LiOH抑制碱-硅酸反应膨胀及其应用研究

研究了沸石化珍珠岩混凝土在KOH,LiOH溶液中压蒸膨胀行为,通过扫描电镜和能量散射谱对产物的形貌和组成进行了分析,说明LiOH抑制碱-硅酸反应膨胀的机理主要是在集料周围形成了含锂盐的非膨胀性产物,含锂产物层的形成对活性集料起保护作用而阻止了碱的进一步侵蚀。研究了由碱-硅酸活性集料和碱-碳酸盐活性集料制成的混凝土在各种碱中的膨胀行为。结果表明：混凝土在相同摩尔浓度的碱中压蒸,在NaOH溶液中膨胀最大,在LiOH溶液中膨胀最小。在应用LiOH抑制碱-硅酸反应膨胀促进碱-碳酸盐反应膨胀的双重作用下,在Spratt细粒硅质灰岩中,少量的白云石在碱环境中可发生去白云石化作用而对膨胀有贡献,也即尽管Spratt灰岩中碱-硅酸反应是主要的,但也存在碱-碳酸盐反应。     

用溶胶-凝胶膨胀法对碱-硅酸反应机理的研究

利用溶胶-凝胶膨胀法,将碱与蛋白石直接反应再一次证实,渗透压是碱-硅酸反应的主要膨胀力的来源,而凝胶膨胀所引起的膨胀量确实是有限的;并利用蛋白石对碱-硅酸反应的“最劣点”现象进行了研究,发现最劣点的产生实际上与溶液中碱的有限度含量密切相关。当活性矿物中的SiO_2与碱的摩尔比在某一值附近时,溶解出来的SiO_2浓度最大,粒子数最多,有可能产生最大的渗透压,因而此时产生的膨胀力与膨胀量最大。通过调整骨料的掺量和混凝土中可溶碱的含量有可能达到抑制碱骨料反应的目的。     

高温下锂化合物抑制碱硅酸反应的研究

系统研究了高温条件下锂化合物对碱硅酸反应(ASR)的抑制作用.含沸石化珍珠岩活性集料砂浆, 在150 ℃压蒸24 h后, 置于80 ℃养护至20 个月.研究发现:分别掺加n(Li)/ n(Na)为0.6的Li2CO3, LiOH·H2O, Li2SO4·H2O, LiCH3COO·2H2O, LiNO3, LiF能长期有效地抑制ASR膨胀, 且抑制效果依次增强.在碱含量为2.0%时, 掺加相同n(Li)/n(Na)的锂化合物, 其对膨胀的长期抑制效果与溶解度有关.随着锂化合物阴离子表面电荷密度的增加, 其对膨胀的抑制效果依次增强.此外 , 本工作还探讨了锂化合物抑制ASR的作用机理.     

溶胶-凝胶法制备的SiO2催化生长单壁碳纳米管

溶胶-凝胶法是制备纳米粒子的一种重要方法。采用高化学活性的化合物作反应前驱体经溶胶、凝胶过程,再经热处理而生成颗粒较均一的纳米粒子。分别在酸催化和碱催化条件下以原硅酸四乙酯（TEOS）为前躯体制备出SiO2纳米颗粒,用于生长单壁碳纳米管。最后发现,此SiO2粒子作为一种非金属催化剂,其催化生长的碳纳米管密度和结构均一而且产物中无残留催化剂颗粒,扩大了碳纳米管的性能及应用。     

关于碱-集料反应的几个理论问题

本文详细评述了碱-集料反应的分类、膨胀机理、Ca(OH)_2的作用和混合材的抑制机理。认为所谓的碱-硅酸盐反应实质上很可能是传统的碱-硅酸反应。碱-硅酸反应主要是吸水引起膨胀。碱-碳酸盐反应是由原地化学反应和结晶压引起膨胀。目前比较一致的意见认为Ca(OH)_2对促进碱-集料反应起着重要作用。最后本文从水泥的碱度和界面化学反应的角度分析了混合材的抑制机理。     

矿物掺合料和锂盐对碱-硅反应的抑制作用

碱-硅反应是混凝土碱集料反应中最易发生的环节,且潜伏期长,一般是1-10年.其一旦发生,就难以抑制,导致混凝土的膨胀和开裂,直至混凝土被破坏.本文综述了碱-硅反应的机理,并介绍了采用粉煤灰等矿物掺合料和锂盐以抑制碱-硅反应的效果.矿物掺合料主要通过减少孔溶液中碱的含量抑制碱-硅反应,锂盐主要通过生成非膨胀性的产物抑制碱...     

