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北京工业大学博士学位论文
题目：硅酸盐―硫铝酸盐复合体系水泥研究
英文并列题目： Investigation on the Silicate-sulphoaluminate Compound System Cement
摘要
水泥的生产和水泥混凝土的应用为基础设施建设带来了巨大的变化，也为全人类社会经济发展奠定了雄厚的基础。在我国2004年的水泥年产量已超过9亿吨，约占世界水泥产量的50%。随着我国经济建设的跨越发展及基础设施建设的高速增长，对水泥的需求仍有进一步的增长。然而，水泥的生产需要消耗大量的
自然资源和能源。例如生产1t水泥需要1.3t的石灰石、0.3t的黏土质材料。水泥熟料生产的平均热耗为4000KJ/Kg，而综合电耗则达到120KW·h/t。此外，每生产1t水泥熟料还会产生1t左右的二氧化碳。
水泥及水泥混凝土在当今社会具有不可替代的位置，而困扰全球的资源短缺及环境污染又与水泥的生产直接有关。长期以来人们一直努力采取多种措施走水泥生产可持续发展的道路，而最大限度地改善水泥的性能,以用最少的水泥用量满足高性能水泥混凝土的要求，则是国内外专家学者、ZF部门科研生产和施工
企业达成的共识。
水泥是建筑施工中所用的胶凝材料的统称，包括硅酸盐水泥、铝酸盐水泥、硫铝酸盐水泥等系列。硅酸盐系列水泥(PC)是应用广泛的经济型建筑材料，而硫铝酸盐系列水泥(CSA)是具有我国自主知识产权的性能优良的特种工程材料，两个系列均具有自己独特的矿物组成和性能特点，通过复合如能将其优良性能组
合，将是改善水泥性能的又一条途径。本课题通过研究硅酸盐-硫铝酸盐复合体系性能及水化硬化机理，并在与硅酸盐系列水泥对比的基础上，对其进行多方面的综合评价，对于硅酸盐-硫铝酸盐复合体系水泥的应用具有重要的指导意义，对于复杂体系水化理论的研究，有一定的参考价值。
本论文运用了“均匀设计”的思想方法，在较大范围内设计了符合约束条件的实验方案，保证了复合体系组成实验的科学性和代表性。通过对所设计的实验方案中不同配比试样进行常规物理力学性能试验，全面地研究了硅酸盐水泥熟料—硫铝酸盐水泥熟料—石膏所组成的三元复杂系统中材料组成与性能之间的关系。在靠近硅酸盐的P区以组成配比为PC熟料：CSA熟料：石膏=86.4%：4.5%：9.1%的P3试样综合性能最佳。另外，有快凝特点的P2、P15、P16可以满足有快硬要求的特殊工程，其中又以P2最为经济。在靠近硫铝酸盐的C区，可以通过调整材料组成，在较大范围内调整其凝结时间和强度，满足不同的工程需要。
研究结果表明，在硫铝酸盐水泥熟料中，加入10%以下的硅酸盐水泥熟料和15%以下的石膏，可以得到强度持续发展的早强高强型复合水泥材料；在硫铝酸盐水泥熟料中，加入10—20%的硅酸盐水泥熟料和5—15%的石膏，可以得到强度持续发展的快凝早强型复合水泥材料。
在基本了解了组成与性能关系的基础上，本论文还研究了原材料特性及体系颗粒尺寸分布对复合体系性能的影响规律，并分析了原材料特性影响复合体系性能的原因。研究结果说明了复合体系性能的绝对值与原材料特性尤其是PC熟料的特性密切相关，但是随组成的变化规律是一致的。组成及原材料相同时，体系
颗粒分布对其性能有较大的影响。
在对复合体系水泥宏观性能研究的基础上，通过对复合体系水泥水化浆体进行X-射线衍射、差热/热重、扫描电子显微镜等测试分析，研究了复合体系水泥水化产物的组成和微观结构。与此同时，还对其水化过程的水化放热行为、浆体电阻率变化、交流阻抗响应等热电特性进行了测试，并结合水泥化学的有关理论，对复合体系水泥的异常凝结行为给予了解释，深入讨论了复合体系水泥的水化硬化机理。
最后对复合体系水泥在实际工程应用中必然要遇到的与粉煤灰的相容性问题以及复合体系水泥混凝土的工作性、耐久性和力学性能进行了试验研究。
研究结果证明，复合体系对粉煤灰水化有良好的促进作用。与硅酸盐水泥混凝土相比，用复合体系水泥配制的混凝土，有较好的工作性能、力学性能，大部分耐久性指标也优于硅酸盐水泥混凝土。
本论文的研究特色在于，运用“均匀设计”思想方法进行实验方案设计，在较大范围内全面系统地研究了全新的硅酸盐-硫铝酸盐复合体系组成与性能的关系，并比较了不同特性原材料对复合体系性能的影响；本论文首次深入讨论了硅酸盐-硫铝酸盐复合体系水泥的水化硬化机理；对复合体系-粉煤灰混合系统和复合体系水泥混凝土进行了研究，为复合体系水泥的应用奠定了理论基础和设计依据。
关键词：水泥,硅酸盐-硫铝酸盐复合体系,性能,水化机理
Abstract
The cement production and the cement concrete application has brought the huge change for the infrastructure construction,and established the abundant foundation for the universe social economy development.In 2004 cement annual output has surpassed 900 million tons in our country,approximately 50%of the world cement output.With the swift development of our country’s economics and high advance of infrastructure construction,further growth is expected for the cement demand.However,the cement production needs to consume the massive natural resource and the energy.For example 1.3 t limestone and 0.3 t other materials are needed to produces only 1 t cement clinker.The energy consumption for cement clinker production is 4000 kJ/kg and the comprehensive electricity consumption 120 kW·h/t. In addition,1t carbon dioxide would be released with the production of 1t cement clinker.Cement and cement concrete has the un-substituted position in this society,but the shortage of resources and the environmental pollution,which puzzle the whole world,are also directly related with the cement production.For long time people diligently