How carbonation curing influences ca leaching of Portland cement paste: Mechanism and mathematical modeling

Carbonation curing provides a promising method for both CO₂ sequestration and strength improvement of cement-based materials. To date, there is little knowledge about the influence of carbonation curing on Ca leaching resistance of cement-based materials due to the occurrence of both physical and chemical transformation. It was the first time that Ca solid-liquid equilibrium curves were experimentally established for cement pastes with different carbonation degrees in this paper. Experimental results demonstrated that on the one hand, carbonation curing improves the leaching resistance of cement paste by sequestrating Ca in insoluble CaCO₃; on the other hand, potential negative effects may occur due to the accelerated decalcification and increased solubility of C–S–H after carbonation curing. Results of NMR showed that both carbonation curing and Ca leaching can increase the Si chain length and polymerization degree of C–S–H. Additionally, a modified mathematical model was established to simulate the leaching process of carbonation-cured cement paste and it was also verified by energy-dispersive spectroscopy (EDS) results. Therefore, the long-term leaching resistance of cement-based materials is possibly degraded by the carbonation curing treatment.     

水泥的碳酸化工艺研究

通过设计正交实验,测定碳酸化水泥复合胶凝材料与纯水泥的水化产物及观察硬化浆体的微观形貌,研究了水泥的碳酸化工艺条件。结果表明：碳酸化水泥复合胶凝材料3d、28d的抗压强度普遍高于纯水泥,且强度等级由42．5提高至52．5;水量、碳酸化温度对碳酸化复合胶凝材料3d抗压强度有显著影响,且水量的影响作用较大;水泥的碳酸化最佳工艺条件为水量：0．2％、CO2压力：0．2MPa、碳酸化温度：25℃、碳酸化时间：30min;复合胶凝材料3d水化产物中有CaCO3微晶析出,28d水化产物中有较多的碳铝酸钙生成。     

Application of the random pore model to the carbonation cyclic reaction

Calcium oxide has been proved to be a suitable sorbent for high temperature CO₂ capture processes based on the cyclic carbonation‐calcination reaction. It is important to have reaction rate models that are able to describe the behavior of CaO particles with respect to the carbonation reaction. Fresh calcined lime is known to be a reactive solid toward carbonation, but the average sorbent particle in a CaO‐based CO₂ capture system experiences many carbonation‐calcination cycles and the reactivity changes with the number of cycles. This study applies the random pore model (RPM) to estimate the intrinsic rate parameters for the carbonation reaction and develops a simple model to calculate particle conversion with time as a function of the number of cycles, partial pressure of CO₂, and temperature. This version of the RPM model integrates knowledge obtained in earlier works on intrinsic carbonation rates, critical product layer thickness, and pore structure evolution in highly cycled particles. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

铬酸钠碳化反应动力学研究

研究了铬酸钠碳化反应动力学,在1个2 L反应釜内,通过监测反应过程中CO2压力的变化,计算反应速率,避免了因逆反应过快造成的溶液取样分析的困难。实验发现反应速率有一个下降-升高-下降的变化过程。通过反应机理分析,导出了动力学方程,并根据动力学方程较好地解释了实验现象。     

Accelerated carbonation of Friedel's salt in calcium aluminate cement paste

The stability of Friedel's salt with respect to carbonation has been studied in calcium aluminate cement (CAC) pastes containing NaCl (3% of Cl⁻ by weight of cement). Carbonation was carried out on a powdered sample in flowing 5% CO₂ gas at 65% relative humidity to accelerate the process. At an intermediate carbonation step, a part of the sample was washed and dried up to 10 cycles to simulate a dynamic leaching attack. The two processes were followed by means of X-ray diffraction (XRD), pH and Cl⁻ analyses in the simulated pore solution.     

Impact of accelerated carbonation on OPC cement paste blended with fly ash

Cement is a huge carbon dioxide producer. Supplementary cementitious materials can help reduce this outcome. However, carbonation of these blended cements remains an active subject of research. Accelerated carbonation tests (10% CO₂, 25 °C and 62% RH) are performed on fly ash blended cement pastes. Experiments are performed at varying ages of carbonation (1 to 16 weeks) to measure the evolution of the carbonation depth over time and to quantify key parameters: thermogravimetric analysis (TGA), mercury intrusion porosimetry (MIP) and gamma ray attenuation method (GRAM). The total porosity decreases with a rearrangement of the microstructure due to carbonation and the creation of big capillary pores for the paste with the highest contents of fly ash (60 vol.%). The C-S-H molar volume evolution during fly ash-blended cement carbonation is calculated using a method combining MIP, TGA and GRAM formerly successfully applied to OPC paste in a paper published in the same journal.     

