水泥超胶凝化理论及技术研究

发布时间：2018-05-08 18:35

本文选题：超胶凝 + 微研磨介质　；参考：《武汉理工大学》2014年博士论文

【摘要】：在普通硅酸盐水泥基础上，面向低水胶比、高流态的现代混凝土要求，建立水泥超胶凝化的低能耗、在线设计方法及技术体系。其目的是解决现代混凝土要求与通用技术存在的重大问题：混凝土中存在20%~40%的未充分水化的水泥，其胶凝效率不能充分发挥；当水胶比低于0.437时，不能完全水化的水泥熟料，仅作为骨料填充而造成巨大的浪费；未水化的水泥会在混凝土的界面过渡区产生氢氧化钙富集，导致混凝土耐久性恶化等。基于上述问题，本文提出了一种全新的面向混凝土应用的水泥在线加工理论和技术。依托国家973重点基础研究发展规划和国家自然科学基金（51178363）等项目，基于颗粒整形与精修、级配调控与优化、表面改性与电荷平衡等技术，针对水泥的低碳制备、表面改性和胶凝效率的提升进行系统研究。通过水泥进行加工，提高水泥的胶凝效率，减少高资源、能源消耗和高碳排放的水泥熟料的用量，改善混凝土界面过渡区，提升混凝土耐久性。本文主要成果和创新点如下： 1、基于粒度分布函数和分形理论，突破传统粉磨效率低、能耗高的问题，建立面向混凝土应用的水泥低能耗在线加工制备技术。突破粉磨效率低、大部分能耗转化为热量散失的传统粉磨方式，创造性的提出采用微研磨介质（M）对普通硅酸盐水泥（C）进行加工，，建立面向混凝土应用的低能耗水泥超胶凝化系统理论和关键技术。基于正态、对数、高登-舒曼、罗逊-莱蒙勒分布函数和粒度分形维数理论，采用两种粉磨方式，对三种物料体系（C、M和CM）的颗粒粒径（频度分布和累计分布）、特征参数（D50、D10、D25、D75和D90）和粒度分形维数D进行系统研究，建立高效率、低能耗水泥超胶凝化的理论基础。实验条件下，当颗粒粒径D50为8um时，与采用传统粉磨技术处理普通水泥相比，添加5%的M处理10min和添加20%的M处理5min，单位质量粉磨能耗分别降低29.83%和58.33%；当颗粒粒径D50为7um时，添加20%的M处理10min和添加30%的M处理5min，单位质量粉磨能耗分别降低37.50%和64.29%。 2、基于IPP图像技术、分形原理和电子层理论等理论，面向低水胶比、高流态混凝土要求，针对水泥颗粒粒径减小，团聚加剧的问题，建立水泥超胶凝化表面改性和调控技术。通过不同种类和掺量的表面改性剂等处理，对水泥浆体的絮凝结构的分形维数、颗粒表面电位和流变性能进行调控。实验条件下，超胶凝水泥浆体的分形维数1.2~1.4，水化60min的ζ电位-60mW~-30mW，，剪切速率为100r/s-1时，剪切应力320pa~500pa，黏度4.00pa·s~5.00pa·s。而普通水泥的分形维数为1.4632，剪切速率为100r/s-1时，水化60min的ζ电位为-0.89mW，剪切应力为579.27pa，黏度为9.45pa·s。超胶凝水泥分形维数减少，ζ电位电负性增加，剪切应力减小，黏度降低，为其应用于低水胶比、高流态、高强和高耐久性的现代混凝土奠定理论基础。通过对超胶凝水泥表面改性和调控，建立水泥颗粒分形维数-ζ电位-流变性能模型，形成水泥分散技术与理论基础，建立快速评价和分析颗粒分散程度的方法。 3、基于超胶凝水泥的水化产物、水化程度和界面过渡区特征，建立超胶凝水泥水化理论与模型，为超胶凝水泥应用于高强和高耐久性的现代混凝土奠定理论基础。采用XRD、SEM和DTA-TG等手段，分析超胶凝水泥在不同龄期、不同水胶比的水化特征和水化程度，建立超胶凝水泥水化理论与模型。与普通水泥相比，同等实验条件下，超胶凝水泥在水化1d的水化程度明显提高19.05%，水化3d的水化程度提高22.04%，水化180d的水化程度提高达20%以上。超胶凝水泥水化产物结构更加致密，水化产物中Ca(OH)2的特征衍射峰峰值强度增加，水化产物的失重量明显增多。与普通水泥相比，实验条件下超胶凝水泥的界面过渡区的硬度提高20.95%，尺寸减小24.14%，浆体的硬度提高14.29%，水化产物结构更致密，Ca(OH)2富集现象减少，为其应用于混凝土提高强度和耐久性奠定理论基础。 4、研究超胶凝水泥的在不同体系的混凝土的应用效果，建立面向混凝土的系统体系和关键技术，奠定超胶凝水泥应用和推广的理论基础。研究超胶凝水泥的在不同体系的混凝土的应用效果，建立面向混凝土应用的系统体系和关键技术。力学性能相当的情况下，单位体积混凝土中，采用超胶凝水泥和矿粉取代普通水泥，超胶凝水泥掺量为8.33%，水泥用量减少30.00%；采用超胶凝水泥和粉煤灰取代普通水泥，超胶凝水泥掺量为16.67%，水泥用量减少25.00%；采用超胶凝水泥、粉煤灰和矿粉取代普通水泥，超胶凝水泥掺量为8.33%，水泥用量减少30.00%。研究并分析超胶凝水泥的工业化应用的物料流平衡，并绘制工业化应用流程图，奠定超胶凝水泥应用和推广的理论基础和关键技术。
[Abstract]:On the basis of ordinary portland cement, the modern concrete requirements for low water glue ratio and high flow state are required to establish low energy consumption, on-line design method and technical system for cement super gel condensation. The purpose is to solve the major problems existing in modern concrete requirements and general technology: concrete in concrete with insufficient hydration of 20%~40%, and its gelation The efficiency can not be fully utilized; when the water to glue ratio is less than 0.437, the cement clinker that can not be completely hydrated is a huge waste only as the aggregate filling; the unhydrated cement will lead to the enrichment of calcium hydroxide in the transition zone of the concrete interface, which leads to the deterioration of the durability of concrete.