碱活性集料在不同碱液中压蒸后产物的研究

通过X射线衍射及扫描电镜／能谱分析法对2种典型的碱硅酸活性集料(Spratt limestone,SL)和碱碳酸盐活性集料(Pittsburg limestone,PL)在KOH,NaOH及LiOH溶液中于150℃压蒸150h后的产物进行了研究,结果表明：NaOH对2种集料有最强的腐蚀作用,腐蚀作用最弱的是LiOH。2种集料在不同的碱介质中压蒸后,产物的结晶度、形貌及分布是不同的。PL在碱液中除了去白云化反应外,PL中的隐晶石英也与KOH和NaOH反应生成典型的碱一硅酸产物,与LiOH反应形成硅酸锂。SL在不同碱液中除生成大量碱一硅酸产物外,SL中的少量的白云石在碱溶液中也发生了去白云石化反应,对膨胀作出贡献。     

天然沸石对碱-硅酸反应的抑制及其机理

用高碱水泥和天然沸石制备了含沸石水泥，测定了其砂浆棒的膨胀率，可溶性碱量和有效碱量。用能谱分析（EDXA）了C－S－H凝胶的化学组成。讨论了总碱量，可溶性碱量和有效碱量与膨胀率的关系。结果显示，由碱－硅酸反应（ASR）引起的膨胀与可溶性碱量和有效碱量之间有很好的关系。沸石主要通过离子交换和提高C－S－H凝胶对Na^ 和K^ 的吸收，使可溶性碱量和有效碱量降低，从而起到抑制ASR的作用。     

新疆大石峡水利枢纽混凝土碱-硅酸反应抑制研究

新疆大石峡水利枢纽混凝土选用的骨料存在碱活性,可能导致工程产生碱骨料破坏问题,本文研究了当地粉煤灰和矿粉对碱-硅酸反应(ASR)的影响,并采用XRD和SEM-EDS测试分析了水化产物和界面过渡区的形态。结果表明：粉煤灰掺量≥20%(质量分数)或矿粉掺量≥40%(质量分数)都能显著抑制碱-硅酸反应;在纯水泥样品界面过渡区可以观察到无定形相,在含有粉煤灰或矿粉的样品中未观察到无定形相,这意味着碱-硅酸反应发生在纯水泥样品中;添加粉煤灰或矿粉降低了界面过渡区物相的Ca/Si摩尔比,抑制了碱-硅酸反应。     

集料粒径与ASR膨胀关系及膨胀预测研究进展

综述了集料粒径与碱硅酸反应(ASR)膨胀关系的研究现状,指出了ASR膨胀研究存在的局限性,阐述了大粒径、多级配集料ASR膨胀规律研究的必要性.介绍了几种ASR膨胀机理及ASR膨胀预测模型,并指出基于碱硅酸反应活化能的测定预测ASR膨胀将可能成为今后研究的一个热点.     

Effects of lithium salts on ASR gel composition and expansion of mortars

Suppression of alkali-silica reaction (ASR) expansion in mortar and concrete by the addition of lithium salts has been confirmed by some workers. It has been revealed that lithium hydroxide tended to reduce the reaction between sodium or potassium hydroxide and reactive silica, and that the ASR gel incorporating lithium was less expansive. However, it has not been reported how the addition of a lithium salt influenced the composition of the ASR gel. The calcium in ASR gel is considered to play an important role in the expansion of the gel. Thus, it is significant to characterize ASR gel composition in mortars containing lithium salts by BSE-EDS analysis. This study aims to discuss the mechanisms of suppression of ASR expansion in mortar by lithium salts from the viewpoint of ASR gel composition. The average CaO/SiO₂ ratio in ASR gels decreased with increasing amount of added lithium salts. It should be noted that the extent of variations in the CaO/SiO₂ ratio in ASR gels significantly decreased with increasing amount of lithium salts. The addition of relatively small amounts of LiOH and Li₂CO₃ resulted in increased expansion. We also obtained an unexpected result that ASR gels became homogeneous with respect to their CaO contents at high dosage levels. However, the reduction in average CaO/SiO₂ ratios and the homogenization in the CaO content of ASR gels due to the addition of lithium salts may not be related to the expansion of mortars.     

