目 录

中文摘要**........................................................................................................................ I**
ABSTRACT................................................................................................................IV
第一章绪论**..................................................................................................................1**
1.1 研究背景及意义..............................................................................................1
1.2 粉煤灰特性及其胶凝材料化研究..................................................................1
1.2.1 粉煤灰的产生及特性............................................................................1
1.2.2 粉煤灰胶凝材料的研究现状................................................................2
1.3 钢渣特性及其胶凝材料化研究......................................................................6
1.3.1 钢渣的产生及特性................................................................................6
1.3.2 钢渣胶凝材料的研究现状....................................................................8
1.4 脱硫石膏在复合胶凝材料中的作用............................................................10
1.4.1 脱硫石膏的产生及特性......................................................................10
1.4.2 脱硫石膏在复合胶凝材料中的作用..................................................11
1.5 超微粉磨技术研究现状................................................................................12
1.6 本文研究思路与主要内容............................................................................13
第二章粉煤灰的超微粉磨特性及对水泥胶凝体系的影响研究**............................17**
2.1 实验部分........................................................................................................17
2.1.1 实验原料..............................................................................................17
2.1.2 实验方法..............................................................................................17
2.1.3 分析表征..............................................................................................18
2.2 结果与讨论....................................................................................................19
2.2.1 粉煤灰超微粉的特性研究..................................................................19
2.2.2 粉煤灰-水泥胶凝试块的特性研究.....................................................24
2.3 本章小结........................................................................................................27
第三章钢渣的超微粉磨特性及对粉煤灰**-水泥胶凝体系的影响研究.................. 29**
3.1 实验部分........................................................................................................29
3.1.1 实验原料..............................................................................................29
3.1.2 实验方法..............................................................................................29
3.2 结果与讨论....................................................................................................33
3.2.1 钢渣超微粉的特性研究......................................................................33

3.2.2 粉煤灰-钢渣-水泥胶凝试块的特性研究........................................... 38
3.3 本章小结........................................................................................................42
第四章钢渣**-粉煤灰-脱硫石膏复合胶凝体系的协同效应和水化特性.................45**
4.1 实验部分........................................................................................................45
4.1.1 实验原料..............................................................................................45
4.1.2 实验方法..............................................................................................47
4.2 结果与讨论....................................................................................................49
4.2.1 抗压强度..............................................................................................49
4.2.2 吸水率和耐水性..................................................................................51
4.2.3 水化产物的XRD分析........................................................................52
4.2.4 水化产物的SEM/EDS分析...............................................................53
4.2.5 水化产物的TGA分析........................................................................54
4.3 本章小结........................................................................................................56
第五章钢渣**-粉煤灰-脱硫石膏复合胶凝体系的反应动力学.................................57**
5.1 实验部分........................................................................................................57
5.1.1 实验原料..............................................................................................57
5.1.2 实验方法..............................................................................................57
5.2 结果与讨论....................................................................................................58
5.2.1 钢渣-粉煤灰-脱硫石膏浆体的pH值................................................ 58
5.2.2 钢渣-粉煤灰-脱硫石膏胶凝试块抗压强度的发展........................... 59
5.2.3 钢渣-粉煤灰-脱硫石膏胶凝试块化学键的演变............................... 60
5.2.4 钢渣-粉煤灰-脱硫石膏胶凝试块物相组成的演变........................... 62
5.2.5钢渣-粉煤灰-脱硫石膏胶凝试块的水化程度.................................... 64
5.2.6 钢渣-粉煤灰-脱硫石膏复合胶凝体系的水化机理........................... 66
5.3 本章小结........................................................................................................66
第六章钢渣**-粉煤灰-脱硫石膏复合胶凝体系的养护优化和碳化增强实验研究.69**
6.1 实验部分........................................................................................................69
6.1.1 实验原料..............................................................................................69
6.1.2 实验方法..............................................................................................69
6.2 结果与讨论....................................................................................................70
6.2.1 养护条件对胶凝试块的特性影响......................................................70