Based on the above problems, this paper puts forward a new theory and technology of cement on-line processing for concrete applications. Relying on the national 973 key basic research development planning and National Natural Science Foundation (51178363), and other projects, such as particle shaping and refinement, grading regulation and optimization, surface modification and charge balance, and so on, for cement The low carbon preparation, surface modification and cementitious efficiency are systematically studied. Through the processing of cement, the cementitious efficiency of cement is improved, the amount of high resources, energy consumption and high carbon cement clinker are reduced, the transition zone of concrete interface is improved and the durability of concrete is improved.
The main achievements and innovation points in this paper are as follows:
1, based on the particle distribution function and fractal theory, the problem that the traditional grinding efficiency is low and the energy consumption is high, the low energy consumption on-line processing technology of cement for concrete application is established.
To break through the traditional grinding method with low grinding efficiency and most energy consumption converted to heat loss, it is creatively proposed that micro grinding medium (M) is used to process ordinary portland cement (C), and the theory and key technology of low energy cement super gelation system for concrete application are established. Based on normal, logarithmic, Gordon Schuhmann, Roxon lrinler The distribution function and fractal dimension theory are used to systematically study the particle size (frequency distribution and cumulative distribution) of the three material systems (C, M and CM), characteristic parameters (D50, D10, D25, D75 and D90) and the fractal dimension D, and establish the theoretical basis for high efficiency and low energy cement super gel condensation. When the particle size D50 is 8um, the energy consumption per unit mass grinding is reduced by 29.83% and 58.33%, respectively, by adding 5% M treatment 10min and adding 20% M treatment 5min by traditional grinding technology. When particle size D50 is 7um, 20% M treatment 10min and 30% M processing 5min are added, and the energy consumption per unit mass grinding is reduced 37.50%, respectively. And 64.29%.
2, based on the IPP image technology, the fractal theory and the theory of the electronic layer theory, facing the low water glue ratio and high flow state concrete requirements, the surface modification and regulation technology of cement super gel agglomerate are established to reduce the particle size and agglomeration of cement.
The fractal dimension of the flocculation structure of cement paste, the surface potential and the rheological properties of the cement paste are regulated by different kinds of surface modifiers and other additives. Under the experimental conditions, the fractal dimension 1.2~1.4 of the cementitious cement paste, the zeta potential -60mW~-30mW of the hydrated 60min, and the shear rate of 100r/s-1, the shear stress 320pa~500pa, and the viscosity 4 The fractal dimension of.00pa s~5.00pa S. and ordinary cement is 1.4632. When the shear rate is 100r/s-1, the zeta potential of the hydrated 60min is -0.89mW, the shear stress is 579.27pa, the viscosity is 9.45pa. S. super gel cement fractal dimension decreases, the zeta potential electronegativity increases, the shear stress decreases, and the viscosity decreases, which is applied to low water gel ratio, high flow state, high strength and high strength. The modern concrete with high durability has laid a theoretical foundation. Through the modification and regulation of the surface of super gel cement, the fractal dimension of cement particles, zeta potential and rheology model is established, and the cement dispersion technology and theoretical foundation are formed, and the method of rapid evaluation and analysis of the degree of particle dispersion is established.
