Analysis of calcium leaching behavior of plain and modified cement pastes in pure water

The calcium ion leaching behavior of cement pastes modified with a high-alkali fine glass powder, silica fume, and fly ash, exposed to deionized water, is reported in this paper. Porosity enhancement in pastes subjected to leaching is attributed both to the dissolution of calcium hydroxide (CH) as well as decalcification of C–S–H gel. A methodology that combines the measured porosity increase along with the CH and C–S–H contents remaining after leaching for a particular duration is developed to separate the porosities created due to CH and C–S–H leaching. In order to quantify the influence of leaching on the amounts of Ca ions remaining in the CH and C–S–H phases, solid–liquid equilibrium curves for calcium are developed for the unleached and leached pastes. Leaching depths are also calculated using the CH contents of the leached and unleached specimens. All the modified pastes show better leaching resistance than the plain paste. In addition to the microstructure densification, the lower Ca–Si molar ratio in modified pastes that reduces the equilibrium liquid Ca ion concentration contributes to this observation. For the glass powder modified paste, the presence of higher alkali content in the pore solution further reduces the dissolution of CH due to common ion effect, thus providing it with the highest leaching resistance. Fly ash and silica fume modified pastes demonstrate leaching resistance in between those of the plain and glass powder modified mixtures.     

Influence of leaching on the local mechanical properties of an aggregate-cement paste composite

This paper presents an experimental study to characterize the mechanical behaviour, at the local scale, of sound and degraded concrete after leaching. An experimental protocol was developed to study the effects of the calcium leaching mechanism at the interfacial transition zone (ITZ) on the mechanical properties of the cement-aggregate interface and bulk paste of model material. The process of lixiviation with deionised water occurs very slowly. The experimental study in the laboratory was accelerated by replacing the water with an ammonium nitrate solution. To quantify the development and kinetics of degradation at the cemented bond, the concrete leaching fronts were characterized at different levels of degradation using phenolphthalein and local mechanical tests (compression and tensile) and performed on samples consisting of two aggregates bound by cement paste. Tests were performed on sound samples at different hydration times and on chemically degraded samples. The results show the effect of leaching on the mechanical properties of the samples and making it possible to correlate the progress of leaching to the evolution of these locally considered properties. The experimental results show that there is an ITZ effect on the alteration of the mechanical properties due to leaching.     

Comparative study of accelerated decalcification process among C3S, grey and white cement pastes

This study compared the resistance of Triclinic-C₃S, grey (OPC) and white (WOPC) Portland cement paste to decalcification induced by accelerated leaching in concentrated ammonium nitrate solutions. Paste microstructure was studied with scanning and backscattering electron microscopy (SEM and BSEM) and nitrogen BET surface area techniques. Ca²⁺ leached content was quantified by ICP, XRD and FTIR techniques were used to study phase mineralogy. The conclusions drawn from the findings were that calcium leaching-induced decay in the cementitious materials studied (C₃S, OPC and WOPC), accelerated by immersion in ammonium nitrate, affected the main calcium phases in the samples (CH, C-S-H gel and ettringite), i.e., both the anhydrous and the hydrated phases. The present study showed that the Ca/Si ratio of C-S-H gels declines on a gradient from the sample core outward. Specimen surface area and nanoporosity rose in cementitious materials after Ca leaching-induced decay and subsequently declined as a result of the collapse of the structure of the hydrated cement, and in particular of the C-S-H gel. C₃S paste was impacted more quickly and intensely by leaching than the WOPC and OPC pastes. Further to the findings of this study, the leaching resistance of these three materials, in descending order, is: OPC > WOPC > C₃S.     

基于碟片法的溶蚀作用下水泥净浆微观结构演变研究

溶蚀作用下水泥基材料的微结构变化导致混凝土材料服役性能退化。为了克服传统试验因试样厚度影响而产生的脱钙不均匀现象,以NH4NO3溶液对约1mm的碟片状水泥净浆试件进行加速脱钙,通过控制质量损失来控制溶蚀程度。然后把质量损失作为衡量溶蚀程度的参数,结合压汞法(MIP)、环境扫描电子显微镜(ESEM)及能谱分析(EDS),研究不同溶蚀程度下水泥净浆的微观形貌、化学组成和孔隙结构变化规律。试验结果表明:试件钙硅比(Ca/Si)与质量损失大致呈两段线性关系。在第一阶段,水泥浆体试件Ca/Si逐渐降低,氢氧化钙(CH)分解,质量损失10%试件中CH已被严重溶蚀;水化硅酸钙(C-S-H)凝胶的Ca/Si随着溶蚀程度增加而降低,证明C-S-H凝胶第一阶段已开始分解。在第二阶段,主要表现为C-S-H凝胶继续分解。试验还发现,溶蚀后水泥净浆试件内部孔径小于50nm的孔略微增加,50~200nm的孔含量有部分减少;孔径大于200nm的多害孔大量增加。     