6.2.2 胶凝试块的碳化和强化碳化研究......................................................76
6.3 本章小结........................................................................................................78
第七章钢渣**-粉煤灰-脱硫石膏复合胶凝体系的应用初探.....................................81**
7.1 “机械造孔-静压成型”制备新型高性能透水砖新技术................................81
7.2 透水砖模具设计............................................................................................82
7.3 透水砖制备及性能检测................................................................................83
7.3.1 透水砖的制备......................................................................................83
7.3.2 性能测试..............................................................................................84
7.4 透水砖中试生产示范....................................................................................85
7.5 本章小结........................................................................................................87
第八章结论与建议**....................................................................................................89**
8.1 本文主要结论................................................................................................89
8.2 创新点............................................................................................................90
8.3 建议和展望....................................................................................................91
参考文献**................................................................................................................93**
攻读学位期间取得的研究成果**................................................................................107**
致 谢**........................................................................................................................109**
个人简况及联系方式**................................................................................................110**
承 诺 书**................................................................................................................111**
学位论文使用说明**....................................................................................................112**

Contents

Chinese Abstract...........................................................................................................I
ABSTRACT................................................................................................................IV
Chapter 1 Introduction................................................................................................1
1.1 Research background and significance............................................................. 1
1.2 Characteristics of fly ash and its application in cementing materials............... 1
1.2.1 Generation and characteristics of fly ash................................................ 1
1.2.2 Research of fly ash in cementitious materials.........................................2
1.3 Characteristics of steel slag and its application in cementing materials........... 6
1.3.1 Generation and characteristics of steel slag............................................ 6
1.3.2 Research of steel slag in cementitious materials.....................................8
1.4 Effect of desulfurized gypsum in composite cementitious materials..............10
1.4.1 Generation and characteristics of desulfurized gypsum........................10
1.4.2 Effect of desulfurized gypsum in composite cementitious materials....11
1.5 Research of ultrafine grinding technology......................................................12
1.6 Research idea and contents..............................................................................13
Chapter 2 Study on ultrafine grinding characteristics of fly ash and its effect on
cement cementitious system.....................................................................17
2.1 Experimental................................................................................................... 17
2.1.1 Materials................................................................................................17
2.1.2 Methods.................................................................................................17
2.1.3 Characterization.....................................................................................18
2.2 Results and discussion.....................................................................................19
2.2.1 Properties of ultrafine fly ash................................................................19
2.2.2 Properties of fly ash-cement cementitious blocks.................................24
2.3 Summary of the chaper....................................................................................27
Chapter 3 Study on ultrafine grinding characteristics of steel slag and its effect
on fly ash-cement cementitious system................................................... 29
3.1 Experimental................................................................................................... 29
3.1.1 Materials................................................................................................29
3.1.2 Methods.................................................................................................29

3.2 Results and discussion.....................................................................................33
3.2.1 Properties of ultrafine steel salg............................................................33
3.2.2 Properties of fly ash-steel salg-cement cementitious blocks.................38
3.3 Summary of the chaper....................................................................................42
Chapter 4 Synergy and hydration properties of steel slag-fly ash-desulfurized
gypsum composite cementitious system..................................................45
4.1 Experimental................................................................................................... 45
4.1.1 Materials................................................................................................45
4.1.2 Methods.................................................................................................47
4.2 Results and discussion.....................................................................................49
4.2.1 Compressive strength............................................................................ 49
4.2.2 Water absorption and water resistance.................................................. 51
4.2.3 XRD analysis.........................................................................................52
4.2.4 SEM/EDS analysis................................................................................ 53
4.2.5 TGA analysis......................................................................................... 54
4.3 Summary of the chaper....................................................................................56
Chapter 5 Kinetics of steel slag-fly ash-desulfurized gypsum composite
cementitious system.................................................................................. 57
5.1 Experimental................................................................................................... 57
5.1.1 Materials................................................................................................57
5.1.2 Methods.................................................................................................57
5.2 Results and discussion.....................................................................................58
5.2.1 pH value of steel slag-fly ash-desulfurized gypsum slurry...................58
5.2.2 Compressive strength of steel slag-fly ash-gypsum blocks...................59
5.2.3 Chemical bonds in steel slag-fly ash-desulfurized gypsum blocks.......60
5.2.4 Phase of steel slag-fly ash-desulfurized gypsum blocks....................... 62
5.2.5 Hydration degree of steel slag-fly ash-desulfurized gypsum blocks.....64
5.2.6 Hydration mechanism of steel slag-fly ash-desulfurized gypsum
composite cementitious system...............................................................66
5.3 Summary of the chaper....................................................................................66

