%二水石膏可以促进阿利尼特水泥水化,较普通硅酸盐水泥更快,阿利尼特水泥可以作为一种早强快硬型水泥使用;阿利尼特水泥主要水化产物除含有硅酸盐水泥中常见的CSH凝胶、棒状AFt和Ca(OH)2晶体外,还含有C3A·CaCl·210H2O晶体。     

Atomic hydrogenation-induced paramagnetic-ferromagnetic transition in zinc ferrite

A paramagnetic-ferromagnetic transition was observed in normal spinel zinc ferrite (ZnFe₂O₄) during atomic hydrogenation at room temperature. Magnetic measurements showed enhanced ferromagnetic property with increasing hydrogenation time. The hydrogenated ZnFe₂O₄ has normal spinel structure according to X-ray diffraction (XRD) and Raman analyses. Iron hydride was found from the XRD and X-ray absorption fine structure results. No A–B site ions exchange was observed in the x-ray absorption spectra while the atomic distances of Fe–O, Zn–O, Fe–Fe, Zn–Zn and Fe–Zn coordinations were reduced. A hybrid of Fe²⁺ and Fe³⁺ in hydrogenated ZnFe₂O₄ can be further revealed through deconvolution of x-ray absorption near edge structure. The paramagnetic-ferromagnetic transition and enhanced ferromagnetic property were mainly due to the formation of iron hydride and the B-site super-exchange interactions of Fe²⁺ and Fe³⁺.     

Activation of ethyl acetate over metal substituted MCM-41: application to alkylation and acylation

Al-MCM-41, Fe,Al-MCM-41 and Zn,Al-MCM-41 materials with different silicon to metal ratios were synthesized hydrothermally and characterized by XRD, BET, FT-IR, Acidity measurement by pyridine adsorbed FT-IR spectroscopy, ²⁹Si and ²⁷Al MAS NMR and ESR techniques. The orderly arrangement of mesoporous materials was clearly revealed from the XRD patterns. ²⁹Si and ²⁷Al MAS NMR established the co-ordination environment of silicon and aluminium. Electron paramagnetic resonance (EPR) study confirmed the co-ordination environment of Fe in Fe,Al-MCM-41 framework. The catalytic activity of these materials was evaluated in the vapour phase alkylation and acylation of ethylbenzene with ethyl acetate in the temperature range between 250 and 400 °C. The products were found to be 1,3-diethylbenzene (1,3-DEB), 1,4-diethylbenzene (1,4-DEB), 1,2-diethylbenzene (1,2-DEB), 4-ethylacetophenone (4-EAP) and acetophenone (AP). The reaction products revealed that activation of ethyl acetate is a convenient route for both alkylation and acylation reactions. The order of the catalysts activity for the reaction is found to be Fe,Al-MCM-41 (50) > Fe,Al-MCM-41 (100) > Zn,Al-MCM-41 (50) > Zn,Al-MCM-41 (100) > Al-MCM-41 (50) > Al-MCM-41 (100). In addition to the density of acid sites, the strength of acid sites is also important for this reaction. The effects of temperature, feed ratio, WHSV and time on stream were also examined and the results are discussed.     

Investigation of early hydration dynamics and microstructural development in ordinary Portland cement using 1H NMR relaxometry and isothermal calorimetry

Benchtop ¹H NMR relaxometry was used to measure the fine temporal resolution of microstructural development during the early hydration of ordinary Portland cement under different levels of retardation. Isothermal calorimetry was used to correlate the various distinct events in water transformation with the progress of hydration reactions. The low field (2 MHz) NMR technique used in this study detected signals from only the mobile water contained in the capillary and gel pores with water incorporation into hydration products highly correlated with heat production, including the reproduction of subtle features. Following the induction period, an initial T₂ decline period, which encompassed the acceleration period of hydration, was characterized by incorporation of water into hydration products without any associated gel pore formation. Gel pore formation commenced at the peak in hydration rate, indicating a change in the morphology of C–S–H growth. All the observed features of microstructural development were preserved under retardation.     