take the many kinds of measures to make cement production to be sustainable.To improve the performance of cement and to use the least cement content to satisfy the requirement of high performance cement concrete is the mutual recognition,which the domestic and foreign experts,the government department,the production and the construction enterprise have achieved.Cement is a general designation of cementitious materials,which are used in the construction,including Portland cement(silicate cement)series,aluminate cement series,sulphoaluminate cement series.The silicate cement series is widely applied as they are economical building materials,whereas the sulphoaluminate cement series have our country’s independent intellectual property rights and are special engineering materials with high performance.The two series have the different unique mineral composition and the performance characteristics,and fine performance combination may improve their properties.This also raises a new method for improvement of cements.This project studied the performance and properties of the silicate-sulphoaluminate compound system and the hydration as well as hardening mechanism,in compare with silicate cement series.The research conducted the investigation on various aspects of the system,which has the important instruction significance regarding the silicate-sulphoaluminate compound cement system and its application.The research results can be highly referred for the hydration theory research in compound system.
The present paper utilized the concept of"the even design"and designed experimental plan in comparatively wide range conformed to the restraint condition,which guaranteed the scientific nature and the representation of the composition experiment in the compound system.Through the conventional physics and mechanics performance test of specimens in the experimental plan,which have different proportions,the relationships between the compositions and properties of the materials in the three compound system of Portland cement-sulphoaluminate cement-gypsum composes have been investigated in detail.It is illustrated that the proportions near the P area of silicate with Portland cement:sulphoaluminate cement:Gypsum=86.4%:4.5%:9.1%P3 shows the best comprehensive performance.Besides,specimens of P2,P15,P16 have the rapid setting characteristic and may satisfy the requirement of quick hardening for some special projects.Among them P2 is most economical.In C area near sulphoaluminate,the material composition may be regulated so as to adjust the setting and strength in comparatively wide range and meet the needs of different projects.The results also indicated when 10%of sulphoaluminate cement clinker and 15%of gypsum were added,compound cement material with early high strength can be obtained,the later strength of which may continues to develop obviously.When added with 10-20%Portland cement and 5-15%gypsum,sulphoaluminate cement clinker may turn to a compound cement exhibiting a rapid setting,early high strength and later continuous strength development.
