碱激发碳酸盐矿胶凝-灌浆材料的研究
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摘要
节约资源和能源,保护生态环境,提高耐久性是建筑材料工业实现可持续发展的三大要素,而传统无机胶凝材料——硅酸盐水泥的生产带来了日趋严峻的环境和资源问题,因此,利用低品位、边缘性资源研制开发新型胶凝材料具有重要的战略意义。本文率先在国内外开展碱激发碳酸盐矿凝胶-灌浆材料的研究,对这种新型胶凝材料的反应热力学、反应影响因素、反应产物、结构形成机理和原材料的选择与加工进行了深入探讨,并就碱激发碳酸盐矿灌浆材料的制备方法、性能及其影响因素进行了系统的试验研究,在此基础上完成了实验室模拟灌浆试验。
反应热力学研究表明,常温下碳酸盐矿与碱硅酸钠溶液可以反应生成水合硅酸钙(镁)胶凝产物。反应动力学研究表明,碳酸盐矿组成、碳酸盐矿中白云石的结晶度和晶体尺寸,碱硅溶液的SiO_2/Na_2O 摩尔比、浓度和pH 值以及温度影响反应速率和反应程度。当选用MgO 含量为10~20%,并粉磨至小于5μm的颗粒达80%以上的碳酸盐矿粉与模数为1.6~2.0,波美度为40 左右(此时pH值为13~13.5)的碱硅溶液,可以加快反应,获得具有一定胶凝强度的碱激发碳酸盐矿胶凝材料。
确定碱硅溶液与高镁碳酸盐矿粉的反应产物对这种新型胶凝材料的研究开发具有重要意义,但由于反应产物为无定形凝胶,仅用单一的常规的测试分析方法难以确定其组成和结构,本文采用扫描电镜分析(SEM),X 射线光电子能谱元素定量分析(XPS),红外光谱分析(IR),X 射线衍射分析(XRD),差热分析(DTA),固体高分辨核磁共振分析((29)~Si NMR MAS 谱)等多种微观测试分析手段对反应产物进行了联合分析,确定了碱硅溶液与高镁碳酸盐矿粉的反应产物主要是水合硅酸钙(镁)凝胶和一定数量的硅凝胶,并确定水合硅酸钙(镁)凝胶的组成和结构是蛇纹石型的水合硅酸镁和白钙沸石型的水合硅酸钙。
研究了碱激发碳酸盐矿用作灌浆材料的可能性。结果表明,浆液粘度可调,稳定性好,可灌性较好,可实现单液灌浆;浆液凝胶时间在5~20 小时范围,结石体和固砂体28 天抗压强度为1~4MPa,并随时间延长强度持续增长,满足灌浆材料要求;固砂体抗渗透性能达到防水砂浆标准的要求。
探讨了碱激发碳酸盐矿灌浆材料的适用范围,认为该灌浆材料尤其适用于地层固砂固土和软基加固灌浆,据此作者设计了相应的浆液制备和灌浆施工连续化的工艺。按渗透灌浆理论在实验室进行了碱激发碳酸盐矿灌浆材料模拟地层固砂的可灌性研究和灌浆试验,完成了这种新型灌浆材料迈向工程化的初步
Saving resources and energy, protecting ecological environment, and improvingdurability are the three primary essentials for sustainable development of buildingmaterial industry. Because the production of traditional cementitiousmaterial-Portland cement, has led to increasingly severe environmental deteriorationand resource problems, it is of strategic meaning to develop new types ofcementitious materials using “low-grade”raw materials. In this paper, a initiativeresearch of the “Alkali-Activated-Carbonatites Cementitious Materials (AACCM)for grouting engineering was presented, in which, the reaction thermodynamics, thereaction products, the mechanism of structure formation, the influence factors, andselection and manufacture of raw materials were studied in detail. Besides, themanufacture process, the properties and performance, and the influence factors ofAACCM were also studied. A simulated grouting experiment was carried out basedon the systematic work above.
Thermodynamics investigation indicate that the reaction between carbonatiteand sodium silicate solution, forming hydration calcium (magnesium) silicate gel,can occur at normal temperature. Kinetics studies show that the rate and degree ofthe reaction are influenced by several factors: the composition of carbonatites, thecrystallinity and crystal size of dolomite in carbonatites, the mole ratio of SiO2/Na2O,the concentration and pH value of sodium silicate solution and the reactiontemperature, etc. When some specific carbonatites, with MgO content ranging from10 to 20% and the particle portion of less than 5μm diameter taking up over 80%,was selected to react with certain industrial water-glass, which was modified andwith modulus ranging between 1.6 and 2.0, Baume degree being about 40, pH valuevarying from 13 to 13.5, the reaction could be accelerated and AACCM with certainstrength was obtained.
