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。     

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.     

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。     

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。     

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。     

碱-白云石反应机理与预防

根据颗粒堆积原理计算了碱白云石反应引起的固相框架体积的变化,并用图象分析技术研究了反应产物间的孔隙体积。研究了碱白云石反应机理,从热力学和通过实验分析了溶液ｐＨ值对碱白云石反应程度与速率的影响。通过监测白云岩粉末样压实体和基本不含粘土及石英的白云质灰岩在碱溶液中的膨胀行为,研究了碱白云石反应本身的膨胀性。评估了低碱度的硫铝酸盐水泥对碱白云石反应的抑制作用。结果表明：球形产物如呈最紧密堆积,则固体产物的孔隙率为２５．９５％,碱白云石反应后固相框架体积将增加２９．２３％。实际上,固体产物的孔隙率为１５％,反应后固相框架体积将增加１２．５％,这为反应产生膨胀提供了前提条件。白云石与碱作用生成水镁石、方解石和碳酸碱,该过程能直接引起膨胀。反应和膨胀的速率取决于溶液的ｐＨ值,ｐＨ值越高,反应和膨胀越快,当ｐＨ值低于某一值后,碱白云石反应将不发生,相应地,岩石不产生膨胀。碱白云石反应膨胀的驱动力为去白云化反应生成的方解石和水镁石晶体在受限空间生长产生的结晶压力。硫铝酸盐水泥能有效地抑制碱白云石反应膨胀,从而能防止混凝土的开裂破坏。     

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     

波茨坦砂岩的微观结构和碱活性快速检测方法的适应性

为研究集料微观结构对碱活性快速检测方法中对岩石适应性的影响,采用混凝土棱柱体法、快速砂浆棒法、压蒸法、中国快速砂浆棒法研究了波茨坦砂岩的膨胀行为,并研究了膨胀后试件的微观结构.结果表明:快速砂浆棒法、压蒸法、中国快速砂浆棒法均不能正确判定波茨坦砂岩的碱活性,主要是由于这些方法使用的集料中含大量粒径太小、不能反映该砂岩特殊结构特征的颗粒;对该类岩石,除活性组分的类型、数量外,岩石的微观结构特征能够显著影响碱-集料反应发生的位置和膨胀行为.在快速法中采用能够保持岩石原有结构特征的集料粒径是正确鉴定类似波茨坦砂岩微观结构岩石及其它非均质、多矿物岩石碱活性的关键.     

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。     

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。     

Alteration of alkali reactive aggregates autoclaved in different alkali solutions and application to alkali-aggregate reaction in concrete (II) expansion and microstructure of concrete microbar

The effect of the type of alkalis on the expansion behavior of concrete microbars containing typical aggregate with alkali-silica reactivity and alkali-carbonate reactivity was studied. The results verified that: (1) at the same molar concentration, sodium has the strongest contribution to expansion due to both ASR and ACR, followed by potassium and lithium; (2) sufficient LiOH can completely suppress expansion due to ASR whereas it can induce expansion due to ACR. It is possible to use the duplex effect of LiOH on ASR and ACR to clarify the ACR contribution when ASR and ACR may coexist. It has been shown that a small amount of dolomite in the fine-grained siliceous Spratt limestone, which has always been used as a reference aggregate for high alkali-silica reactivity, might dedolomitize in alkaline environment and contribute to the expansion. That is to say, Spratt limestone may exhibit both alkali-silica and alkali-carbonate reactivity, although alkali-silica reactivity is predominant. Microstructural study suggested that the mechanism in which lithium controls ASR expansion is mainly due to the favorable formation of lithium-containing less-expansive product around aggregate particles and the protection of the reactive aggregate from further attack by alkalis by the lithium-containing product layer.     