Accelerated carbonation of cement pastes in situ monitored by neutron diffraction

In-situ monitoring of the changes that take place in the phase composition of cement pastes during accelerated carbonation (100% CO₂) for different binders, has been carried out, by taking Neutron Diffraction patterns in parallel with the carbonation experiments. The variation of the intensity of chosen reflections for each phase along the experiment has been used to monitor concentration changes and has supplied data, in real time, for fractional conversion of different phases (Portlandite, Ettringite and CSH gel) of the hydrated cement pastes. Fitting of these results has allowed to make a qualitative approach to the kinetics of the carbonation of the different phases and extracting conclusions on the microstructural changes that takes place during the carbonation of cement pastes.     

碳酸锂碳化反应过程分析与机理探讨

用双膜理论揭示了碳酸锂气、液、固三相碳化反应的规律.从化学反应动力学和工程学的角度,分析了碳化反应的过程并对反应的机理进行了探讨,对实验结果进行了理论解释,为优化工艺参数提供了理论依据,对实际生产也具有一定的参考价值.     

Effect of alkalis on alumina refractories in cement rotary kilns

Causes of failure of the refractory lining of a cement rotary kiln are investigated for specimens taken from the preliminary firing and decarbonizing zone. It is established that at temperatures above 1400°C sodium-aluminum silicates are formed on the hot surface of the refractories and an increased content of alkali leads to the formation of compounds of the feldspar group.Translated from Ogneupory, No. 6, pp. 21–25, June, 1995.     

利用碳酸化动力学研究确定Mg（OH）2中残余氯的存在形式

通过碳酸化反应对Ｍｇ（ＯＨ）２中残余氯的溶出动力学进行了研究，得到两种显著不同的表观活化能，可定量、简便地确定杂质氯的存在形式，为氯化镁溶液通氨法生产试剂级Ｍｇ（ＯＨ）２工艺条件的选择提供了理论依据。     

纳米CaCO3孔径调控及其对碳酸化反应性能的影响

研究了纳米CaCO₃颗粒间孔径调控对CaO与CO₂碳酸化反应性能的影响。通过有机模板法制备得到一系列比表面积相近、孔径分布不同的纳米CaCO₃,并考察其再生和碳酸化反应性能差异。结果表明：增大平均孔径能促进纳米CaCO₃的热分解反应,并降低分解温度约15℃。将平均孔径由15 nm增大至113 nm可显著提高碳酸化反应速率和转化率。研究认为平均孔径和比表面积对碳酸化反应转化率的影响存在交互作用;比表面积小的纳米CaCO₃,表现出碳酸化反应转化率受扩散控制影响较大,而比表面积较大的表现为碳酸化反应转化率以表面反应影响控制为主的规律。     

Dynamics of the internal reaction layer arising during carbonation of concrete

Carbonation is the reaction of environmental carbon dioxide with alkaline species in concrete. It is one of the major degradation mechanisms affecting the durability of reinforced concrete structures. In this paper, a mathematical model of the carbonation process is formulated and simulated using the finite-element method. Nonlinear reaction rates, Robin boundary conditions and a decrease of the concrete porosity in time are taken into account. A dimensional analysis based on a nondimensionalisation of the entire model is introduced to identify the key parameters and the different characteristic time and length scales of the whole process. Numerical simulations show the occurrence of an internal reaction layer travelling through the material. The speed and the width of the layer are rigorously defined via dimensionless quantities. A parameter study shows that the speed and the width are strongly related to the size of the Thiele modulus which is typically large. The relevance of other parameters is also investigated. The model is validated for accelerated and natural carbonation settings.     

Effect of carbonation on microstructural properties of cement stone

The carbonation of concrete is an ever-present phenomenon affecting the properties of concrete in various ways. In this paper different aspects of the effect of carbonation on the properties of cement stone have been briefly discussed on the basis of experimental results, the central part of which is the thermogravimetric analysis of CO₂ and H₂O content in cement stone samples kept at different humidities.     

ESEM analysis of polymeric film in EVA-modified cement paste

Portland cement pastes modified by 20% weight (polymer/cement ratio) of poly(ethylene-co-vinyl acetate) (EVA) were prepared, cured, and immersed in water for 11 days. The effects of water saturation and drying on the EVA polymeric film formed in cement pastes were observed using environmental scanning electron microscopy (ESEM). This technique allowed the imaging of the EVA film even in saturated samples. The decrease of the relative humidity inside the ESEM chamber did not cause any visual modification of the polymeric film during its drying.     

