【作者】 朱洪波；

【导师】 马保国；

【作者基本信息】 武汉理工大学 ， 材料学， 2005， 博士

【摘要】 我国每年近10亿吨的水泥生产消耗大量资源和能源，使水泥行业的可持续发展面临严峻挑战。利用工业废渣作为水泥混合材和制备特殊功能胶凝材料是解决问题的有效途径之一，不仅节约资源、能源，减少污染，还可以利用废渣特性克服硅酸盐水泥自身缺陷。论文依托国家“863”课题《低环境负荷型水泥及胶凝材料关键制备技术》，通过开发联合激发技术，显著提高高钙灰安定性和早期活性，利用高钙灰研制出系列42.5P.C水泥、高活性混凝土掺合料和新型长效膨胀剂，并系统研究其使用性能和耐久性能。 高钙灰特性研究表明，除了组分含量波动、f-CaO含量高以外，高钙灰中粗颗粒含量高于低钙灰4倍，粗颗粒中烧失量高于细颗粒1倍以上，而CaO含量低于细颗粒25％，显著延长凝结时间，掺50％高钙原灰的复合水泥不能正常凝结。 利用煅烧磷石膏、干法电石渣、复合化学激发剂NF和机械活化等措施，研制出联合激发技术对高钙灰进行改性，使安全掺量和制备42.5P.C水泥的最高掺量均由高钙原灰的20％增加到50％。联合激发技术的化学激发机理是，煅烧石膏溶解度高及晶体结构松弛，比天然石膏的活性激发效率高，但降低石膏的缓凝作用，与天然石膏混合既可提高活性又能保持缓凝作用；干法电石渣提供碱激发，促进高钙灰中硅、铝玻璃体解聚，并克服高钙灰对凝结时间的不利影响；硫酸钠虽然早强作用明显，但使后期强度倒缩，NF使各龄期活性都得到提高；磨细的物理激发使高钙灰大颗粒中的CaO和富集碳组分被磨细、分散，活性增加而危害性降低。 首次提出“与水化程度相适应的最紧密堆积”模型概念；在现有“Stovall”数学模型基础上，通过增加“水膜厚度”等参数，推导出适用于复合水泥颗粒设计的“最紧密堆积”模型；在“次第水化”理论指导下，优化高钙灰与其他工业废渣的复合设计并制定高钙灰系列复合水泥的制备技术路线。 运用理论研究结果和联合激发技术，采用20％-30％改性高钙灰与30％-20％矿渣粉或钢渣粉在年产120万吨生产线上实现42.5P.C水泥的工业化生产；实际生产改性高钙灰混凝土掺合料2万吨，活性指数达到S95矿渣粉指标，在不降低强度前提下等量替代20％-30％水泥生产混凝土25万m~3，混凝土的工作性明显提高；实际应用获得显著经济效益。 利用高钙灰、钢渣和氟石膏含有多种膨胀源的特性开发出新型长效膨胀剂WUT，使混凝土零收缩保持时间由UEA及CAS型膨胀剂的28d左右增加到90d，更有效地克服硅酸盐水泥自身体积稳定性差的缺陷；WUT产生长效膨胀的机理是，高钙灰中的f-CaO产生钙矾石和羟钙石膨胀，钢渣中的f-CaO及MgO产生钙矾石更多还原

【Abstract】 Large of resources and energy have to be used up for about 1000 million tons cement production every year in China, which results in the serious problem about how to develop continually. To result this question, one of effective techniques is to utilize the industrial solid waste as cement admixture or cementitious with special function, which reduces not only consumes of resources and energy, but also industry pollutions else. The shortcomings of Portland cement itself can be resulted by utilizing characteristic of industrial solid waste as while as. Funded by the national 863 project, The key Techniques for Preparation of Low Environment Burthen Type of Cement and Cementitious, high calcium ash (HF) are used to produce series low environment burthen type of 42.5 P.O HF blend cement (HBC) and cementitious with special performance. Workability and durability are studied in this paper.Study results of HF characteristic show that the content of coarse grain is 4 times higher than that of fine grain, loss on ignition in coarse grain is 2 times higher than that in fine grain, the content of CaO in coarse grain is 25% less than that in thin grain, HF prolongs the setting time obviously and blend cement with 50% HF shows abnormally setting, expect high f-CaO and instability of content.Unite activating step (UA), including of calcined phosphor gypsum (CG), dry-process calcium carbide sludge (CS), composite chemical active agent NF and milling, is developed to active HF (AF) and improve the soundness. Soundness addition and max addition of 42.5P.C increase from 20%HF to 50%AF. The chemical activating mechanism of UA is that CG can stimulate pozzolanicity more effective than gypsum because of higher solubility and looser crystal structure; but CG has poor property on retardation setting, and this shortage can be solved by mixing with gypsum; CS can offer alkali activity, which can depolymerize silica and aluminum glass, and benefit for other activity methods and overcome the disadvantage of HF on setting time; Sodium sulfate improves early strength greatly but loses the final strength. NF can improve both early and final strengths. The physical mechanism of UA is that activity increases and hazardiess decreases when both of CaO and C are grineded and spreaded around.The model concept of the most compactly pile, closed to hydration degree, is brought forward first time. Basing on Stovall model, the most compactly pile model, which adapts to the designing grain of blend cement, is calculated by ways of thinking over the water film. According to the hydration sequence theory, technique and theory how to produce HBC are developed through the investigation of the hydrating rule of minerals respectively and cooperation with HF.Utilizing UA and theory study result, 2000 million tones HBC and 20 thousand tones AF are industrial produced. Activity index of AF is equal to that of S95 slag. Without strength loss, AF is carried on concrete by replacing 20%-30% cement in equal mass. HBC and AF win remarkable economic performance.Expanding agent WUT with multi-expensive source and long terms expanding, made from HF, steel slag and fluorin gypsum, is developed. Zero shrinkage keeping time of concrete delays to 90d from 28d keepped for by expanding agent UEA and CAS,更多还原