活化煤矸石及其胶砂混凝土对钢筋腐蚀行为的影响研究
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摘要
煤矸石作为煤炭行业排放量最大的固体废弃物,其综合利用已经成为亟待解决的重要问题。其中利用煤矸石制备硅铝基胶凝材料是实现其大规模综合利用的有效途径。作为一种合格的胶凝材料仅仅满足其活性,是远远不够的。耐久性尤其是钢筋腐蚀性能也是决定其能否大规模综合利用的重要指标,本文以北京房山煤矸石为研究对象,在研究其活性优化规律的基础上,揭示了活化煤矸石对钢筋腐蚀行为的影响规律和影响机理。
本文研究了简单热活化及复合热活化对北京房山煤矸石胶凝活性的影响规律,优化了其火山灰活性,并揭示了煤矸石活性提高的机理。在核磁共振(NMR)分析的基础上,提出采用相对桥氧数(RBO)指标来表征活化煤矸石中[SiO_4]聚合度,发现煤矸石的硅氧多面体聚合度在活化过程中明显降低,而水化过程则聚合度升高,并且[SiO_4]聚合度与胶凝活性之间存在较好的负相关性。
通过对比研究普通水泥以及活化煤矸石硬化体中模拟孔溶液的成分差异,并通过模拟不同孔溶液的离子种类及浓度特点,有针对性的研究了钢筋在模拟孔溶液中的腐蚀行为,揭示了不同离子对钢筋腐蚀行为的影响规律。钢筋在煤矸石胶凝材料硬化体中的腐蚀电位明显高于普通水泥,表明其耐腐蚀性能较好。ACI分析表明煤矸石胶凝材料中表征混凝土的电阻R_c明显增加是导致其腐蚀电位升高的主要原因。
活化煤矸石能够显著提高胶凝材料在水化过程中的氯离子固化能力,并且氯离子的固化率随着煤矸石掺量的增加而有所增加;在煤矸石活化过程中加入少量磷酸盐,可以与体系中的氯离子结合,生成难溶于水的氯代磷灰石,从而进一步提高对原料中原有的氯离子的固化量。(31)~P的NMR分析表明,(31)~P在水化过程中可以与体系中的硅氧多面体和铝氧多面体一起形成超磷酸盐结构,这有利于形成稳定的架状结构。孔结构仍然是影响氯离子的迁移速率的主要因素,但煤矸石自身对氯离子的良好固化性能有利于降低氯离子的扩散系数。
利用传统的水泥生产线开展了煤矸石胶凝材料的工业化生产试验,生产出了3000吨煤矸石胶凝材料。并利用煤矸石胶凝材料,对房山双山水泥厂的道路进行硬化,为煤矸石的大规模工业化应用,提供借鉴。
Coal gangue is a complex industrial solid waste of coal industry. Comprehensive utilization of coal gangue has already become an important problem to be solved urgently. Gangue is used for preparation construction materials which have good prospects for comprehensive utilization. Current research is focused mainly on improving cementitious activity. However, the cementitious activity is currently insufficient for these materials to qualify as suitable for use in construction. Durability problems, especially the corrosion of reinforcement steel, limit the large-scale application of this byproduct in construction materials. Coal gangue from Beijing Fangshan was studied in this paper. Pozzolanic activity of coal gangue and reinforcement corrosion behavior in coal gangue-based mortars was analyzed to provide a reference for further extensive utilization of gangue in the field of building cementitious materials.
In order to optimize the pozzolanic activity of coal gangue, the influence of simple calcination and co-calcination method on pozzolanic activity of coal gangue was studied, and pozzolanic activity optimization was achieved. Mechanism of activity optimization was investigated. Based on MAS NMR analysis technology, we proposed the concept of relative number of bridging oxygen (RBO) to evaluate [SiO_4] polymerization. It is found that [SiO_4] polymerization of coal gangue decreased during the aactivation process, while increase during the hydration process. There is obvious inverse correlation between RBO and cementitious activity.
According to the difference of pore solution component between OPC and coal gangue based pastes, the corrosion behavior of steel bar in simulated pore solution was studied. The influence of ions in pore solution on corrosion behavior was analyzed. It is shown that the corrosion potential of reinforcement in coal gangue cementitious mortar is much higher than that in OPC which is mainly due to higher concrete resistance R_c from ACI analysis.
The solidification for chloride is higher in coal gangue cementitious mortar than in OPC mortar. The solidification rate of chloride ion increased with coal gangue admixture. Phosphate improve solidification rate of chloride ion consolidate further during the activation process of coal gangue which benefit from chlorapatite product. (31)~P NMR results showed that (31)~P combine with silicon-oxide polyhedron and aluminum-oxygen polyhedron to form super phosphate structure. This is helpful to stable frame structure construction in mortar.