SiO2凝胶/铝硅纤维复合材料的高温损坏机理研究

本文采用浸渍法制备了SiO2凝胶/铝硅纤维复合材料,通过分析材料的热失重-差示扫描热、微观形貌、物相组成及热传导等特性,得出了复合材料高温损坏机理.研究结果表明,SiO2凝胶/铝硅纤维复合材料相对于硅铝纤维,析晶温度可提高200℃;随着热处理温度由900℃升至1200℃,复合材料的气孔率由55％升至75％,体积密度由0.85 g/cm3降至0.45 g/cm3,导热系数由0.0767 W/(m·K)增至0.0908 W/(m·K),压缩回弹率由90％降至43％;当热处理温度达到1200℃,复合材料的力学性能损坏,主要原因是莫来石和方石英的析晶,以及硅凝胶与纤维之间的粘结失效.     

Effect of synthesis procedure on carbonation of calcium‐silicate‐hydrate

Carbonation of synthesized calcium‐silicate‐hydrate (C–S–H) is difficult to avoid and can have significant impact on the molecular structure. Considerable carbonation was observed in C–S–H synthesized from the double decomposition of sodium silicate and calcium nitrate solutions but not in C–S–H synthesized from the direct reaction of fumed silica and calcium hydroxide solution. In order to isolate the cause of the greater carbonation in C–S–H synthesized by double decomposition, carbonation was induced in phase‐pure C–S–H by reaction with four different water‐based solutions containing dissolved CO₂ with varying pH and alkali content. Powder X‐ray diffraction, thermogravimetric analysis, and ²⁹Si nuclear magnetic resonance were used to probe the carbonation and the resulting changes in molecular structure. The pH of the solution was seen to strongly influence the degree of carbonation, while the alkali content had much less effect.     

白云灰乳碳酸化工艺研究

中国白云石蕴藏量巨大,白云灰乳碳酸化是白云石碳化法制备轻质碳酸镁、氧化镁等镁化合物的关键步骤之一,关系到镁的产率、产品中钙的含量及生产成本。通过单因素实验和正交实验,研究了碳酸化过程镁的溶出率及重镁水中的钙含量与碳酸化反应温度、反应终点pH、白云灰乳质量浓度的关系,从而为提高碳酸化过程镁的溶出率,实现钙镁的有效分离提供可靠的依据。研究表明：影响镁的溶出率及重镁水中钙含量的主要因素为pH。白云灰乳碳酸化最佳工艺条件：白云灰乳质量浓度为9.00 g/L（以氧化镁计）,反应温度为30 ℃,反应终点pH为7.50。在此条件下镁的溶出率为74.49%,重镁水中钙的质量浓度为0.10 g/L。     

生产轻质碳酸镁的碳酸化工艺试验

探讨了白云石碳酸化法生产轻质碳酸镁过程中碳酸化反应机理，通过碳酸化工艺试验，优选出较合理的碳酸化工艺条件，即：第一步碳酸化在常压下进行，消化浆液中氧化镁浓度控制在30－50g/L，第二步碳酸化在加压状态下进行，压力控制在0．30MPa以上，温度控制在35℃以下，浆液中氧化镁浓度控制在10－12g/L，碳酸化反应时间为50min。     

白云石的灰乳碳酸化工艺条件初探

本文在模拟碳化塔中用人工模拟窑气成分，对由白云石制灰乳碳化制取重镁水的工艺条件进行了研究，讨论了灰乳中的液固比在不同气体组成下对MgO提取率的影响，确定了MgO提取率最大时液固比为40：1，窑气中CO2的体积分数为30％。并为提高MgO的提取率寻找到合适的添加剂DETA，得出与未加添加剂相比，在相同碳化条件下，相应提取率提高了16．77％。     

熟料细度对粉煤灰水泥浆体强度和自收缩的影响

通过实验室球磨机制备出比表面积分别为280m2/kg、370m2/kg和670m2/kg的3种水泥熟料,与不同掺量的粉煤灰配制成不同颗粒级配的粉煤灰水泥,并测试了粉煤灰水泥浆体的抗压强度、自收缩、孔隙率和显微结构。结果表明：提高熟料细度能在很大程度上降低粉煤灰水泥浆体的孔隙率并提高复合水泥浆体早期抗压强度;粉煤灰的掺入降低了水泥体系的自收缩,提高了粉煤灰水泥浆体的体积稳定性;粉煤灰水泥浆体背散射图像表明,提高熟料细度可显著减少粉煤灰水泥浆体中未水化的水泥颗粒含量,并在一定程度上减少未水化粉煤灰颗粒含量。