Based on the understanding of the relationship between the composition and the performance,the present paper has also studied the influence of the raw material’s characteristic and the particle size distribution to the performance of the compound system,and has analyzed the mechanism of the influence of raw material’s characteristic on the compound system.The findings showed that there exists a close relationship between the absolute value of the performance of compound system and the raw material characteristic,especially Portland cement characteristic,but change rule is consistent along with the composition.When the composition and the raw material are the same,the particle size distribution of the system has a more influence on its performance.
After the research on the macroscopic performance of the compound system,modern analyses with X-ray diffraction,thermal analysis and scanning electron microscope were conducted on the cement hydrates and microscopic structure in the compound system.At the same time,exothermic behavior during hydration,electronic receptivity change of hydrates as well as other thermoelectricity characteristics have been tested in reference to some related cement chemistry theory.The abnormal setting behavior of the compound system has been explained and the mechanism of hydration and hardening of the compound system have been thoroughly discussed.
Finally the issue of compatibility of the compound system with fly ash,which is unavoidable in practical application,and the workability,the durability as well as the mechanics’properties have been studied.The results proved that,the compound system has a good promoting action to the hydration of fly ash.Compared with the Portland cement concrete,concrete made of the compound system cement has a better workability and better mechanics’performance,and the majority of durable indexes also surpass that of the Portland cement concrete.
The research characteristic of the present paper lies in the utilization of the concept of"the even design"for experimental plan design,comprehensive and systematical study of the brand-new silicate-sulphoaluminate compound system as well as their properties,and comparison of the influences of the raw materials with different properties on the compound system in comparatively wide range.The present paper thoroughly discussed the cement hydrated and hardening mechanism in the silicate-sulphoaluminate compound system for the first time;the paper also conducted the research on the compound system-fly ash mix system and the compound system cement concrete,and set up the rationale and the design basis for the practical application of compound system cement and concrete.
Keyword:cement;silicate-sulphoaluminate compound system;performance;hydrated mechanism
北京工业大学博士学位论文
题目：硅酸盐―硫铝酸盐复合体系水泥研究
英文并列题目： Investigation on the Silicate-sulphoaluminate Compound System Cement
摘要
水泥的生产和水泥混凝土的应用为基础设施建设带来了巨大的变化，也为全人类社会经济发展奠定了雄厚的基础。在我国2004年的水泥年产量已超过9亿吨，约占世界水泥产量的50%。随着我国经济建设的跨越发展及基础设施建设的高速增长，对水泥的需求仍有进一步的增长。然而，水泥的生产需要消耗大量的
自然资源和能源。例如生产1t水泥需要1.3t的石灰石、0.3t的黏土质材料。水泥熟料生产的平均热耗为4000KJ/Kg，而综合电耗则达到120KW·h/t。此外，每生产1t水泥熟料还会产生1t左右的二氧化碳。
水泥及水泥混凝土在当今社会具有不可替代的位置，而困扰全球的资源短缺及环境污染又与水泥的生产直接有关。长期以来人们一直努力采取多种措施走水泥生产可持续发展的道路，而最大限度地改善水泥的性能,以用最少的水泥用量满足高性能水泥混凝土的要求，则是国内外专家学者、ZF部门科研生产和施工
企业达成的共识。
水泥是建筑施工中所用的胶凝材料的统称，包括硅酸盐水泥、铝酸盐水泥、硫铝酸盐水泥等系列。硅酸盐系列水泥(PC)是应用广泛的经济型建筑材料，而硫铝酸盐系列水泥(CSA)是具有我国自主知识产权的性能优良的特种工程材料，两个系列均具有自己独特的矿物组成和性能特点，通过复合如能将其优良性能组
合，将是改善水泥性能的又一条途径。本课题通过研究硅酸盐-硫铝酸盐复合体系性能及水化硬化机理，并在与硅酸盐系列水泥对比的基础上，对其进行多方面的综合评价，对于硅酸盐-硫铝酸盐复合体系水泥的应用具有重要的指导意义，对于复杂体系水化理论的研究，有一定的参考价值。
