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粉煤灰早期活性激发及其机理研究(钱文勋)

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q8X Nqpcp/T5}0【作者】钱文勋 【导师】蔡跃波
fy"y} ce0【作者基本信息】南京水利科学研究院,材料学,2002年,硕士水利论文#Ys:u`h0x

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:@&A u}~Eq0【中文摘要】 近年来,随着现代混凝土技术的发展以及对粉煤灰潜在效应认识的不断深入,高掺量粉煤灰混凝土在土木工程中的应用研究越来越受到人们的重视,尤其是在水工大坝大体积混凝土结构中。但是研究资料显示:粉煤灰高量掺入混凝土后带来了早期强度过低的问题。因此,如果可以通过适宜的技术途径激发粉煤灰早期活性,调整粉煤灰潜在活性在水化期的时段分布,使高掺量粉煤灰混凝土早期强度明显提高,无疑将促进粉煤灰大规模利用技术更加完善与实用。同时,粉煤灰活性激发机理是高掺量粉煤灰混凝土设计与应用的理论基础,也是该领域研究的热点和难点。 粉煤灰活性激发剂及其激发机理研究是本文的重点。 本文采用化学激发措施激发粉煤灰活性,具体研究路线为:首先以砂浆为试验载体(粉煤灰60%+水泥40%,质量百分比),优选单掺效果显著的化学激发剂,在此基础上,考察各种激发剂的不同组合对粉煤灰活性激发的效果,得到较优复掺配方,随后通过正交试验优化配方掺量,最终得到激发剂配方;将配方应用于高掺量粉煤灰混凝土中(粉煤灰占总胶凝材料质量百分比的60%),检验其实际效果。 实验结果表明:所得七组激发剂配方在粉煤灰-水泥砂浆体系中激发效果显著,与同条件下不掺激...更多发剂的对比组相比,3d抗压强度都有超过150%的增长,最高的达210%,同时,正交试验优化激发剂配方后,激发剂掺量(不计高效减水剂)均在1.0%~1.5%,经济上较为合理,工艺上较为可行;掺入混凝土中时,部分配方激发混凝土早期强度效果明显,3d抗压强度可提高55%,强度等级从C25提高至C35。 从激发剂研制的整个过程来看,粉煤灰早期活性的激发效果主要取决于激发剂内在的化学特性。此外,有两个因素也不容忽视:其一是激发剂是否具有降低高掺灰砂浆或者混凝土水胶比的能力;其二是激发剂的拌入工艺,这是因为激发剂掺量少,容易产生搅拌不均匀而影响激发效果。 在粉煤灰活性激发机理的研究中,采用了X射线衍射技术(XRD)考察掺与不掺激发剂组间Ca(O广量的变化和水化产物的特征,同时采用扫描电于显微镜(SEM)和微区能谱分析(EDS),从水化产物的形貌和微区元素组成的角度系统分析了激发剂对粉煤灰活性激发的机理;此外,在国内首次将固体核磁共振(NMR)技术应用于粉煤灰一水泥体系中,从硅氧、铝氧聚合态结构角度分析了激发剂对粉煤灰一水泥浆体中硅氧结构和铝氧结构的活化作用。同时,本文在机理探讨时结合了宏观定性研究,以此验证激发剂的作用对象。 结果显示:激发剂激发了粉煤灰一水泥体系中粉煤灰的早期活性;激发剂的确破坏了粉煤灰玻璃体中部分硅氧结构和铝氧结构,使之解聚成活性较高的小分于结构,同时,随着激发剂中网络变性体(碱金属离子Na和 K等)或者网络中间体川的引入,也使得活性低的粉煤灰玻璃体出现断裂解聚,所得的高活性个分子消耗大量的水泥水化产物Ca(OH方,生成具有早强性质的水化产物,这里主要是水化硅酸钙、水化铝酸钙和钙矾石等。值得注意的是,XRD分析和 SEM形貌观察得到一致结果:粉煤灰在激发剂的作用下,早期水化产物有大量的C干一H(I)生成 XRD显示为 CXI。SIO3厂 XH。O人该结果与 NMR分析结果也吻合。拧SINMR分析显示:激发剂掺入浆体后,使粉煤灰由集中的高聚体结构向分散的低聚体结构转化,激发了粉煤灰中玻璃体的早期活性;刀AINMR分析显示:激发剂的激发作用在于破坏了粉煤灰玻璃体结构中铝氧六配位结构,使之解聚并生成较多小分于结构参与早期水化,从而提高粉煤灰早期活性。 固体NMR技术在本文探讨粉煤灰活性激发机理时提供了很多有价值的微观结构信息,这为今后进一步深入探讨粉煤灰活性激发机理可以抛砖引玉。  还原