Development of Hydrothermally Synthesized Hydroxyapatite Coatings on Metallic Substrates and Weibull's Reliability Analysis of its Shear Strength

Hydroxyapatite (HA) and Mg‐substituted HA coatings were synthesized on Mg‐9Al‐1Zn and Ti‐6Al‐4V by the hydrothermal process. Grazing‐incidence X‐ray diffractograms showed the formation of calcium–magnesium–phosphate is resulted from the substitution of Mg²⁺‐ions into HA crystal. The chemical state of Mg²⁺‐ions in Mg‐substituted HA coatings was examined by X‐ray photoelectron spectroscopy. The shear test results showed the Mg‐substituted HA coatings deposited on Mg‐9Al‐1Zn have higher shear strength than those coatings on Ti‐6Al‐4V. The Weibull model provided a powerful statistical method for assessing failure mechanism of hydrothermal coatings, which is attributed to a wear‐out failure model with a Weibull modulus m > 3.     

Thermodynamic modeling of hydrated white Portland cement–metakaolin–limestone blends utilizing hydration kinetics from 29Si MAS NMR spectroscopy

Hydration kinetics for the principal phases of Portland cement blends have been incorporated in thermodynamic modeling (GEMS package), utilizing degrees of hydration from ²⁹Si MAS NMR. An empirical relationship for the reaction of these phases is established which includes three variable parameters that all can be estimated from the degrees of hydration. This approach is compared with thermodynamic equilibrium modeling (full hydration) for white Portland cement–metakaolin (0–30 wt.%) blends and for ternary blends of white Portland cement (65 wt.%)–metakaolin–limestone. The predicted phase assemblages have been compared with the phases identified by XRD, ²⁷Al and ²⁹Si MAS NMR which reveals that the incorporation of hydration kinetics improves the agreement between modeling and experiments. The results show also that the formation of strätlingite depends critically on the quantity of charge-balancing anions in the AFm phases, especially carbonate and sulfate anions, and on the degree of hydration for metakaolin.     

Effect of Zn substitution on the structural and magnetic properties of nanocrystalline NiFe2O4 ferrites

Nanocrystalline Ni_1?xZn_xFe₂O₄ (where, x = 0.0, 0.2, 0.4, 0.6, 0.8 & 1) samples were synthesized through solution combustion technique using oxylyl de-hydrazide (ODH) as a fuel and the effect of dopant and its concentration on the structural and magnetic properties was investigated. As-prepared samples were characterized using different characterization techniques such as, XRD, SEM-EDS, TEM and Raman spectroscopy for their phase-purity, crystallinity, surface morphology and elemental composition; also magnetic properties were investigated through EPR, Mossbauer spectroscopy and vibrating sample magnetometer (VSM). Rietveld fitted XRD and Raman studies confirm the formation of cubic spinel structured ferrites and substitution of Zn ion at Ni site without formation of impurity phases. No other structural changes were observed and the structure remains in cubic phase with increase of Zn concentration. SEM and TEM micrographs reveal that the particles are agglomerated and the particles size were found in the nano range. Also good stoichiometric composition was observed in all the compositions of Zn substituted Ni ferrite samples. Magnetic measurements (VSM) reveal that pure Ni ferrites exhibits soft magnetic behaviour. Further the ferromagnetic behaviour suppressed with the substitution of diamagnetic Zn ion and with increase of its concentration in Ni ferrites, which was further evidenced in the Mossbauer spectroscopic results. At room temperature, electronic paramagnetic resonance spectra exhibits a broad resonance signal with Lande's g factor varies from 2.23 to 1.95 with increase in Zn content, which is attributed to spin exchange interactions between Fe³⁺, Ni²⁺ and Zn²⁺ ions also asymmetric EPR spectra was observed. The investigated results show that, Zn substitution has greater impact on the magnetic properties of Ni ferrites due to the diamagnetic nature of Zn, which inturn alters the cationic distribution and the exchange interactions between Ni-Fe and Fe-Fe.     

