碱－白云石反应及碱－碳酸盐岩反应的膨胀机理

应用分析电镜／能谱仪（ＡＥＭ／ＥＤＳ）和薄膜试样分析技术，研究了与碱反应前后活性碳酸盐岩的结构和组成变化，采用ＥＤＳ定量分析测定了白云石晶体中的Ｃａ／Ｍｇ（Ｃ）的分布，从理论上求出了碱－白云石反应碱溶液的ｐＨ临界值与白云石的组成Ｃ有关。认为采取降低混凝土溶液ｐＨ值的措施不能保证以活性碳酸盐岩作集料的混凝土的耐久性，提出碱－碳酸盐岩反应膨胀机理是：固相产物吸水肿胀加上产物水镁石和方解石晶体生长及重排产生的结晶压力。膨胀值的大小不仅取决于碱－白云石反应进行的程度，而且取决于产物的晶粒尺寸和结晶度。     

碱—白云石反应及碱—碳酸盐岩反应的膨胀机理

应用分析电镜／能谱仪（ＡＥＭ／ＥＤＳ）和薄膜试样分析技术，研究了与碱反应前后活性碳酸盐岩的结构和组成变化，采用ＥＤＳ定量分析测定了白云石晶体的Ｃａ／Ｍｇ（Ｃ）的分布，从理论上求出了碱－白云石反应碱溶液的ｐＨ临界值与白云石的组成Ｃ有关。认为采取降低混凝土溶液ＰＨ值的措施不能保证以活性碳酸盐岩作集料的混凝土的耐久性。提出碱－碳酸盐岩反应膨胀机理是：固相产物吸水肿胀加上产物水镁石和方解石晶体生长及重排产     

碱－碳酸盐岩反应的膨胀机理

应用分析电镜／能谱仪（ＡＥＭ／ＥＤＳ）和薄膜试样分析技术，研究了与碱反应前后活性碳酸盐岩的结构和组成变化。根据研究结果把碱－碳酸盐岩反应膨胀机理归为：固相产物吸水肿胀和产物水镁石和方解石晶体生长和重排产生的结晶压力。膨胀值的大小取决于产物层的表观体积。     

碱碳酸盐反应的膨胀机理

将具有碱碳酸盐反应活性的骨料置于已知浓度的碱溶液中,通过分析溶液中碱离子浓度的变化,分析和探讨碱碳酸盐反应的膨胀机理。实验证实：去白云石化反应的产物层中除了方解石和水镁石外,还有K^ ,Na^ 和CO3^2-,即去白云石化反应的反应产物K^ ,Na^ 和CO3^2-并不回到孔溶液中,而是保留在产物层中占据一定的空间。因此,去白云石化反应产物所占据的空间大于参加反应的白云石所占据的空间,从而引起膨胀。     

方解石颗粒尺寸对白云质灰岩中碱白云石反应的影响

探讨了白云质灰岩中方解石基质对Na＋在岩石中迁移及其对碱白云石反应的影响。采用图像分析法测定不同白云质灰岩样本中方解石颗粒的尺寸,采用N2吸附法测定岩石孔径分布,采用火焰光度计测定养护在80℃、1 mol／L NaOH溶液中岩石柱内部的Na＋含量,采用X-射线内标法定量分析白云质灰岩中碱白云石反应（ ADR）生成的水镁石含量。结果表明,白云质灰岩TS-1、TS-2、GS-2及FHS-1中方解石颗粒中位径分别为4μm、12μm、15μm和33μm;方解石颗粒越小,迁移到岩石内部的Na＋含量越高,岩石中白云石的碱白云石反应程度越高。     

岩石材料的碱-碳酸盐和碱-白云石反应

用含碳酸盐和白云石的岩石粉末置于40℃不同浓度的碱溶液中一年或6个月，研究其碱-碳酸盐和碱-白云石反应。根据热力学计算，碱-碳酸盐和碱-白云石反应是可以进行的。XRD分析证实，岩石粉中的确有水镁石生成，ESEM和EDX检测出岩石表面存在水镁石，沉淀的产物和化学溶液的测定证明了岩石的分解和新产物的形成。但在细颗粒砂浆试验中碱-白云石反应未得到证实。德国魏玛的Finger建筑材料研究院宣称的碱-白云石反应的破坏也未检测到。     