浓度对硝酸铵水溶液热稳定性的影响研究

目前硝酸铵水溶液常被用于工业炸药和农用肥料生产中。在实际生产中,氯化物是极易混入的一种杂质。在酸性条件下,Cl-浓度高的硝酸铵溶液,短时间内会加剧自催化热分解过程,导致高热、高温气体产物高度聚集而爆炸。为了防止生产过程中发生爆炸事故,利用临界爆炸测试系统对硝酸铵水溶液的临界爆炸温度进行测定。实验结果表明:一定浓度范围的纯硝酸铵溶液,浓度越高,越容易促进溶液的分解爆炸。当其接近固体硝酸铵浓度时,爆炸反而不容易发生;含有500 mg/kg KCl的硝酸铵酸性溶液中,浓度的增高会使其临界爆炸温度变低,且浓度每增加10%,临界爆炸温度就会降低5～6℃。在硝酸铵溶液的运输、贮存过程中,应将浓度控制在合理的范围内,以确保其安全。     

Leaching effect on mechanical properties of cement-aggregate interface

This study concerns the characterization of the mechanical properties of the cement paste and of the cement-aggregate interface in the degraded state by a chemical leaching mechanism. This study is carried out within the framework of the MIST laboratory. The experimental tests were carried out on cement paste and composites consisting of aggregates bound by the same cement paste prepared with a water/cement ratio of 0.5. The particular experimental devices, designed and produced for the purposes of this study, made it possible to directy solicit the composites at the cement-aggregate interface. As the process of leaching with the deionized water occurs very slowly, the experimental study is accelerated in the laboratory by replacing water by ammonium nitrate solution. To quantify the development and kinetics of chemical degradation at the cemented bond, the concrete leaching fronts are characterized at different times of degradation by using phenolphthalein. The local mechanical tests (tensile and shear) are performed on cement paste and composite at different degradation rate. The experimental results show a fast drop in shear or tensile strength of about 45% at the beginning of degradation. These results confirm the effect of the cement paste-aggregate interface degradation on the mechanical properties.     

Preparation and characterization of submicron-cerium oxide by hypergravity coprecipitation method

Submicron-cerium oxide particles were synthesized by applying hypergravity using ammonium bicarbonate (precipitant) and cerium nitrate hexahydrate (precursor). The influence of the concentration, pH, dispersant loading, flow rate, rotation speed of the hypergravity rotating bed, calcination temperature, and time on the cerium oxide particle size were examined by zeta potential, solid–liquid contact angle, thermo-gravimetry–differential scanning calorimetry, scanning electron microscopy, X-ray diffraction, and transmission electron microscopy. The cerium oxide particles were highly dispersed, with an average particle size of 200 nm. Calcining at 650 °C for 1.5 h afforded the smallest particles. The crystallite size and fraction crystallinity increased with prolonged calcination. Crystalline cerium dioxide grew along three crystal planes, forming a complete face-centered cube, affording high hardness and activity of the polishing powder. The optimal conditions were: cerium nitrate concentration: 0.7 mol/L, cerium nitrate/ammonium bicarbonate molar ratio: 1:3, dispersant mass fraction: 3%, cerium nitrate initial pH: 4–5; the precursor solution was adjusted to pH 9 with ammonia water. Hypergravity coprecipitation with 1.5 h calcination afforded submicron-sized cerium oxide with a uniform size distribution using ammonium bicarbonate in an industrially viable process. The simple and low-cost manufacturing process may enable the development of hypergravity-assisted chemical synthesis technology.     

提高岩石膨化硝铵炸药的堆积密度研究

文章通过对影响膨化硝铵炸药产品性能的配方、膨化硝酸铵密度等因素的研究,分析了影响膨化硝酸铵密度和颗粒尺寸分布的真空度、膨化剂、硝铵浓度、溶液温度、设备等关键因素,结合连续化工艺设备特点,提出了一些提高膨化硝铵炸药堆积密度的方法,以达到改善炸药体积威力的目标。     

Diffusivity evolution under decalcification: influence of aggregate natures and cement type

Since the decalcification of cement paste has been largely reviewed, we focus our studies on the influence of aggregate nature on this phenomenon in relation to the type of cement used, Ordinary Portland Cement or blended cement with fly ash and slag. Some characteristics of similar mortar mixtures where only aggregate nature differs (lime and siliceous sand) are therefore compared for the two types of cement before and after chemical decalcification induced by ammonium nitrate attack: mechanical strength, microstructure (porosity observed by mercury intrusion and profiles of oxide content trough degraded and sound zones determined by electronic microprobe analysis), transport properties (chloride ions diffusivity, gas and water permeabilities). The characterization of sound mortars underlines that siliceous aggregates promote less porous cementitious matrix. The duplication of ammonium nitrate attacks on same material allows testing the experimental parameters governing the degradation. The flows of calcium leached, the microstructure and the evolution of transport properties with decalcification suggest that limestone aggregates are not inert material. Consequently, for the mortars incorporating siliceous sand, the cementitious matrix is more decalcified and this leads to an amplification of ionic transports, especially through blended cement paste.     