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B,d1L+?|II6@#D*O0【英文摘要】 Recently, with the development of modem concrete technology and being deeply understood for the potential effect of fly ash in concrete, the study of using high volumes of fly ash concrete (HVFC) in civil engineering is paid more and more attention, especially in hydraulic structure of large volume concrete or large dam. However, researches are also indicated that the problem of over-low early strength should be concerned because of high volumes fly ash in HVFC. Therefore, if fly ash can be activated through suitable technological way and the distribute of its potential activity can be adjusted during hydrating period, then the early strength of HVFC can be obviously increased, the technology of utilizing fly ash on a large scale will be undoubtedly promoted to be perfect and practical. Meanwhile, the mechanism of activating fly ash is theoretical foundation on the design and application of HVFC and it is also a popular and difficult point in this'field.This paper focuses attention on ...更多the investigations of fly ash activator and the mechanism of activating.Chemical measure was taken to activate fly ash. Firstly, the mortar was selected as test carrier (fly ash 60%+cement 40%, by weight), seeking for activators that showed remarkable result. Secondly, examining the effect of combining activators and getting final prescriptions after optimizing activators dosage by means of orthogonal design. Lastly, the results of these prescriptions in HVFC (fly ash is 60% of total binder) were tested.Test results indicate that seven groups of optimized prescription were remarkable on activating fly ash in the mortar system. Comparing compressive strength with control group without activator, there was more than 150% growth in 3-day age and the highest one up to 210%. Besides, due to the dosage of activator used were in the range of 1.0%1.5% (disregarding superplasticizer), it was economical and feasible. The early compressive strength of HVFC with some activators was also increased obviously, the highest one was up to 55% in 3-day age and its strength grade was improved from C25 to C35.According to the whole course of investigation, the result of activators was mainly depended on their chemical characteristics. Besides, there were two factors that should not be ignored: One was the effect of activators of reducing water-binder ratio of mortar or concrete, the other was the leveling of mixing.X-ray diffraction (XRD) technique was adopted to investigate the quantity change of Ca(OH)2 and the character of hydrated products of mortar system with or without activators. At the same time scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) technique were used to systematic analyze the morphology of hydrated products and elementary composition of microstructure. In addition, nuclear magnetic resonance (NMR) technique was used to test fly ash-cement system for the first time at home. And the activating influence of activators on structure of silicon-oxygen and aluminum-oxygen was analyzed. Besides, the macroscopic qualitative research was also combined to prove the effect of activating.The results show that fly ash was activated in early hydrate. The structure of silicon-oxygen and aluminum-oxygen was partly depolymerized into little activated molecular. And the net-modified ion (such as K, Na) or net-neutral ion (Al) from activator destroyed low activated glassiness in fly ash. Thus the more hydrated products owning early strength was appeared, such as hydrate calcium silicate, hydrate aluminum silicate and ettringite. What merited attention was, an unanimous result was received by XRD and SEM analysis: A large amount of C-S-H( I ) was produced owing to the function of activator and the result was identical with that of NMR analysis. 29Si-NMR analysis show that micro-structure of fly ash was changed from concentrated high-polymerization to scattered low-polymerization by the activator and the glassiness in fly ash was activated. 27A1-NMR analysis express that it is the function of activator to dest  还原水利论文xA xW'K7h

-z?)D.UN0【中文关键词】 粉煤灰; 高掺量粉煤灰混凝土; 早期活性激发; 机理; 核磁共振(NMR)
D} |/?MhK0【英文关键词】 Fly ash; High volumes of fly ash concrete; Early activating; Mechanism; Nuclear magnetic resonance (NMR)
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TAG: 粉煤灰 机理 研究 钱文勋 活性
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