用溶胶-凝胶膨胀法对锂化合物抑制碱-硅酸反应膨胀机理的研究

利用溶胶-凝胶膨胀法对锂化合物在碱硅酸反应中膨胀的抑制机理进行了研究,对加入锂盐后的碱-硅酸反应产物的膨胀量进行了测定,并借助扫描电镜对试样的微观形貌进行了观察,同时还测定了反应后溶液中SiO2的含量,证实了锂化合物的作用在于：抑制骨料中活性SiO2的溶出;改变凝胶产物的性质,使凝胶的吸水能力和膨胀量变小。     

Ca(OH)_2对碱-硅酸反应的影响

本文首先研究了不同的pH溶液对蛋白石的侵蚀作用,发现当pH值大于12～12.5时,SiO_2的溶出量急剧增加。其次对比研究了硅酸盐水泥、矾土水泥、石膏矿渣水泥和赤泥硫酸盐水泥中的碱-硅酸反应。发现当碱含量相同时,硅酸盐水泥中碱-硅酸反应最剧烈。原因是其水泥石液相中OH~-浓度较高,即使碱含量很低,由于有Ca(OH)_2存在,液相pH值也在12.5以上。其他水泥则不同。从Ca(OH)_2的作用出发,阐明了混合材对碱-硅酸反应的抑制机理,并通过试验予以证实。文中还提出采用不含或少含Ca(OH)_2的水泥以避免其他来源的碱引起的碱-硅酸反应。     

混凝土中碱—骨料反应膨胀机理的探讨

本文从碱—硅络合物的一系列物理化学特性着手,通过显微观察和模型的综合论证试验,初步认为在实际混凝土中碱与活性SiO_2骨料反应的膨胀机理,肿胀压与渗透压两者均能存在。随水和碱不断进入到反应产物中,渗透压力的比重随吸水时间的增长而增长。早期以肿胀压为主导,后期以渗透压为主导。从有关资料分析,Ca(OH)_2不能促进碱—骨料反应,pH值也不是控制这一反应的绝对条件。膨胀发生的充分而必要的条件是碱—骨科反应的Na_2O—SiO_2—H_2O体系中三者的量必须同时相应具备。     

关于碱-骨料反应的几个问题

对于碱-骨料反应,去年我们曾撰文论述Ca(OH)_2的作用和膨胀的机理。承各位专家教授提出不少宝贵意见,启发颇大。一年多来通过补充试验和对资料的分析,现将目前我们对几个主要问题的认识申述如下。 一、关于膨胀机理 1944年W.C.Hansen首次提出碱-骨料膨胀反应的渗透压理论。 Kalaulsek在时论Hansen的论文时指     

含碱集料对碱-硅酸反应的影响

采用80℃蒸汽养护快速实验方法,研究了2种不同类型含碱集料--霞石正长岩和白岗岩对碱-硅酸反应的影响,并通过在150℃不同的碱溶液中压蒸集料的方法,对含碱集料的析碱机理进行了分析.结果表明:霞石正长岩和白岗岩对碱-硅酸反应膨胀的影响与使用水泥的碱含量有关.在使用低碱水泥时,霞石正长岩和白岗岩使碱罐酸反应膨胀显著增大,而在使用高碱水泥时,霞石正长岩和白岗岩对碱-硅酸反应膨胀促进作用均减弱;在饱和Ca(OH)2溶液中的霞石矿物能稳定存在,随着碱含量的增加,霞石矿物发生分解,而长石矿物均能稳定存在,与碱溶液的反应仅在长石矿物表面区域进行.长石矿物与混凝土孔溶液中Ca2 之间的离子交换反应是混凝土中长石矿物析碱的主要原因.     

碱激发偏高岭土-矿渣砂浆的碱骨料反应机理研究

碱激发胶凝材料是一种新型低碳材料，其液相环境的碱度普遍高于水泥基材料，势必导致碱骨料反应引起的体积变形不同于水泥基材料。为探究碱激发胶凝材料的碱骨料反应行为与液相碱度的关系，选取花岗岩为代表性骨料制备碱激发偏高岭土-矿渣砂浆，研究在不同浓度NaOH溶液浸泡下的砂浆变形行为。结合微观分析表明，碱激发胶凝材料的体积收缩能很好地抑制碱骨料反应产生的膨胀，不同浸泡条件下碱激发偏高岭土-矿渣砂浆会呈现不同的变形行为。碱激发偏高岭土-矿渣砂浆的膨胀是由碱骨料反应生成产物以及原类沸石结构的水化硅铝酸钠凝胶向沸石结构转化所造成的。当碱激发胶凝材料的孔溶液氢氧根离子浓度大于0.209 mol/L时，碱骨料反应会发生。     