Chapter 6 Study on the curing conditions and carbonization enhancement of

steel slag-fly ash-desulfurized gypsum composite cementitious system69
6.1 Experimental................................................................................................... 69
6.1.1 Materials................................................................................................69
6.1.2 Methods.................................................................................................69
6.2 Results and discussion.....................................................................................70
6.2.1 Results and discussion...........................................................................70
6.2.2 Carbonization and enhanced carbonization of blocks...........................76
6.3 Summary of the chaper....................................................................................78
Chapter 7 Application of steel slag-fly ash-desulfurized gypsum composite
cementitious system.................................................................................. 81
7.1 Technology for preparing new high-performance permeable bricks by the
method of "mechanical hole making-static press forming"........................... 81
7.2 Design of permeable brick mould................................................................... 82
7.3 Preparation and performance testing of permeable bricks..............................83
7.3.1 Preparation of permeable bricks............................................................83
7.3.2 Performance test....................................................................................84
7.4 Pilot production and site laying.......................................................................85
7.5 Summary of the chaper....................................................................................87
Chapter 8 Conclusion and suggestion...................................................................... 89
8.1 Conclusion.......................................................................................................89
8.2 Innovation........................................................................................................90
8.3 Suggestion and further work........................................................................... 91
References................................................................................................................... 93
Research achievements............................................................................................ 107
Acknowledgment...................................................................................................... 109
Personal profiles....................................................................................................... 110
Letter of commitment.............................................................................................. 111
Authorization statement.......................................................................................... 112

中文摘要

作为典型的的大宗工业废弃物，钢渣、粉煤灰、脱硫石膏等大量的排放和堆 存对环境带来严重的危害。利用钢渣、粉煤灰、脱硫石膏制备无机胶凝材料以替 代部分水泥用于工业生产，不仅可以促进工业固废的大规模处置，同时可以实现 水泥减产降耗、节约成本等目的。本文采用超音速蒸汽粉碎机对粉煤灰和钢渣进 行超微粉磨，通过理论分析与实验研究，探讨了粉煤灰、钢渣的超微粉化作用机 理和其对胶凝材料的增强作用机制。同时选用所制备的钢渣超微粉、粉煤灰超微 粉为主要胶凝材料，脱硫石膏微粉作为辅助胶凝材料和活性激发剂，设计一种钢 渣-粉煤灰-脱硫石膏（SS-FA-DG）全固废三元胶凝体系，对此胶凝体系的水化产 物、反应机理、反应过程进行了重点研究。并通过养护条件优化、强化碳化实验， 进一步提升了胶凝材料的力学性能。最后，在理论研究的基础上，初步探索了 SS-FA-DG 全固废三元胶凝体系在高性能免烧透水砖方面的工程应用。主要工作 和结论如下：