Alteration of alkali reactive aggregates autoclaved in different alkali solutions and application to alkali-aggregate reaction in concrete: (I) Alteration of alkali reactive aggregates in alkali solutions

Surface alteration of typical aggregates with alkali-silica reactivity and alkali-carbonate reactivity, i.e. Spratt limestone (SL) and Pittsburg dolomitic limestone (PL), were studied by XRD and SEM/EDS after autoclaving in KOH, NaOH and LiOH solutions at 150 °C for 150 h. The results indicate that: (1) NaOH shows the strongest attack on both ASR and ACR aggregates, the weakest attack is with LiOH. For both aggregates autoclaved in different alkali media, the crystalline degree, morphology and distribution of products are quite different. More crystalline products are formed on rock surfaces in KOH than that in NaOH solution, while almost no amorphous product is formed in LiOH solution; (2) in addition to dedolomitization of PL in KOH, NaOH and LiOH solutions, cryptocrystalline quartz in PL involves in reaction with alkaline solution and forms typical alkali-silica product in NaOH and KOH solutions, but forms lithium silicate (Li₂SiO₃) in LiOH solution; (3) in addition to massive alkali-silica product formed in SL autoclaved in different alkaline solutions, a small amount of dolomite existing in SL may simultaneously dedolomitize and possibly contribute to expansion; (4) it is promising to use the duplex effect of LiOH on ASR and ACR to distinguish the alkali-silica reactivity and alkali-carbonate reactivity of aggregate when both ASR and ACR might coexist.     

Alkali mass balance during the accelerated concrete prism test for alkali-aggregate reactivity

The alkali mass balance was calculated in concrete specimens submitted to the storage conditions of the Canadian standard CSA A23.2-14A concrete prism test for expansion due to alkali-aggregate reaction (AAR). The alkali concentration of both the concrete pore solution expressed under high pressure and the water below specimens in storage pails (bottom water) was measured. Measurements were conducted over a 1-year period, which corresponds to the length of the above test. Two reactive aggregates were tested [Potsdam sandstone (PO) and Spratt limestone (SP)]. Each aggregate was incorporated in two concrete mixtures (mass concrete and structural concrete), for a total of four batches. Significant alkali leaching occurred at 38 °C while performing tests in high moisture storage conditions even though prisms were covered with plastic sleeves. After 52 weeks, the alkali loss ranged from 12% to 25% of the original Na₂O_e content of the concrete, depending on the mixture proportioning and the aggregate type. After estimation of the proportion of alkalis fixed in cement hydrates, it appears that about 23% to 39% of the original alkalis released by the cement are quickly sorbed on aggregate surfaces or have rapidly migrated inside aggregate particles, which may have been incorporated with time in the AAR product. After 52 weeks at 38 °C, the pore solution alkalinity expressed from mass concrete made with PO was 250 mmol/l, whereas the alkalinity was 270 mmol/l in mass concrete incorporating SP. Since prisms of both mixtures were still expanding at 1 year, these alkalinity values are above the thresholds required for sustaining AAR in these concrete mixtures.     

Lithological influence of aggregate in the alkali-carbonate reaction

The reactivity of carbonate rock with the alkali content of cement, commonly called alkali-carbonate reaction (ACR), has been investigated. Alkali-silica reaction (ASR) can also contribute in the alkali-aggregate reaction (AAR) in carbonate rock, mainly due to micro- and crypto-crystalline quartz or clay content in carbonate aggregate. Both ACR and ASR can occur in the same system, as has been also evidenced on this paper.Carbonate aggregate samples were selected using lithological reactivity criteria, taking into account the presence of dedolomitization, partial dolomitization, micro- and crypto-crystalline quartz. Selected rocks include calcitic dolostone with chert (CDX), calcitic dolostone with dedolomitization (CDD), limestone with chert (LX), marly calcitic dolostone with partial dolomitization (CD), high-porosity ferric dolostone with clays (FD). To evaluate the reactivity, aggregates were studied using expansion tests following RILEM AAR-2, AAR-5, a modification using LiOH AAR-5Li was also tested. A complementary study was done using petrographic monitoring with polarised light microscopy on aggregates immersed in NaOH and LiOH solutions after different ages. SEM-EDAX has been used to identify the presence of brucite as a product of dedolomitization. An ACR reaction showed shrinkage of the mortar bars in alkaline solutions explained by induced dedolomitization, while an ASR process typically displayed expansion. Neither shrinkage nor expansion was observed when mortar bars were immersed in solutions of lithium hydroxide.Carbonate aggregate classification with AAR pathology risk has been elaborated based on mechanical behaviours by expansion and shrinkage. It is proposed to be used as a petrographic method for AAR diagnosis to complement the RILEM AAR1 specifically for carbonate aggregate. Aggregate materials can be classified as I (non-reactive), II (potentially reactive), and III (probably reactive), considering induced dedolomitization ACR (dedolomitization degree) and ASR.     