碱-碳酸盐岩反应机理

本文应用光学显微镜、扫描电子显微镜、透射扫描电子显微镜和能谱仪(SEM/EDAX和召TEM/EDAX)比较详细地研究了活性碳酸盐岩石的微观结构。实验表明,在活性碳酸盐岩石中,菱形白云石晶体孤立地分布在由微晶方解石和粘土所构成的墓质中,粘土呈网络状分布在微晶方解石之间。活性岩石经碱液作用后,在白云石晶体外面生成平行排列的水镁石晶体。根据微观结构的研究结果可以提出碱-碳酸盐岩反应的膨胀机理:OH~-,M~+和水分子通过粘土网络间的通道进入岩石内部与白云石晶体反应,这些离子和水进入限制空间以及白云石晶体表面,由于反白云化而产生的晶体生长和重排是引起膨胀的根本原因。     

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。     

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。     

碱—碳酸盐反应和pH值

热力学计算表明,碱—碳酸盐反应的AG_(298)~0=-12.19kJ。这是去白云石化反应得以进行的化学推动力。文中列出了计算所得的白云石稳定区和不稳定区的范围。由此得出,溶液中的pH愈高,CO_3~(2-)浓度愈低,则白云石愈不稳定。这就从理论上阐明了为什么水泥中碱含量愈高,碱—碳酸盐反应愈烈,膨胀破坏作用就愈大。混合材掺量很高时,才能显著降低水泥石液相中的pH值,从而缓和碱—碳酸盐反应。这再一次证明碱—碳酸盐反应与去白云石化密切相关。实验和理论证明,碱—碳酸盐反应是由于去白云石化在原地产生,这种局部化学反应和结晶压是引起膨胀的根本原因。要抑制碱—碳酸盐反应,防止混凝土工程遭受破坏,最根本的途径是采用高混合材掺量的低碱水泥。     

Mechanism of dedolomitization and expansion of dolomitic rocks

Based on thermodynamic analysis of the dedolomitization reaction and calculation of the volume change associated with this reaction by the principle of the tightest pile of particles, the influences of pH value on alkali-dolomite reaction and expansion were investigated. Dedolomitization reaction and its expansibility were evaluated by examination of dolostone powder-cement compacts and dolomitic rocks containing few clays and quartz. Dolomite reacts with hydroxyl to form CO₃²⁻ ion, brucite and calcite, which are fine, generally smaller than 1 μm, and enclose many voids. It is confirmed by seveal means that dedolomitization reaction can directly bring about expansion. The rates of both the reaction and expansion depend markedly on the pH value of solutions. The higher the pH value, the larger the rates. When pH value is low enough, the reaction does not take place, thus no expansion appears.     

混凝土中白云岩的去白云石化反应与机理

采用岩相分析、扫描电子显微分析、电子探针、电泳试验等研究了混凝土内白云岩中的去白云石化过程和机理。结果表明 ,白云岩中的去白云石化反应属原位化学反应 ,反应仅限定在界面处集料边缘反应环的窄小区间内 ,反应生成的胶体尺寸的水镁石吸附 OH-离子形成带负电的扩散双电层 ,阻止 OH-离子向白云岩内部迁移 ,水镁石和方解石在有限空间成核与生长 ,形成无序排列的水镁石和方解石晶体     

Alkali Silica Reaction (ASR) as a root cause of distress in a concrete made from Alkali Carbonate Reaction (ACR) potentially susceptible aggregates

The mechanism of Alkali Carbonate Reaction (ACR) in concrete made from fine-grained, argillaceous dolomitic limestone coarse aggregates remains controversial. ACR distress is described as an increase in volume caused by the crystallization of brucite during the dedolomitization process. However, recent studies by Katayama suggest that ACR is a combination of the “deleteriously expansive Alkali Silica Reaction (ASR) of cryptocrystalline quartz in the matrix of the reactive aggregates and a harmless dedolomitization that produces brucite and a carbonate halo.” We investigated ACR susceptible concrete extracted from a wharf structure in Quebec, Canada, and determined that ASR was the cause of damage. Optical and SEM-EDS analyses identified ASR gel extending from reactive aggregates to the paste, and X-ray elemental mapping confirmed the gel composition. Silica (Si) was found in the matrix of the aggregate and is the source of reactive silica. These results support ASR as the mechanism in ACR susceptible concrete.     