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。     

霞石正长岩对碱-硅酸反应的影响

以霞石正长岩为代表,研究了含碱集料对碱-硅酸反应膨胀的影响。研究结果表明,80℃或150℃蒸汽养护条件下可快速检测出霞石正长岩对碱-硅酸反应的影响;霞石正长岩在混凝土中的分解反应在增加混凝土可溶碱含量的同时,反应本身还将降低孔溶液OH-浓度,因此由霞石正长岩分解析出的碱与水泥中的碱对碱-硅酸反应影响不同,只有在适当的条件下才能显著增大碱-硅酸反应膨胀。     

燧石粉对ASR膨胀性抑制作用的研究

当存在碱硅酸反应风险时,如何抑制混凝土的膨胀破坏是很重要的.本文探讨将磨细碱活性骨料作为混凝土掺合料,研究其对ASR膨胀性的抑制作用.文中对比燧石粉不同比表面积和不同掺量的胶砂试件,采用快速砂浆棒法测定其在各龄期膨胀率,并结合扫描电子显微镜( SEM)和能谱分析( EDS),研究磨细燧石粉对于ASR (Alkali-Silica Reaction, ASR)膨胀性的影响.结果表明:通过掺加一定比表面积和掺量燧石粉可以有效地抑制胶砂试件因ASR产生的膨胀;SEM和EDS分析显示掺入一定比表面积和适量的燧石粉后,燧石骨料周围碱硅酸凝胶产量减少,说明燧石粉的掺入可以有效减少活性骨料表面发生ASR;同时水化硅酸钙的钙硅比亦有所降低,提升水化硅酸钙的固碱能力,进一步有效抑制ASR.本研究结果能为使用潜在碱活性骨料时,抑制其ASR反应措施提供一定的参考.     

粉煤灰抵制碱骨料反应研究

研究优质Ⅰ级粉煤灰对碱骨料反应的抑制效果,结果表明,用粉煤灰抑制碱骨料反应,其掺量因素的影响大于品质因素的影响;探讨了粉煤灰中的碱在不同浓度碱溶液中的溶出情况及用高碱含量粉煤灰抑制碱骨料反应时,低掺量促进膨胀,高掺量抑制膨胀的机理.     

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.     

激发剂对碱矿渣水泥砂浆中碱-硅酸反应的影响

采用硅酸钠溶液为激发剂制备碱矿渣(AAS)水泥砂浆,在80 ℃的1 mol/L氢氧化钠溶液中养护以加速碱-硅酸反应(ASR)进程,研究了激发剂碱含量和硅酸盐模数对ASR膨胀破坏的影响。结果表明,AAS砂浆中出现了危险性ASR膨胀破坏。激发剂中Na₂O掺量大于4%(质量分数)时,砂浆在14 d龄期的ASR膨胀率超过0.1%,且当激发剂硅酸盐模数在1.2~2.0范围内时膨胀率更大。ASR产物主要分布在集料颗粒表面与AAS凝胶相接触的界面区,附近可观测到明显的裂缝扩展。ASR膨胀破坏同时引发了砂浆抗压强度损失。     

Mechanical approach in mitigating alkali-silica reaction

The effect of steel microfibers (SMF) on alkali-silica reaction (ASR) was investigated using two types of reactive aggregates, crushed opal and a Pyrex rod of constant diameter. Cracks are less visible in the SMF mortars compared with the unreinforced mortars. Due to crack growth resistance behavior in SMF mortar specimens, the strength loss is eliminated and the ASR products remained well confined within the ASR site. The expansion and the ASR products were characterized by microprobe analysis and inductive coupled plasma (ICP) spectroscopy. The confinement due to SMF resulted in a higher Na and Si ion concentration of the ASR liquid extracted from the reaction site. The higher concentration reduced the ASR rate and resulted in a lower reactivity of the reactive Pyrex rods in SMF mortars.     

Modified model of alkali-silica reaction

Experimental studies have been carried out for understanding why soft and fluid hydrated alkali silicate generated by the alkali-silica reaction (ASR) of aggregate with alkaline pore solution accumulates the expansive pressure for cracking the aggregate and the surrounding concrete. The elemental analysis of aggregate (andesite) embedded in a cement paste has revealed that the alkali silicate has no ability of generating expansive pressure unless the aggregate is tightly packed with a reaction rim. The reaction rim is slowly generated from the alkali silicate that covers the ASR-affected aggregate. Consumption of alkali hydroxide by the ASR induces the dissolution of Ca²⁺ ions into the pore solution. The alkali silicate then reacts with Ca⁺ ions to convert to an insoluble tight and rigid reaction rim. The reaction rim allows the penetration of alkaline solution but prevents the leakage of viscous alkali silicate, so that the alkali silicate generated afterward by the ASR is accumulated in the aggregate to give an expansive pressure enough for cracking the aggregate and the surrounding concrete. The ASR of very tiny aggregate such as fly ash and municipal waste incinerator bottom ash may not cause the deterioration of concrete, since the ASR is completed before the formation of reaction rims.     