本论文运用了“均匀设计”的思想方法，在较大范围内设计了符合约束条件的实验方案，保证了复合体系组成实验的科学性和代表性。通过对所设计的实验方案中不同配比试样进行常规物理力学性能试验，全面地研究了硅酸盐水泥熟料—硫铝酸盐水泥熟料—石膏所组成的三元复杂系统中材料组成与性能之间的关系。在靠近硅酸盐的P区以组成配比为PC熟料：CSA熟料：石膏=86.4%：4.5%：9.1%的P3试样综合性能最佳。另外，有快凝特点的P2、P15、P16可以满足有快硬要求的特殊工程，其中又以P2最为经济。在靠近硫铝酸盐的C区，可以通过调整材料组成，在较大范围内调整其凝结时间和强度，满足不同的工程需要。
研究结果表明，在硫铝酸盐水泥熟料中，加入10%以下的硅酸盐水泥熟料和15%以下的石膏，可以得到强度持续发展的早强高强型复合水泥材料；在硫铝酸盐水泥熟料中，加入10—20%的硅酸盐水泥熟料和5—15%的石膏，可以得到强度持续发展的快凝早强型复合水泥材料。
在基本了解了组成与性能关系的基础上，本论文还研究了原材料特性及体系颗粒尺寸分布对复合体系性能的影响规律，并分析了原材料特性影响复合体系性能的原因。研究结果说明了复合体系性能的绝对值与原材料特性尤其是PC熟料的特性密切相关，但是随组成的变化规律是一致的。组成及原材料相同时，体系
颗粒分布对其性能有较大的影响。
在对复合体系水泥宏观性能研究的基础上，通过对复合体系水泥水化浆体进行X-射线衍射、差热/热重、扫描电子显微镜等测试分析，研究了复合体系水泥水化产物的组成和微观结构。与此同时，还对其水化过程的水化放热行为、浆体电阻率变化、交流阻抗响应等热电特性进行了测试，并结合水泥化学的有关理论，对复合体系水泥的异常凝结行为给予了解释，深入讨论了复合体系水泥的水化硬化机理。
最后对复合体系水泥在实际工程应用中必然要遇到的与粉煤灰的相容性问题以及复合体系水泥混凝土的工作性、耐久性和力学性能进行了试验研究。
研究结果证明，复合体系对粉煤灰水化有良好的促进作用。与硅酸盐水泥混凝土相比，用复合体系水泥配制的混凝土，有较好的工作性能、力学性能，大部分耐久性指标也优于硅酸盐水泥混凝土。
本论文的研究特色在于，运用“均匀设计”思想方法进行实验方案设计，在较大范围内全面系统地研究了全新的硅酸盐-硫铝酸盐复合体系组成与性能的关系，并比较了不同特性原材料对复合体系性能的影响；本论文首次深入讨论了硅酸盐-硫铝酸盐复合体系水泥的水化硬化机理；对复合体系-粉煤灰混合系统和复合体系水泥混凝土进行了研究，为复合体系水泥的应用奠定了理论基础和设计依据。
关键词：水泥,硅酸盐-硫铝酸盐复合体系,性能,水化机理
Abstract
The cement production and the cement concrete application has brought the huge change for the infrastructure construction,and established the abundant foundation for the universe social economy development.In 2004 cement annual output has surpassed 900 million tons in our country,approximately 50%of the world cement output.With the swift development of our country’s economics and high advance of infrastructure construction,further growth is expected for the cement demand.However,the cement production needs to consume the massive natural resource and the energy.For example 1.3 t limestone and 0.3 t other materials are needed to produces only 1 t cement clinker.The energy consumption for cement clinker production is 4000 kJ/kg and the comprehensive electricity consumption 120 kW·h/t. In addition,1t carbon dioxide would be released with the production of 1t cement clinker.Cement and cement concrete has the un-substituted position in this society,but the shortage of resources and the environmental pollution,which puzzle the whole world,are also directly related with the cement production.For long time people diligently take the many kinds of measures to make cement production to be sustainable.To improve the performance of cement and to use the least cement content to satisfy the requirement of high performance cement concrete is the mutual recognition,which the domestic and foreign experts,the government department,the production and the construction enterprise have achieved.Cement is a general designation of cementitious materials,which are used in the construction,including Portland cement(silicate cement)series,aluminate cement series,sulphoaluminate cement series.The silicate cement series is widely applied as they are economical building materials,whereas the sulphoaluminate cement series have our country’s independent intellectual property rights and are special engineering materials with high performance.The two series have the different unique mineral composition and the performance characteristics,and fine performance combination may improve their properties.This also raises a new method for improvement of cements.This project studied the performance and properties of the silicate-sulphoaluminate compound system and the hydration as well as hardening mechanism,in compare with silicate cement series.The research conducted the investigation on various aspects of the system,which has the important instruction significance regarding the silicate-sulphoaluminate compound cement system and its application.The research results can be highly referred for the hydration theory research in compound system.