Examination of the effects of LiOH, LiCl, and LiNO3 on alkali-silica reaction

Lithium additives have been shown to reduce expansion associated with alkali-silica reaction (ASR), but the mechanism(s) by which they act have not been understood. The aim of this research is to assess the effectiveness of three lithium additives—LiOH, LiCl, and LiNO₃—at various dosages, with a broader goal of improving the understanding of the means by which lithium acts. The effect of lithium additives on ASR was assessed using mortar bar expansion testing and quantitative elemental analysis to measure changes in concentrations of solution phase species (Si, Na, Ca, and Li) in filtrates obtained at different times from slurries of silica gel and alkali solution. Results from mortar bar tests indicate that each of the lithium additives tested was effective in reducing expansion below an acceptable limit of 0.05% at 56 days. However, different lithium additive threshold dosages ([Li₂O]/[Na₂O_e]) were required to accomplish this reduction in expansion; these were found to be approximately 0.6 for LiOH, 0.8 for LiNO₃, and 0.9 for LiCl. Quantitative elemental analysis indicated that sodium and lithium were both bound in reaction products formed within the silica gel slurry. It is also believed that lithium may have been preferentially bound over sodium in at least one of the reaction products because a greater percent decrease in dissolved lithium than dissolved sodium was observed within the first 24 h. It appears that lithium additives either decreased silica dissolution, or promoted precipitation of silica-rich products (some of which may be nonexpansive), because the dissolved silica concentration decreased with increasing dosage of lithium nitrate or lithium chloride additive.     

锂盐抑制ASR的长期有效性研究

较系统地研究了三种锂盐对沸石化珍珠岩集料砂浆ASR膨胀的影响,证实了锂盐抑制效果的长期有效性,确立了不同碱含量条件下锂盐有效抑制ASR膨胀的Li与Na的摩尔比,并从机理上加以探讨.     

Effects of externally supplied lithium on the suppression of ASR expansion in mortars

Lithium salts are being externally supplied for mitigating the progress of deterioration of ASR-affected concrete structures. However, it is not clear whether the sodium or potassium in the ASR gel in concrete is replaced by the lithium supplied from the outside. In this article, we examine changes in the composition of the ASR gel, previously formed in mortar specimens, after they are immersed in LiOH solution, using backscattered electron (BSE) imaging and energy-dispersive X-ray (EDX) analysis, associated with length change measurement of the mortar prisms. The intrusion of lithium ions into mortar specimens containing a reactive aggregate could arrest their further expansion within a relatively short time after immersion in 0.50 N LiOH solution. The alkali ions incorporated in most ASR gels, located not far away from interfaces between the cement paste and reactive aggregate particles, appear to be replaced by the lithium ions supplied from the solution. However, the ASR gel within the reacted aggregate particles did not appear to have been affected by the lithium ions.     

Summary of research on the effect of LiNO3 on alkali-silica reaction in new concrete

This paper summarizes findings from a research study conducted at the University of New Brunswick in collaboration with the University of Texas at Austin, and CANMET-MTL, on the effect of LiNO₃ on ASR in new concrete. The studies included expansion testing, silica dissolution measurements and microstructural examinations of cement systems containing glass and two different reactive aggregates (NB and NS). Only a small proportion of the data are presented here for the purpose of highlighting the principal findings of this investigation.Based on these findings, it is proposed that the inhibiting effect of LiNO₃ against ASR in new concrete is attributed to the formation of two reaction products in the presence of lithium, these being a crystalline lithium silicate compound (Li₂SiO₃) crystal and a Li-bearing, low Ca silica gel. These two phases could serve as a diffusion barrier and protective layer to prevent the reactive silica from further attack by alkalis.It was found that the reason the two reactive aggregates selected responded differently to LiNO₃ was due to the difference in their textural features. The NB aggregate contained reactive volcanic glass particles, the surface of which was immediately and equally available to sodium, potassium and lithium, and thus a Li-Si barrier was able to form quickly. The reactive phase in the NS aggregate was microcrystalline and strained quartz, which was embedded in a dense matrix of a non-reactive predominantly alumino-silicate phase and was not easily accessible to lithium.     