Comparing the Concentration of Calcium Hydroxide in the Diffuse Double Layer by Modeling and Experiment

The leaching of elements from the surface of charged fly ash particles is known to be an unsteady process. The mass transfer resistance provided by the diffuse double layer has been quantified as one of the reasons for this delayed leaching. In this work, a model based on mass transfer principles for predicting the concentration of calcium hydroxide in the diffuse double layer is presented. The significant difference between predicted calcium hydroxide concentration and the experimentally measured is explained.     

Hydroxyapatite-based ceramic materials prepared using solutions of different concentrations

Hydroxyapatite, Ca₁₀(PO₄)₆(OH)₂, powders with enhanced sinterability have been synthesized through precipitation from calcium nitrate and ammonium hydrogen phosphate solutions at pH 9, t= 60°C, and a Ca/P atomic ratio of 1.67, and their properties have been studied: phase composition, particle size distribution, loose density, and green density. The initial solution concentration is shown to influence the properties of the powders and the ceramics fabricated from them. Comparison of the particle size distributions in disaggregated powders and the grain size distributions in the ceramics indicates that the ceramics inherit the structure of the corresponding powders. Optimizing the synthesis conditions in order to enhance the sinterability of the powders, we obtained green compacts with the highest shrinkage rate in the range 850–950°C and shrinkage onset at 600°C, which is 100–150°C lower in comparison with powders synthesized in earlier studies from calcium nitrate and ammonium hydrogen phosphate.     

Comparing the Concentration of Calcium Hydroxide in the Diffuse Double Layer by Modeling and Experiment

Abstract

The leaching of elements from the surface of charged fly ash particles is known to be an unsteady process. The mass transfer resistance provided by the diffuse double layer has been quantified as one of the reasons for this delayed leaching. In this work, a model based on mass transfer principles for predicting the concentration of calcium hydroxide in the diffuse double layer is presented. The significant difference between predicted calcium hydroxide concentration and the experimentally measured is explained.     

The effects of simulated environmental attack on immobilization of heavy metals doped in cement-based materials

Environmental corrosion as is manifested in the form of CO₂ attack has been found to have a profound effect on the leaching characteristics of heavy metals and the microstructure of the cement binder. An external peripheral leached zone was formed, followed by a calcium carbonate-rich layer, and an intact unleached core. The heavy metals did not substitute for calcium in the calcium silicate hydrate gel, rather nickel and cadmium gradually reacted to form hydroxides. This reaction is diffusion controlled, and depends on the initial grain size distribution of the heavy metal compounds. The incorporation of metals results in a decrease of the Ca(OH)₂ content of the cement paste and increases its vulnerability to carbonation and resistance against acidic corrosion. A pH decrease to about 9 in the leached zone can account for the cadmium and nickel concentration in the leachates.     

Determination of soil nitrate and water content using attenuated total reflectance spectroscopy

Direct determination of nitrate and soil moisture can significantly improve N-application management and thus reduce N-derived environmental pollution related to agriculture. Several studies have shown that Fourier transform infrared attenuated total reflectance (FT-IR/ATR) spectroscopy could be used to estimate the nitrate content of standardized soil pastes. Paste standardization appeared to be the main obstacle to in situ application of this approach, and the present study shows how FT-IR/ATR can be used to estimate both water content and nitrate concentration of field soil samples. Water content and nitrate concentration are determined sequentially using two subsamples of the initial soil sample. An a priori determined amount of highly concentrated nitrate solution is added to the first subsample and the ATR spectrum of this paste is used to estimate the sample water content. It is then possible to calculate the amount of water that should be added to the second subsample so that the resulting paste is very close to the ideal standard paste. Nitrate concentration, mg [N]/kg [dry soil], is estimated using the FT-IR/ATR spectrum of this second paste. Results are presented for a laboratory experiment with four agricultural soils, as well as for a field trial with a calcareous soil. For water content, the determination errors range from 0.01 to 0.02 g [water]/g [dry soil]. For nitrate concentration, the errors for three of the soils range from 5.9 to 8.4 mg [N]/kg [dry soil], while for the fourth, calcareous clay soil, the determination error is 13.6 mg [N]/kg [dry soil]. The determination errors obtained for the field trial are similar to the ones obtained for a similar soil under laboratory conditions, which shows the potential usefulness of the approach for improving N-application management and reducing environmental pollution.     