Comparison of the morphology of alkali–silica gel formed in limestones in concrete affected by the so-called alkali–carbonate reaction (ACR) and alkali–silica reaction (ASR)

The morphology of alkali–silica gel formed in dolomitic limestone affected by the so-called alkali–carbonate reaction (ACR) is compared to that formed in a siliceous limestone affected by alkali–silica reaction (ASR). The particle of dolomitic limestone was extracted from the experimental sidewalk in Kingston, Ontario, Canada that was badly cracked due to ACR. The siliceous limestone particle was extracted from a core taken from a highway structure in Quebec, affected by ASR. Both cores exhibited marked reaction rims around limestone particles. The aggregate particles were polished and given a light gold coating in preparation for examination in a scanning electron microscope. The gel in the ACR aggregate formed stringers between the calcite crystals in the matrix of the rock, whereas gel in ASR concrete formed a thick layer on top of the calcite crystals, that are of the same size as in the ACR aggregate.     

The development and stability of surface layers on concrete exposed to sea-water

Concrete exposed to sea-water may develop a surface skin causing a marked reduction in permeability. The skin typically consists of a layer of brucite (magnesium hydroxide) of aroun 30 μm thickness, overlain by a thicker, but more slowly developing, layer of aragonite (calcium carbonate). The aragonite may convert to calcite in an aqueous environment free from magnesium ion.The degree of saturation of sea-water with aragonite or brucite is primarily a function of its pH value. Uncontaminated sea-water has a pH within the range 7.8 to 8.3 and is supersaturated with aragonite at pH values greater than around 8.1. For good correlation of laboratory tests with natural exposure conditions appreciable increases in pH should therefore be prevented. Temperature variations may have a significant effect on layer precipitation, but the range of pressures encountered by offshore structures has negligible effect. Organic compounds present in sea-water may inhibit precipitation.     

The so-called alkali-carbonate reaction (ACR) — Its mineralogical and geochemical details, with special reference to ASR

Typical examples of so-called alkali-carbonate reaction (ACR) in the Canadian field concretes in Ontario, CSA concrete prism, RILEM concrete microbars and RILEM mortar bar containing Pittsburg aggregate, were examined petrographically based on polarizing microscopy, SEM observation and quantitative SEM-EDS analysis of the reaction products. It was revealed that ASR gel was the main product responsible for the crack formation in concretes, and that this gel had a common nature to that in the typical ASR. That is, ASR gel presented distinctive compositional trend lines, passing from low-Ca ASR gel at [Ca/Si] = 1/2-1/6, [Ca]/[Na + K] = 1.0 to the “convergent point” with [Ca/Si] = 1.3-1.8, [Ca]/[Na + K] = 100 at which chemical equilibrium is attained with CSH gel. The so-called ACR is a combination of deleteriously expansive alkali-silica reaction (ASR) of cryptocrystalline quartz, and harmless dedolomitization which produces brucite and carbonate halo. In laboratory specimens, fine dolomitic aggregate undergoes dedolomitization, and brucite and ASR gel react to form non-expansive Mg-silicate gel on the dolomite crystals. This explains why the mortar bar produces smaller expansion than the concrete microbar, and why the reaction products are so minute that they escape attention by optical microscopy. As a crystalline counterpart, mountainite is a candidate for low-Ca ASR gel, while sepiolite is one for Mg-silicate gel. Concealed ASR was detected in ACR-affected field concretes undergoing ingress of deicing salt which formed Friedel's salt and Cl-doped CSH gel. Compositions of ASR products, methods of sample preparation and analysis for correct identification of ACR, and artifacts were critically reviewed.     

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.     

A model investigation of the influence of particle shape on portland cement hydration

The NIST Virtual Cement and Concrete Testing Laboratory (VCCTL) is used to simulate the influence of particle shape on the hydration kinetics and setting of portland cement. Building on previous work in reconstructing particle shapes from real cements, real-shape particles are used to produce three-dimensional digitized cement paste microstructures, and the hydration of these microstructures is tracked using VCCTL. The degree of hydration and percolation of solids is monitored and compared to experimental data at several water-cement ratios. The simulations predict that shapes of particles influence cement hydration in two ways: the additional surface / volume ratio relative to spherical particles results in greater rates of hydration, and the anisometry in shape influences the degree of hydration at which the particles and hydration products percolate to form a stiff three-dimensional network.