Synthesis of weakly crystallized hydroxyapatite with Zn substitution and its effect on the calcium phosphate and calcium sulfate cements

Zn is an essential trace element in the normal growth and loading Zn into biomaterials for biomedical applications has always been a hot topic due to its immune regulation. The preparation and characterization of Zn-substituted weakly crystallized hydroxyapatite (WCH) are studied in this work, and Zn-substituted WCH was added to calcium phosphate and calcium sulfate cements (CPC and CSC) to address the effect of Zn²⁺ on the hydration crystallization behavior of calcium phosphate and calcium sulfate. Our results demonstrate that Zn²⁺ will inhibit the transformation of α-TCP to HA during the hydration reaction of CPC. And the adding of Zn²⁺ in CSC changed the crystallization morphology of calcium sulfate. The regulation of Zn on the crystallization behavior of calcium phosphate and calcium sulfate resulted in the different in vitro degradation behaviors of CPC and CSC. With the purpose of improving the biological effects of materials, the polarization of Zn²⁺ released from cements on macrophages was also characterized in this work, and the results showed that appropriate concentrations of Zn²⁺ can inhibit inflammation after stimulating RAW264.7 cells for an appropriate period of time. The presented results may be useful guidelines for the preparation and design of composite bone cement with specific Zn content.     

Electrodeposition of zinc–iron alloy from an alkaline bath in the presence of sorbitol

The chronopotentiometric technique was used to analyze the electrodeposition of Fe–Zn film on a Pt electrode. Three different Fe³⁺/Zn²⁺ molar ratios, Fe26.8 wt.%–Zn73.2 wt.%, Fe46 wt.%–Zn54 wt.% and Fe66.6 wt.%–Zn33.4 wt.%, were used in a solution containing sorbitol as the Fe³⁺-complexing agent, with a total concentration of the two cations of 0.20 M. Coloration of Fe–Zn films were light gray, dull dark gray and bright graphite, depending on the Fe³⁺/Zn²⁺ ratios in the deposition bath. The highest stripping to deposition charge density ratio was 47.5%, at 15 mA cm⁻² in the Fe26.8 wt.%–Zn73.2 wt.% bath. Energy dispersive spectroscopy indicated that the codeposition type of Fe and Zn in the Fe26.8 wt.%–Zn73.2 wt.% and Fe46 wt.%–Zn54 wt.% baths was normal at all j_d tested, while in the Fe66.6 wt.%–Zn33.4 wt.% bath there was a transitional current density from normal to equilibrium codeposition at 50 mA cm⁻². Scanning electron microscopy showed that Fe–Zn films of high quality were obtained from the Fe66.6 wt.%–Zn33.4 wt.% and Fe26.8 wt.%–Zn73.2 wt.% baths, since the films were smooth. X-ray analysis of the Zn–Fe films obtained at 15, 25 and 50 mA cm⁻², in the Fe26.8 wt.%–Zn73.2 wt.%, Fe46 wt.%–Zn54 wt.% and Fe66.6 wt.%–Zn33.4 wt.% plating baths, suggested the occurrence, in general, of a mixture of Fe₁₁Zn₄₀, Fe₄Zn₉, βFe, αFe, Fe₂O₃, Zn and PtZn alloys in the deposit.     

The impact of Fe dosage on the ettringite formation during high ferrite cement hydration

Illustrating the influence of Fe dosage and temperature on the formation of sulfoaluminate hydrates is of great significance to understand the early hydration process of high ferrite cement under steam curing. Herein, the impact of Fe dosage on the ettringite formation at different temperatures was revealed through the combination of experiments and computational simulations. A Fe dosage no more than 20% conspicuously accelerated the crystal growth of ettringite by increasing the surface energy in the (0 0 1) direction, whereas a higher dosage suppressed the formation of ettringite as the high incorporation of Fe ions into the ettringite crystal was energetically unstable. The chemical environment analysis of Fe in products shows that Fe(OH)₆³⁻, compared with Al(OH)₆³⁻, prefers to participate in the formation of Al₂O₃-Fe₂O₃-mono than ettringite, which is also confirmed by the calculated thermodynamic properties’ results. The understanding of the impact and mechanism of Fe on the formation of ettringite under steam curing conditions plays a pivotal role in the utilization of high ferrite cement.     