The present paper utilized the concept of"the even design"and designed experimental plan in comparatively wide range conformed to the restraint condition,which guaranteed the scientific nature and the representation of the composition experiment in the compound system.Through the conventional physics and mechanics performance test of specimens in the experimental plan,which have different proportions,the relationships between the compositions and properties of the materials in the three compound system of Portland cement-sulphoaluminate cement-gypsum composes have been investigated in detail.It is illustrated that the proportions near the P area of silicate with Portland cement:sulphoaluminate cement:Gypsum=86.4%:4.5%:9.1%P3 shows the best comprehensive performance.Besides,specimens of P2,P15,P16 have the rapid setting characteristic and may satisfy the requirement of quick hardening for some special projects.Among them P2 is most economical.In C area near sulphoaluminate,the material composition may be regulated so as to adjust the setting and strength in comparatively wide range and meet the needs of different projects.The results also indicated when 10%of sulphoaluminate cement clinker and 15%of gypsum were added,compound cement material with early high strength can be obtained,the later strength of which may continues to develop obviously.When added with 10-20%Portland cement and 5-15%gypsum,sulphoaluminate cement clinker may turn to a compound cement exhibiting a rapid setting,early high strength and later continuous strength development.
Based on the understanding of the relationship between the composition and the performance,the present paper has also studied the influence of the raw material’s characteristic and the particle size distribution to the performance of the compound system,and has analyzed the mechanism of the influence of raw material’s characteristic on the compound system.The findings showed that there exists a close relationship between the absolute value of the performance of compound system and the raw material characteristic,especially Portland cement characteristic,but change rule is consistent along with the composition.When the composition and the raw material are the same,the particle size distribution of the system has a more influence on its performance.
After the research on the macroscopic performance of the compound system,modern analyses with X-ray diffraction,thermal analysis and scanning electron microscope were conducted on the cement hydrates and microscopic structure in the compound system.At the same time,exothermic behavior during hydration,electronic receptivity change of hydrates as well as other thermoelectricity characteristics have been tested in reference to some related cement chemistry theory.The abnormal setting behavior of the compound system has been explained and the mechanism of hydration and hardening of the compound system have been thoroughly discussed.
Finally the issue of compatibility of the compound system with fly ash,which is unavoidable in practical application,and the workability,the durability as well as the mechanics’properties have been studied.The results proved that,the compound system has a good promoting action to the hydration of fly ash.Compared with the Portland cement concrete,concrete made of the compound system cement has a better workability and better mechanics’performance,and the majority of durable indexes also surpass that of the Portland cement concrete.
The research characteristic of the present paper lies in the utilization of the concept of"the even design"for experimental plan design,comprehensive and systematical study of the brand-new silicate-sulphoaluminate compound system as well as their properties,and comparison of the influences of the raw materials with different properties on the compound system in comparatively wide range.The present paper thoroughly discussed the cement hydrated and hardening mechanism in the silicate-sulphoaluminate compound system for the first time;the paper also conducted the research on the compound system-fly ash mix system and the compound system cement concrete,and set up the rationale and the design basis for the practical application of compound system cement and concrete.
Keyword:cement;silicate-sulphoaluminate compound system;performance;hydrated mechanism