Chemical Sequence and Kinetics of Alkali‐Silica Reaction Part I. Experiments

The deterioration induced by alkali‐silica reaction (ASR) is initiated by complicated heterogeneous chemical reactions. This study describes the experimental results obtained from the model reactant experiments focused on the kinetics of physical and chemical changes in the reactive aggregate‐simulated pore solution system undergoing ASR. Specifically, the study investigated the products formed by exposing reactive silica mineral (α‐cristobalite) to two alkali solutions in the presence of solid calcium hydroxide [Ca(OH)₂]. The experimental results showed that, as long as the Ca(OH)₂ remains in the system, the dissolution of the silica mineral proceeds at a constant rate and the only reaction product formed is the tobermorite‐type C–S–H. However, once the supply of Ca(OH)₂ in the system is exhausted, the level of dissolved silica ions starts to increase. At the same time, the previously formed C–S–H changes in composition by incorporating silicon and alkali ions from the solution. Continuous increase in the concentration of silica leads to formation of the ASR gel as a result of interaction between silica and alkali ions.     

废玻璃粉作为辅助胶凝材料对砂浆性能影响及作用机理

作为辅助胶凝材料掺入混凝土是废弃玻璃回收利用的途径之一。研究废玻璃粉掺料对砂浆性能影响及作用机理,结果可为该类应用提供指导。本文研究0~0.075 mm、0.075~0.15 mm和0.15~0.3 mm这三组不同粒径废玻璃粉作为辅助胶凝材料对砂浆力学性能及碱硅酸反应(ASR)膨胀作用的影响。研究发现:掺入玻璃粉粒径为0~0.075 mm可将砂浆28 d抗压强度增加5%~15%,ASR膨胀率减小20.2%;掺入玻璃粉粒径为0.15~0.3 mm则使砂浆28 d抗压强度降低5%~8%,ASR膨胀率增加39.7%。采用热重分析、等离子电感耦合、扫描电镜及能谱分析试验对反应产物、孔溶液、微观结构及其元素分布进行检测。分析认为粒径粗的玻璃粉碱骨料活性强,易发生ASR,导致膨胀率增加;粒径细的火山灰活性强,发生火山灰反应生成了膨胀率低的低钙硅比水化硅酸钙凝胶,该产物不仅会吸收Na⁺、K⁺,从而减少用于发生ASR的反应物含量,而且更密实,有利于降低孔隙率,减少水的渗透,提高抗压强度并抵抗膨胀压。     

Influence of stress restraint on the expansive behaviour of concrete affected by alkali-silica reaction

The primary objective of this study was to ascertain whether the Threshold Alkali Level (TAL) of the concrete aggregates may be taken as a suitable reactivity parameter for the selection of aggregates susceptible of alkali-silica reaction (ASR), even when ASR expansion in concrete develops under restrained conditions. Concrete mixes made with different alkali contents and two natural siliceous aggregates with very different TALs were tested for their expansivity at 38 °C and 100% RH under unrestrained and restrained conditions. Four compressive stress levels over the range from 0.17 to 3.50 N/mm² were applied by using a new appositely designed experimental equipment. The lowest stress (0.17 N/mm²) was selected in order to estimate the expansive pressure developed by the ASR gel under “free” expansion conditions. It was found that, even under restrained conditions, the threshold alkali level proves to be a suitable reactivity parameter for designing concrete mixes that are not susceptible of deleterious ASR expansion. An empirical relationship between expansive pressure, concrete alkali content and aggregate TAL was developed in view of its possible use for ASR diagnosis and/or safety evaluation of concrete structures.     

ZnS-opal与反opal结构ZnS光子晶体的组装

以单分散SiO2微球为基元,在75%～80%湿度、30～45 ℃恒温密闭烘箱中垂直快速组装opal模板;以Zn(NO3)2（0.035 mol/L）、TAA乙醇溶液（0.05 mol/L）为前体,通过溶剂热法充填形成ZnS-opal复合光子晶体;ZnS-opal复合光子晶体在2%～5%的HF溶液中浸泡4～5 h后卸载模板,制得反opal结构ZnS基光子晶体;采用XRD、SEM、ＵV-Vis测试手段对反opal结构ZnS基光子晶体形貌、物相和光学性能进行了表征。结果表明：溶剂热法多次充填可使ZnS纳米晶在模板密堆积形成的空隙中均匀成核;经过酸处理的ZnS-opal中SiO2微球溶解、坍塌,形成蜂窝状三维有序介孔和反opal结构ZnS基光子晶体;相同粒径SiO2微球组装的opal模板、ZnS-opal以及反opal结构ZnS光子晶体均表现出光子带隙特性,但反opal结构ZnS光子晶体带隙位置相比前两者发生了蓝移。     

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。