Relationship of manganese with iron and zinc with respect to latex yield and composition in opium poppy (Papaver somniferum Linn) under two fertility conditions

Two different field experiments were conducted for two years during 1985–86 and 1986–87 to study the relationship of Mn (0, 15 and 30 kg ha^–1) with Fe (0, 15 and 30 kg ha^–1) and Zn (0, 10 and 20 kg ha^–1) under two fertility (NPK) conditions on yield and quality of opium poppy. The main effect of these micronutrients with respect to latex yield was highest at 15 kg ha^–1 of Mn or Fe and 10 kg ha^–1 Zn. Increasing the level beyond that resulted in reduction in latex yield. Highest response was observed when 15 kg ha^–1 Mn was applied with either 15 kg ha^–1 Fe or 10 kg ha^–1 Zn. Morphine, codeine, narcotine and thebaine content of the latex was highest with 15 kg Mn, 15 kg Fe or 10 kg ha^–1 Zn or the combined application of 15 kg Mn with 15 kg Fe or 10 kg Zn ha^–1.CIMAP Publication No. 961     

Preparation of highly efficient and stable Fe,Zn,Al-pillared montmorillonite as heterogeneous catalyst for catalytic wet peroxide oxidation of Orange II

Fe,Zn,Al-pillared montmorillonite (Mt) were prepared by ion exchange reaction. Effect of the Fe/Zn molar ratio in Fe,Zn,Al-pillaring solution on the structural properties of Fe,Zn,Al-Mt was examined. Characterization studies were performed by N₂-adsorption/desorption, ICP, FTIR, DR UV–Vis spectroscopy and XRD. The interlayer space, specific surface and volume of micropores of pillared-Mt was 18.8 Å, 157 m² g^?1 and 0.114 cm³ g^?1 respectively. Besides, the catalytic performance of Fe,Zn,Al-Mt was analyzed through wet peroxide oxidation of Orange II under mild experimental condition. The results indicated that the catalytic performance of Fe,Zn,Al-Mt was affected by the Fe/Zn molar ratio as following pattern: the obtained pillared solids with lower Fe/Zn molar ratios exhibited better catalytic performance and less iron leaching during the reaction. Moreover, the introduction of zinc into Mt shortened the induction time of reaction and improved the catalytic behaviour. Throughout this work, the chemical oxygen demand removal of OII was 77.1 % after the solution treated by Fe,Zn,Al(3/7)-Mt (defined as the Fe/Zn molar ratio of 3/7 in the pillaring solution) catalyst at temperature of 60 °C and atmospheric pressure of 1 atm.     

A high resolution 29Si NMR study of the hydration of tricalciumsilicate

A new method for the determination of the structure of silicate anions, formed during hydration of tricalciumsilicate Ca₃SiO₅ (C₃S), is presented. High resolution solid state ²⁹Si NMR spectra of C₃S and its hydration products, formed during selected reaction times from 6 hours to 130 days, provide the kinetics of formation of the end groups and of the middle groups in silicate chains.     

Aluminum Incorporation in the C–S–H Phase of White Portland Cement–Metakaolin Blends Studied by 27Al and 29Si MAS NMR Spectroscopy