Experimental investigation of the mechanisms by which LiNO3 is effective against ASR

Various series of experiments were carried out on cements pastes, concretes made with a variety of reactive aggregates, composite specimens made of cement paste and reactive aggregate particles, and a variety of reactive natural aggregates and mineral phases immersed in various Li-bearing solutions. The main objective was to determine which mechanisms(s) better explain(s) the effectiveness of LiNO₃ against ASR and variations in this effectiveness as well with the type of reactive aggregate to counteract. The principal conclusions are the following: (1), the pH in the concrete pore solution does not significantly decrease in the presence of LiNO₃; (2), the concentration of silica in the pore solution is always low and not affected by the presence of LiNO₃, which does not support the mechanism relating to higher solubility of silica in the presence of lithium; (3), the only reaction product observed in the LiNO₃-bearing concretes looks like classical ASR gel and its abundance is proportional to concrete expansion, thus is likely expansive while likely containing lithium; this does not support the mechanisms relating to formation of a non or less expansive Si-Li crystalline product or amorphous gel; (4), early-formed reaction products coating the reactive silica grains or aggregate particles, which could act as a physical barrier against further chemical attack of silica, were not observed in the LiNO₃-bearing concretes, but only for a number of reactive materials after immersion in 1 N LiOH at 350 °C in the autoclave (also at 80 °C for obsidian); (5), higher chemical stability of silica due to another reason than pH reduction or early formation of a protective coating over the reactive phases, is the mechanism among those considered in this study that better explains the effectiveness of LiNO₃ against ASR.     

New observations on the mechanism of lithium nitrate against alkali silica reaction (ASR)

In the current study, in order to elucidate the mechanisms for the favorable effects of lithium nitrate in controlling alkali silica reaction (ASR), vycor glass disk immersion specimens and glass disk-cement paste sandwich specimens were prepared and examined by XRD, SEM and Laser Ablation Induction Coupled Plasma Mass Spectrometry (LA-ICP-MS). Results showed that when glass disk was immersed in only NaOH solution, the glass was attacked by hydroxyl ions but no solid reaction product was found, thus the presence of calcium was essential for the formation of ASR gel. In the presence of lithium, the glass surface was covered by a thick layer of Li-Si crystal. With the addition of Ca(OH)₂, the glass surface was completely covered by Li-Si crystal and a lithium-bearing low Ca-Na-(K)-Si gel. These two phases either form a dense matrix with Li-Si crystal serving as the framework, and the gel filling in the void space, or the Li-Si crystal serving as the foundation to completely cover the entire reactive SiO₂ surface, and the gel sitting on top of these crystal particles. Hence, the suppressive effects of LiNO₃ were attributed to the formation of a layer of Li-Si crystals intimately at the reactive SiO₂ particle surface and the formation of Li-bearing low-Ca ASR gel products. The Li-bearing low-Ca ASR gels may have a dense and rigid structure, thus having low capacity to absorb moisture from the surrounding paste, and exhibiting a non-swelling property.     

不同结构构造硅质集料的碱硅酸反应模型

正确认识不同结构构造特征集料的碱硅酸反应（ASR）特征，对判定集料碱活性和诊断工程ASR事例以及采取正确预防措施均有重要意义、早期的以单一组分的高活性集料为基础提出的ASR模型只强调集料中活性组分对ASR的作用，仅适用于特定类型的高活性集料，本工作用扫描电镜（SEM）和光学显微镜研究了石英玻璃、沸石化珍珠岩和硅质砾石反尖特征，并综合对慢膨胀型休料ASR研究的文献，提出了结构构造特征不同的硅质活活性集料的ASR基本模型：结构构造特征不同的活性休料其ASR过程及膨胀行为不同；对以无定型SiO2为活性组分的均质高活性集料，反应特征符合传统的ASR模型；对致密、多矿物慢膨胀型集料，除活性组分类型和数量外，活性组分在集料内的分布，即集料的构造特征对ASR的速度和膨胀行为也有重要影响，结构构造特征不同的活性集料其ASR过程及膨胀行为差别的关键在于膨胀的根源和限制条件不同。