The principal factor which affects diffusion rate of chloride ion is pore structure. Coal gangue has good solidification properties for chloride ion,which is helpful to decline the diffusion coefficient of chloride ion.
Commercial experiments on production of coal gangue cementitious materials by co-calcination method were carried out at a clinker production line with capacity of 1200 tons per day. The experimented products has been used in construction of road works.
本文研究了简单热活化及复合热活化对北京房山煤矸石胶凝活性的影响规律,优化了其火山灰活性,并揭示了煤矸石活性提高的机理。在核磁共振(NMR)分析的基础上,提出采用相对桥氧数(RBO)指标来表征活化煤矸石中[SiO_4]聚合度,发现煤矸石的硅氧多面体聚合度在活化过程中明显降低,而水化过程则聚合度升高,并且[SiO_4]聚合度与胶凝活性之间存在较好的负相关性。
通过对比研究普通水泥以及活化煤矸石硬化体中模拟孔溶液的成分差异,并通过模拟不同孔溶液的离子种类及浓度特点,有针对性的研究了钢筋在模拟孔溶液中的腐蚀行为,揭示了不同离子对钢筋腐蚀行为的影响规律。钢筋在煤矸石胶凝材料硬化体中的腐蚀电位明显高于普通水泥,表明其耐腐蚀性能较好。ACI分析表明煤矸石胶凝材料中表征混凝土的电阻R_c明显增加是导致其腐蚀电位升高的主要原因。
活化煤矸石能够显著提高胶凝材料在水化过程中的氯离子固化能力,并且氯离子的固化率随着煤矸石掺量的增加而有所增加;在煤矸石活化过程中加入少量磷酸盐,可以与体系中的氯离子结合,生成难溶于水的氯代磷灰石,从而进一步提高对原料中原有的氯离子的固化量。(31)~P的NMR分析表明,(31)~P在水化过程中可以与体系中的硅氧多面体和铝氧多面体一起形成超磷酸盐结构,这有利于形成稳定的架状结构。孔结构仍然是影响氯离子的迁移速率的主要因素,但煤矸石自身对氯离子的良好固化性能有利于降低氯离子的扩散系数。
利用传统的水泥生产线开展了煤矸石胶凝材料的工业化生产试验,生产出了3000吨煤矸石胶凝材料。并利用煤矸石胶凝材料,对房山双山水泥厂的道路进行硬化,为煤矸石的大规模工业化应用,提供借鉴。
Coal gangue is a complex industrial solid waste of coal industry. Comprehensive utilization of coal gangue has already become an important problem to be solved urgently. Gangue is used for preparation construction materials which have good prospects for comprehensive utilization. Current research is focused mainly on improving cementitious activity. However, the cementitious activity is currently insufficient for these materials to qualify as suitable for use in construction. Durability problems, especially the corrosion of reinforcement steel, limit the large-scale application of this byproduct in construction materials. Coal gangue from Beijing Fangshan was studied in this paper. Pozzolanic activity of coal gangue and reinforcement corrosion behavior in coal gangue-based mortars was analyzed to provide a reference for further extensive utilization of gangue in the field of building cementitious materials.
In order to optimize the pozzolanic activity of coal gangue, the influence of simple calcination and co-calcination method on pozzolanic activity of coal gangue was studied, and pozzolanic activity optimization was achieved. Mechanism of activity optimization was investigated. Based on MAS NMR analysis technology, we proposed the concept of relative number of bridging oxygen (RBO) to evaluate [SiO_4] polymerization. It is found that [SiO_4] polymerization of coal gangue decreased during the aactivation process, while increase during the hydration process. There is obvious inverse correlation between RBO and cementitious activity.
According to the difference of pore solution component between OPC and coal gangue based pastes, the corrosion behavior of steel bar in simulated pore solution was studied. The influence of ions in pore solution on corrosion behavior was analyzed. It is shown that the corrosion potential of reinforcement in coal gangue cementitious mortar is much higher than that in OPC which is mainly due to higher concrete resistance R_c from ACI analysis.
The solidification for chloride is higher in coal gangue cementitious mortar than in OPC mortar. The solidification rate of chloride ion increased with coal gangue admixture. Phosphate improve solidification rate of chloride ion consolidate further during the activation process of coal gangue which benefit from chlorapatite product. (31)~P NMR results showed that (31)~P combine with silicon-oxide polyhedron and aluminum-oxygen polyhedron to form super phosphate structure. This is helpful to stable frame structure construction in mortar.
The principal factor which affects diffusion rate of chloride ion is pore structure. Coal gangue has good solidification properties for chloride ion,which is helpful to decline the diffusion coefficient of chloride ion.
Commercial experiments on production of coal gangue cementitious materials by co-calcination method were carried out at a clinker production line with capacity of 1200 tons per day. The experimented products has been used in construction of road works.
引文
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