The composition and structure of the calcium‐silicate‐hydrate (C–S–H) phases formed by hydration of white portland cement–metakaolin (MK) blends have been investigated using ²⁷Al and ²⁹Si MAS NMR. This includes blends with 0, 5, 10, 15, 20, 25, 30 wt% MK, following their hydration from 1 d to 1 yr. ²⁹Si MAS NMR reveals that the average Al/Si ratio for the C–S–H phases, formed by hydration of the portland cement–MK blends, increases almost linearly with the MK content but is invariant with the hydration time for a given MK content. Correspondingly, the average aluminosilicate chain lengths of the C–S–H increase with increasing MK content, reflecting the formation of a C–S–H with a lower Ca/Si ratio. The increase in Al/Si ratio with increasing MK content is supported by ²⁷Al MAS NMR which also allows detection of strätlingite and fivefold coordinated aluminum, assigned to AlO₅ sites in the interlayer of the C–S–H structure. Strätlingite is observed after prolonged hydration for MK substitution levels above 10 wt% MK. This is at a somewhat lower replacement level than expected from thermodynamic considerations which predict the formation of strätlingite for MK contents above 15 wt% after prolonged hydration for the actual portland cement–MK blends. The increase in fivefold coordinated Al with increasing MK content suggests that these sites may contribute to the charge balance of the charge deficit associated with the incorporation of Al³⁺ ions in the silicate chains of the C–S–H structure.     

A New Sorbent for Selective Separation of Metal: Polyethylenimine Methylenephosphonic Acid

Abstract

A new sorbent, the polyethylenimine methylenephosphonic acid (PEIMPA), was synthesized from commercially available polyethylenimine. After characterization by (¹H, ¹³C, ³¹P) NMR, elementary analysis, UV/VIS and FTIR, the new ion exchange polymer PEIMPA has been investigated in liquid – solid extraction of a mixture of Cd(II), Co(II), Cu(II), Fe(III), Ni(II), Pb(II), and Zn(II) cations from a mineral residue of zinc ore dissolved in nitric acid. The selectivity of this polymer was studied as a function of pH. PEIMPA can sorb much higher amounts of Fe ion than Cd, Co, Cu, Ni, Pb, and Zn ions. The recovery of Fe(III) is almost quantitative. Because of this remarkable affinity, the PEIMPA resin has the potential for application in several fields. Further studies of the polymer are in progress.     

Structure and mechanical properties of aluminosilicate geopolymer composites with Portland cement and its constituent minerals

The compressive strengths and structures of composites of aluminosilicate geopolymer with the synthetic cement minerals C₃S, β-C₂S, C₃A and commercial OPC were investigated. All the composites showed lower strengths than the geopolymer and OPC paste alone. X-ray diffraction, ²⁹Si and ²⁷Al MAS NMR and SEM/EDS observations indicate that hydration of the cement minerals and OPC is hindered in the presence of geopolymer, even though sufficient water was present in the mix for hydration to occur. In the absence of SEM evidence for the formation of an impervious layer around the cement mineral grains, the poor strength development is suggested to be due to the retarded development of C-S-H because of the preferential removal from the system of available Si because geopolymer formation is more rapid than the hydration of the cement minerals. This possibility is supported by experiments in which the rate of geopolymer formation is retarded by the substitution of potassium for sodium, by the reduction of the alkali content of the geopolymer paste or by the addition of borate. In all these cases the strength of the OPC-geopolymer composite was increased, particularly by the combination of the borate additive with the potassium geopolymer, producing an OPC-geopolymer composite stronger than hydrated OPC paste alone.     

Preparation and hydration study of alinite cement

A laboratory alinite clinker was prepared at 1200°C by using industrial raw materials and adding 2.6% CaCl₂ to the raw mix. The structure of the clinker was studied by XRD and SEM. Three cements were prepared by intergrinding the clinker with 4, 6 and 8% gypsum. Compressive Strength development of these cements was studied up to 90 days. Hydration phenomena were also studied by XRD and SEM in pastes cured for 7, 28, and 90 days. Useful information is drawn concerning the structure of alinite clinker and the hydration phenomena of these cements.     

Infrared and Mössbauer study of two Indian cements

The infrared and Mössbauer spectroscopic studies have been carried out for dry and hydrated samples of Indian Ordinary Portland Cement and Portland Pozzolana Cement. The infrared wavebands have been assigned and discussed in the light of available literature. The Mössbauer data show that iron occurs as Fe³⁺ and occupies two sites with 6 and 4 coordinations and that hydration of cement renders the conformation around Fe atoms more symmetric. The possibility of formation of Fe(OH)₃ and its gel is also excluded on the basis of the values of Mössbauer parameters.