（1）对比研究了流化床粉煤灰（CFBFA）和煤粉炉粉煤灰（PCFA）在超微粉 磨前后的特性变化。结果表明，粉煤灰的超微粉化不仅使得其比表面积的增加， 而且导致了粉煤灰中硅铝酸盐矿物的结晶度和阴离子聚合度的降低。对粉煤灰水泥胶凝试块的性能研究表明，粉煤灰超微粉比粉煤灰原灰更有利于水泥胶凝试 块抗压强度的提升，尤其是早期抗压强度的发展。胶凝试块的吸水率和热失重的 研究表明，粉煤灰超微粉提高了胶凝试块的密实度，且提高了试块中 C-S-H 的 含量。与 PCFA 相比，CFBFA 中硅铝酸盐矿物的阴离子聚合度较低，CFBFA 更 有利于提升水泥试块的前期抗压强度，而 PCFA 玻璃体中的活性 SiO2 和 Al2O3 在反应过程中缓慢释放，更加有利于提升试块的后期抗压强度。

（2）详细研究了超音速蒸汽粉碎机对钢渣的超微粉碎特性。结果表明，钢渣 经过超微粉碎后，被分级收集可以获得不同粒度的钢渣超微粉，其中颗粒较小的 钢渣超微粉，颗粒富集较多 CaO 和 SiO2，且其阴离子聚合度也较低，晶体尺寸 较小，活性较高，更加适合用于胶凝材料的制备。研究了钢渣超微粉对粉煤灰水泥胶凝试块性能的影响，结果发现，利用钢渣超微粉替代部分水泥使粉煤灰水泥二元胶凝体系转变为粉煤灰-钢渣-水泥三元胶凝体系，胶凝试块的抗压强 度、抗冻性和耐磨性都得到大幅提高。

（3）以抗压强度为主要指标，考察了钢渣，粉煤灰和脱硫石膏三种固废的协 同胶凝效应，结果表明，不同胶凝体系的协同效应大小为：三元体系>二元体系

I

（钢渣-粉煤灰）>一元体系（钢渣）。采用钢渣超微粉：粉煤灰超微粉：脱硫石 膏微粉为 70:20:10 的配比制备全固废胶凝试块，试块抗压强度较高（28 天抗压 强度为 39.6MPa），耐水性较好（软化系数为 1.09）。对胶凝试块的 SEM、XRD 和 TGA 分析表明，粉煤灰-钢渣-脱硫石膏复合胶凝体系的协同效应为，钢渣自 身具有自胶凝特性；粉煤灰促进了钢渣的二次水化反应，生成更多的 C-S-H 凝 胶；脱硫石膏参与体系反应，生成钙矾石晶体，针杆状的钙矾石晶体与 C-S-H 凝胶交错生长，形成致密网络状结构，降低试块孔隙率，优化试块整体结构，并 且脱硫石膏对粉煤灰起到活性激发作用，加深了反应程度，增加了试块中 C-S-H 含量，同时也促进水化产物中高钙硅比（c/s）水化硅酸钙向低 c/s 水化硅酸钙的 转化，因此提高了胶凝试块的力学性能。

（4）研究了 SS-FA-DG 复合胶凝体系的反应动力学，并考察温度对其反应动 力学特点的影响。结果表明，SS-FA-DG 复合胶凝体系的反应可以分为五个阶段 进行。第一阶段，钢渣水解，体系液相中出现 OH^- 和 Ca²⁺ ；第二阶段，粉煤灰的 活性 Al、Si 在 OH^- 的刺激下开始溶出，在溶液中形成 H2SiO4^2- 与 H2AlO^3- ；第三 反应阶段，液相中 H2SiO4^2- 、H2AlO3^- 与 SO4^2- 、Ca²⁺ 发生反应生成 C-S-H 和钙矾 石等产物，胶凝试块开始硬化，并产生一定的抗压强度。第四阶段，C-S-H 大量 生成，同时大量消耗 Ca(OH)2，C-S-H 开始成核、结晶。第五阶段，C-S-H 和钙 矾石晶体在胶凝材料内部不断扩散、相互生长，形成网络状结构，使胶凝试块更 加密实，抗压强度快速发展。养护温度的提升可以缩短 SS-FA-DG 复合胶凝体系 各阶段的反应时间，加速水化反应速度。同时，温度的提升使水化产物的聚合度 增加，提高水化程度，增加了 C-S-H 的生成量，使得胶凝试块的抗压强度更高。