Relation of expansion due to alkali silica reaction to the degree of reaction measured by SEM image analysis

Scanning Electron Microscopy Image Analysis (SEM-IA) was used to quantify the degree of alkali silica reaction in affected microbars, mortar and concrete prisms. It was found that the degree of reaction gave a unique correlation with the macroscopic expansion for three different aggregates, stored at three temperatures and with two levels of alkali. The relationships found for the concretes and the mortars overlap when normalised by the aggregate content. This relationship seems to be linear up to a critical reaction degree which coincides with crack initiation within the reactive aggregates.     

The behavior of silicocarbonatite aggregates from the Montreal area

In a previous paper, it was concluded that silicocarbonatite aggregates from the Francon quarry, Montreal contributed to durability problems in Portland cement concrete. Results show that, at 2 days after casting, concrete made with silicocarbonatite aggregates contained over 1.5% more Na₂O than similar bars made with Exshaw limestone aggregates. A reaction involving the rare mineral dawsonite in the silicocarbonatite is thought responsible for the higher Na₂O content. In turn, this caused increased expansion of concrete bars made with alkali expansive aggregates. Also, concrete made with alkali-carbonate reactive Pittsburg aggregate showed more expansion when cured at 80 °C than bars cured at 23 °C. Concrete bars made with Exshaw limestone aggregates cured for 4 h at 85 °C showed late-stage expansion, which is attributed to delayed ettringite formation (DEF). However, no expansion was shown by heat-cured concrete prisms or mortar bars made with silicocarbonatite aggregates. Release of alkalis, aluminates and carbonates by the dawsonite reaction may have inhibited DEF. Concrete bars made with nonreactive Nelson dolostone and 10% silicocarbonatite cured at 80 °C for 4 h showed up to 0.15% expansion after several years at 23 °C and 100% relative humidity (R.H.), indicating that a deleterious reaction did occur.     

Long-term effectiveness and mechanism of LiOH in inhibiting alkali-silica reaction

A practical alkali reactive aggregate-Beijing aggregate was used to test the long-term effectiveness of LiOH in inhibiting alkali-aggregate reaction (AAR) expansion. In this paper, the most rigorous conditions were so designed that the mortar bars had been cured at 80 °C for 3 years after being autoclaved for 24 h at 150 °C. At this condition, LiOH was able to inhibit long-term alkali-silica reaction (ASR) expansion effectively. Not only was the relationship between molar ratio of n(Li)/n(Na) and the alkali contents in systems established, but also the governing mechanism of such effects was studied by SEM.     

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.     

不同养护条件下含石英玻璃地质聚合物砂浆的变形行为

为阐明典型活性组分（无定型SiO2）在地质聚合物中的作用行为和效应,探索地质聚合物体系中碱-集料反应评价方法,研究常温（23℃）和38℃湿气养护（相对湿度〉95%）、80℃在1 mol/L NaOH溶液浸泡及150℃在10%（质量分数）的KOH溶液压蒸下,含石英玻璃集料地质聚合物砂浆的变形行为,采用扫描电镜、电子散射能谱研究产物的组成和微观结构。结果表明：4种养护条件下,特别是在传统普通硅酸盐水泥（OPC）体系所规定的养护条件和龄期内,含石英玻璃集料地质聚合物砂浆没有发生有害膨胀;但是随养护条件不同,地质聚合物基体和石英玻璃可能经历不同的化学反应过程,进而导致不同的变形行为,特别是在高温且有外碱介入时,地质聚合物基体在后期会产生膨胀效应。不宜采用单一的适于OPC体系的高温、高碱快速检测混凝土碱-集料反应的检测方法来评价地质聚合物体系中的碱-集料反应行为。