It is of important significance to determine the reaction products of sodiumsilicate solution and carbonatites reaction for this new type of cementitious material.But it is very difficult to ascertain these amorphous products with only one anyanalyze and characterization techniques. Therefore, using the combination of SEM,XPS (X-ray photoelectron spectroscopy for element quantitative analysis), IR, XRD,DTA and (29)~Si NMR ((29)~Si nuclear magnetic resonance) to analyze the reaction
反应热力学研究表明,常温下碳酸盐矿与碱硅酸钠溶液可以反应生成水合硅酸钙(镁)胶凝产物。反应动力学研究表明,碳酸盐矿组成、碳酸盐矿中白云石的结晶度和晶体尺寸,碱硅溶液的SiO_2/Na_2O 摩尔比、浓度和pH 值以及温度影响反应速率和反应程度。当选用MgO 含量为10~20%,并粉磨至小于5μm的颗粒达80%以上的碳酸盐矿粉与模数为1.6~2.0,波美度为40 左右(此时pH值为13~13.5)的碱硅溶液,可以加快反应,获得具有一定胶凝强度的碱激发碳酸盐矿胶凝材料。
确定碱硅溶液与高镁碳酸盐矿粉的反应产物对这种新型胶凝材料的研究开发具有重要意义,但由于反应产物为无定形凝胶,仅用单一的常规的测试分析方法难以确定其组成和结构,本文采用扫描电镜分析(SEM),X 射线光电子能谱元素定量分析(XPS),红外光谱分析(IR),X 射线衍射分析(XRD),差热分析(DTA),固体高分辨核磁共振分析((29)~Si NMR MAS 谱)等多种微观测试分析手段对反应产物进行了联合分析,确定了碱硅溶液与高镁碳酸盐矿粉的反应产物主要是水合硅酸钙(镁)凝胶和一定数量的硅凝胶,并确定水合硅酸钙(镁)凝胶的组成和结构是蛇纹石型的水合硅酸镁和白钙沸石型的水合硅酸钙。
研究了碱激发碳酸盐矿用作灌浆材料的可能性。结果表明,浆液粘度可调,稳定性好,可灌性较好,可实现单液灌浆;浆液凝胶时间在5~20 小时范围,结石体和固砂体28 天抗压强度为1~4MPa,并随时间延长强度持续增长,满足灌浆材料要求;固砂体抗渗透性能达到防水砂浆标准的要求。
探讨了碱激发碳酸盐矿灌浆材料的适用范围,认为该灌浆材料尤其适用于地层固砂固土和软基加固灌浆,据此作者设计了相应的浆液制备和灌浆施工连续化的工艺。按渗透灌浆理论在实验室进行了碱激发碳酸盐矿灌浆材料模拟地层固砂的可灌性研究和灌浆试验,完成了这种新型灌浆材料迈向工程化的初步
Saving resources and energy, protecting ecological environment, and improvingdurability are the three primary essentials for sustainable development of buildingmaterial industry. Because the production of traditional cementitiousmaterial-Portland cement, has led to increasingly severe environmental deteriorationand resource problems, it is of strategic meaning to develop new types ofcementitious materials using “low-grade”raw materials. In this paper, a initiativeresearch of the “Alkali-Activated-Carbonatites Cementitious Materials (AACCM)for grouting engineering was presented, in which, the reaction thermodynamics, thereaction products, the mechanism of structure formation, the influence factors, andselection and manufacture of raw materials were studied in detail. Besides, themanufacture process, the properties and performance, and the influence factors ofAACCM were also studied. A simulated grouting experiment was carried out basedon the systematic work above.
Thermodynamics investigation indicate that the reaction between carbonatiteand sodium silicate solution, forming hydration calcium (magnesium) silicate gel,can occur at normal temperature. Kinetics studies show that the rate and degree ofthe reaction are influenced by several factors: the composition of carbonatites, thecrystallinity and crystal size of dolomite in carbonatites, the mole ratio of SiO2/Na2O,the concentration and pH value of sodium silicate solution and the reactiontemperature, etc. When some specific carbonatites, with MgO content ranging from10 to 20% and the particle portion of less than 5μm diameter taking up over 80%,was selected to react with certain industrial water-glass, which was modified andwith modulus ranging between 1.6 and 2.0, Baume degree being about 40, pH valuevarying from 13 to 13.5, the reaction could be accelerated and AACCM with certainstrength was obtained.
It is of important significance to determine the reaction products of sodiumsilicate solution and carbonatites reaction for this new type of cementitious material.But it is very difficult to ascertain these amorphous products with only one anyanalyze and characterization techniques. Therefore, using the combination of SEM,XPS (X-ray photoelectron spectroscopy for element quantitative analysis), IR, XRD,DTA and (29)~Si NMR ((29)~Si nuclear magnetic resonance) to analyze the reaction
引文
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