（5）对 SS-FA-DG 全固废三元胶凝体系的养护制度进行优化研究。实验发现， 在湿热+蒸压复合养护条件下，SS-FA-DG 三元胶凝试块的抗压强度在较短的养 护时间（＜4 天）内达到了 35.8MPa，符合国标 MU35 的强度要求。XRD，FT-IR 和 TGA 分析表明，湿热养护有利于胶凝试块中 C-S-H 的快速生成，而蒸压养护 则促进了 C-S-H 向托勃莫来石晶体的转化。SEM 分析表明 C-S-H 胶凝与托勃莫 来石晶体互相链接，紧密结合，形成一种更加致密的微观结构，从而使得胶凝试 块的抗压强度较高。对养护完成后的胶凝试块进行强化碳化实验，结果表明，胶 凝试块的抗压强度进一步增长约 19.6%，这主要是因为微纳米级碳酸钙填充孔 隙，使凝胶块更致密。强化碳化后，胶凝试块的质量增加了 1.95％，说明其自身 质量的 1.95％的 CO2 被吸收。

II

（6）采用自主开发的“机械造孔-静压成型”新技术，以 SS-FA-DG 复合微粉为 胶凝材料，以矿渣为骨料，骨胶比为 6:4，水灰比为 0.2，采用梯度蒸压养护制度， 制备高性能免烧透水砖。结果显示，所制备透水砖各项性能均满足或超过相关国 家标准要求。透水砖产品在山西太钢集团进行了中试生产，并对中试产品在山西 襄垣进行实地铺设，经过一年的使用发现，本课题所研制免烧透水砖的长期稳定 性良好，具有较好的市场、经济效益前景。

关键词：钢渣；粉煤灰；脱硫石膏；超微粉磨；胶凝材料；反应动力学；

III

ABSTRACT

As the typical bulk industrial waste, a large amount of discharge and storage of steel slag, fly ash, desulfurized gypsum, etc. bring serious harm to the environment. The use of steel slag, fly ash, and desulfurized gypsum to prepare inorganic cementing materials to replace part of the cement for industrial production can not only promote the large-scale disposal of industrial solid waste, but also achieve the purpose of reducing cement production, consumption, and cost. In this paper, supersonic steam pulverizer is used to ultrafinely pulverize fly ash and steel slag. Through theoretical analysis and experimental research, the ultrafine pulverization mechanism of fly ash and steel slag and its mechanism of strengthening cementitious materials are clarified. At the same time, fly ash ultrafine powder and steel slag ultrafine powder are selected as the main cementitious materials, and desulfurized gypsum powder is used as auxiliary cementitious material and active activator to design a solid waste ternary cementitious system contain steel slag, fly ash and desulfurized gypsum (SS-FA-DG). The hydration products, reaction mechanism and reaction process of this cementitious system have been researched. The mechanical properties of the cementitious material have been further improved by optimizing the curing conditions and testing of enhanced carbonization. Finally, based on the theoretical research, the engineering application of SS-FA-DG full solid waste ternary cementitious system in high-performance and non-firing permeable bricks was explored. Major results included. (1) The characteristics of fluidized bed fly ash (CFBFA) and coal pulverized coal (PCFA) before and after ultrafine grinding were compared and studied. The results show that the ultra-micronization of fly ash not only increases its specific surface area, but also reduces the crystallinity and anionic polymerization degree of aluminosilicate minerals in fly ash. Research on the performance of fly ash-cement cementing block shows that, fly ash ultrafine powder is more conducive

IV