Aging damage model of concrete behavior during the leaching process

This paper deals with the effect of the leaching process of cement-based materials on their mechanical properties. This process mainly induces a total leaching of Ca(OH)₂ and a progressive decalcification of the C-S-H leading in turn to a gradient of C/S ratio in the leaching zone. Modeling of the deterioration of cement paste exposed to leaching consists of a decrease in the local elastic modulus with both a damage function d and an aging function L:E=E₀ (1-d)(1-L). The main parameter fo the aging function is the residual calcium content in the material. This calcium content depends directly on the thickness of the degraded zone and on the different types of hydrates in the cement paste. The non-linearity of the mechanical behavior of the cement-based material is described by a damage function whose main state parameter is the equivalent strain. The characteristic parameters of the material are identified by a compressive loading test. The model of aging damage behavior proposed in this paper corresponds perfectly with the experimental results obtained in the case of a uniaxial compressive load.     

Damaging effects of deicing chemicals on concrete materials

The damaging impact of various deicing chemicals and exposure conditions on concrete materials was investigated. Five deicing chemicals (sodium chloride, calcium chloride with and without a corrosion inhibitor, potassium acetate, and an agricultural product) were studied. Freezing–thawing (F–T) and wetting–drying (W–D) exposure conditions were considered. Mass loss, scaling, compressive strength, chemical penetration, and micro-structure of the paste and concrete subjected to these deicing chemicals and exposure conditions were evaluated. Results indicated that the various deicing chemicals penetrated at different rates into a given paste and concrete, resulting in different degrees of damage. Among the deicing chemicals tested, two calcium chloride solutions caused the most damage. Addition of a corrosion inhibitor into the calcium chloride solution delayed the onset of damage, but it did not reduce the ultimate damage. Chloride-related deicing chemicals often brought about leaching of calcium hydroxide, as well as chemical alterations in concrete. Potassium acetate caused minor scaling, associated with alkali carbonation of the surface layer of concrete. Although producing a considerable number of micro-pores on the surface of the samples, the agricultural deicing product resulted in the least chemical penetration and scaling damage of paste and concrete.     

Zeta potential study of paste blends with slag

Electrokinetic studies of interfaces between solid phase and aqueous solution have most often been undertaken to elucidate the mechanism of adsorption and transport of different species into cementitious materials. The zeta potential is used to understand the electrokinetic properties of interfaces. In the present paper, zeta potential studies of cements and paste, with and without addition of slag, in different electrolyte solutions are carried out to understand the effect of the adsorption of charged species. The amounts of adsorbed ions are also measured to verify the results obtained by zeta potential measurement. This study shows that the cements and paste particles are negatively charged in water, sodium chloride solution, and at low concentration of calcium. At high concentration of calcium a charge inversion is observed. Thus, both calcium and chloride are potential determining ions, whereas sodium behaves as an indifferent ion. Moreover, slag particles strongly influence the surface chemistry not just of the slag but of the whole paste.     

Leaching of different elements from subbase layers of alternative aggregates in pavement constructions

The objective of this study was to analyze the accumulated effects of leaching in two test roads were municipal solid waste incineration (MSWI) bottom ash and aggregate from a railway embankment, respectively, were used as subbase aggregates. Solid samples from the subbase and the subgrade were collected in trenches, which were excavated perpendicular to the road extension. The samples were analyzed with respect to pH, water content, electrical conductivity and extractable fractions of macro and trace constituents. To conclude, spatial distribution patterns of different constituents in subbase and subgrade layers confirms the existence of two major transport processes in a road with permeable shoulders: diffusion underneath surface asphalt layers driven by a concentration gradient directed horizontally towards the shoulder of the road where the dissolved elements are carried away by advection.     

膨化硝铵固体表面自由能的计算及分析

文章通过用双认系法对膨化铵的固体表面接触角进行测定,在此基础上,应用计算模型计算其固体表面自由能,对其分析可得到表面改性较好的表面活性剂及用量,并在一定程度上揭示了膨化硝铵的表面特征。     

Durability of reactive powder composites: influence of silica fume on the leaching properties of very low water/binder pastes

Reactive Powder Composites are new cement-based materials which could be used for the storage of nuclear wastes thanks to their excellent microstructural properties. This paper studies their durability when submitted in the laboratory to a water leaching attack. In order to understand the behaviour of the hydrates (CSH), the study was carried out on a pure cement paste and on a cement + silica fume paste. The beneficial effect of silica fume is demonstrated from considerations on the calcium leaching, from XRD analysis, from SEM observations and from the tritium diffusion and pore distribution analysis. It was found that the leaching greatly affects the microstructure, especially that of the anhydrous cement grains remaining in the paste.