3, based on the hydration products of the cementitious cement, the hydration degree and the characteristics of the interface transition zone, the theory and model of the hydration of super gelatinization cement are established, which lays a theoretical foundation for the application of super gelation cement to the modern concrete with high strength and high durability.
By means of XRD, SEM and DTA-TG, the hydration characteristics and hydration degree of super gel cement at different age and water glue ratio are analyzed. The hydration theory and model of super gel cement cement are established. Compared with ordinary cement, under the same experimental conditions, the hydration degree of super cementitious cement in hydrated 1D is obviously increased by 19.05%, and the hydration degree of hydrated 3D is increased by 22.04%, The hydration degree of hydrated 180d is increased by more than 20%. The structure of hydration products of super gel cement is more compact, the peak intensity of diffraction peak of Ca (OH) 2 in hydration products increases, and the weight loss of hydration products increases obviously. Compared with ordinary cement, the hardness of the boundary surface transition zone of super cementitious cement increases by 20.95% and the size decreases by 24.14%, compared with ordinary cement. The hardness of the slurry increased by 14.29%, the structure of hydrated product was denser, and the enrichment of Ca (OH) 2 decreased, which laid a theoretical foundation for its application in concrete to improve its strength and durability.
4, the application effect of super gel cement in different systems of concrete is studied, and the system system and key technology for concrete are set up, and the theoretical foundation of the application and popularization of super gel cement and cement is laid.
The application effect of super gelation cement in different systems of concrete is studied, and the system system and key technology for concrete application are established. Under the condition of equivalent mechanical properties, super cementitious cement and mineral powder are used in the unit volume concrete to replace the ordinary cement, the amount of super gelation cement is 8.33%, the cement dosage is reduced by 30%, and the super glue is used. Cement and fly ash replace ordinary cement, super cementitious cement content is 16.67%, cement consumption is reduced by 25%, super gel cement, fly ash and mineral powder replace ordinary cement, super cementitious cement content is 8.33%, cement dosage reduced 30.00%. research and analysis of industrial application of super gel cement for material flow balance, and draw industrialization The flow chart is used to lay the theoretical foundation and key technology for the application and promotion of super cementitious cement.

【学位授予单位】：武汉理工大学
【学位级别】：博士
【学位授予年份】：2014
【分类号】：TQ172.1

【参考文献】