硫酸盐侵蚀下石膏的形成及破坏机制研究现状

硫酸盐侵蚀是影响水泥基材料耐久性的重要因素,它不仅会缩短材料的服役寿命,甚至可能危及结构安全。在硫酸盐侵蚀过程中,钙矾石、石膏和碳硫硅钙石等侵蚀产物不断形成,从而导致材料出现膨胀、开裂、软化和剥落等不同形式的破坏。由于不同侵蚀产物的形成条件和对水泥基材料的侵蚀机理存在明显差异,而侵蚀机理是工程实践中指导预防硫酸盐侵蚀的重要依据,因此探明不同侵蚀产物的形成及稳定条件以及各侵蚀产物对材料的作用机理成为该研究课题的主要内容。 从现有研究来看,钙矾石型硫酸盐侵蚀是目前研究最为成熟的一种硫酸盐侵蚀。钙矾石是在高碱性硫酸盐溶液条件下形成的主要侵蚀产物,并且当其在狭小封闭的孔洞中生长时会导致材料发生膨胀、开裂破坏,相应的膨胀机理有吸水肿胀理论、结晶压理论和固相反应理论等。另外,在钙矾石型硫酸盐侵蚀的预防方面,发现通过控制水泥中铝酸三钙含量可有效减小因钙矾石形成而造成的膨胀危害。近年来,世界各地的研究者竞相报道了碳硫硅钙石的形成对混凝土结构造成严重破坏的工程实例,这使得碳硫硅钙石型硫酸盐侵蚀也逐渐受到重视。目前普遍认为碳硫硅钙石的形成主要导致材料出现泥化和分解现象,但其形成条件较为复杂,只在一些特殊环境下才有可能发生。 石膏是水泥基材料在硫酸盐侵蚀下形成的另一种较为常见的腐蚀产物,它的形成同样影响着水泥基材料的耐久性能。研究发现,硫酸盐溶液浓度越高,越利于形成石膏,但后来发现溶液pH值对石膏的形成及稳定影响更为显著,同时溶液温度、离子种类以及腐蚀制度等对石膏的形成也有一定影响。由于石膏的化学组成相对简单且不含铝相,因此采用普通抗硫酸盐侵蚀方法并不能有效抑制石膏的形成及破坏。石膏的形成往往伴随着水化产物的溶解脱钙,从而导致材料出现软化和剥落现象,但在石膏的膨胀问题上仍存在较大争议。 本文综述了硫酸盐侵蚀下水泥混凝土中石膏形成的影响因素,总结了石膏的生长位置及其引起的脱钙作用,最后对石膏的膨胀作用进行了相关探讨。     

超高性能水泥基材料复合盐侵蚀研究:合成Friedel盐和钙矾石在硫酸盐和氯盐溶液中的稳定性

化学合成了氯离子在水泥基材料中的主要侵蚀产物Friedel盐(3CaO·Al_2O_3·CaCl_2·10H_2O)以及硫酸根离子在水泥基材料中的主要侵蚀产物钙矾石(3CaO·Al_2O_3·3CaSO_4·32H_2O),采用XRD和综合热分析(TG-DSC)研究了二者的稳定性与转变机理,通过浸泡实验探究不同侵蚀性离子之间相互作用对水泥基材料的影响。结果表明:硫酸盐对Friedel盐稳定性影响显著,硫酸根离子置换Friedel盐中的氯离子,并最终生成钙矾石;氯盐对钙矾石的稳定性也有影响,氯盐同样可以使钙矾石分解。两种腐蚀产物之间存在平衡,并且在一定条件下可以相互转化。实验证实氯盐与硫酸盐复合溶液对水泥混凝土侵蚀过程中存在复杂的离子交互作用。     

氯盐和硫酸盐交互作用下水泥基材料的破坏机理综述

西部盐湖和海洋环境中存在大量的氯盐和硫酸盐,当水泥基材料处于氯盐-硫酸盐环境中,其破坏规律以及破坏机理与单一侵蚀因素作用明显不同,因此有必要探究两种盐在侵蚀过程中所呈现的交互作用。已有文献对氯盐和硫酸盐侵蚀下水泥基材料破坏规律的研究可以分为两部分:硫酸盐存在下氯盐对水泥基的侵蚀、氯盐存在下硫酸盐对水泥基的侵蚀。硫酸盐可以明显降低水化产物的氯离子结合量,因为硫酸根不仅能够分解Friedel盐,而且能先与C₃A或AFm反应,抑制Friedel盐的产生。但是,氯离子扩散速率高,可以先于硫酸根离子进入水泥基材料内部与水泥水化产物反应,延缓钙矾石的产生,抑制硫酸盐的侵蚀。两种离子在向材料内部侵蚀过程中相互影响,相互牵制。最后,根据目前的研究,提出几个有意义的思考方向。     

含石灰石粉水泥砂浆在低温环境中的硫酸盐侵蚀

分析了掺30%石灰石粉砂浆与纯水泥砂浆在(5±1)℃的2%MgSO4溶液中浸泡不同时间后试件表面层的矿物成分变化与微观结构,研究了强度与外观的变化.结果表明:掺入石灰石粉使水泥水化产物中的单硫型水化硫铝酸钙转变为稳定的单碳水化铝酸钙,物理填充作用使水泥石结构更加致密,因而在短期的低温硫酸盐侵蚀环境下掺石灰石粉砂浆比纯水泥砂浆表现出更好的耐腐蚀性.在经受低温硫酸盐侵蚀后纯水泥砂浆生成大量的石膏和钙矾石,而掺石灰石粉砂浆在经受同条件210 d侵蚀后的腐蚀产物中除了石膏、钙矾石外,还有少量的硅灰石膏生成,表明水泥石中的CSH凝胶体也受到侵蚀.     

硫酸盐侵蚀下掺稻壳灰混凝土的劣化性能及损伤模型

为证实稻壳灰(RHA)对混凝土硫酸盐侵蚀性能的改善作用,优选出掺RHA混凝土配比,并与普通混凝土(NC)对比,研究质量分数5wt%的Na2SO4溶液侵蚀270天内,表观现象、抗压、抗拉强度、有效孔隙率、动弹性模量等性能指标劣化规律,利用SEM观察硫酸盐侵蚀前后试件微观结构变化。结果表明：随侵蚀时间增加,混凝土试件逐渐局部剥落、体积膨胀;抗压、抗拉强度先提高后急剧下降,有效孔隙率先降低后提高,相对动弹性模量先提高后下降;微观分析表明混凝土水化产物与侵蚀介质反应生成钙矾石和石膏,填充内部孔隙,而随侵蚀进行膨胀性钙矾石与石膏超过内部抗拉强度产生裂隙,引起结构膨胀破坏、力学性能劣化。而RHA掺入混凝土生成水化硅酸钙凝胶,提高材料强度和耐腐蚀性,各阶段掺RHA混凝土劣化程度均优于NC。最终建立损伤本构模型,并与实测值对比,准确性较高。     

纳米SiO_2-矿渣-水泥复合胶凝材料的抗硫酸盐侵蚀试验

为研究纳米二氧化硅-矿渣-水泥复合胶凝材料的抗硫酸盐侵蚀性能,将砂浆试件浸泡在不同温度下的3%硫酸钠溶液中进行侵蚀试验,以抗折强度和抗蚀系数作为指标对其抗蚀性进行评价,并与普通硅酸盐水泥和抗硫酸盐水泥试件进行对比。采用微观分析方法对腐蚀产物的成分进行分析。研究结果表明:纳米二氧化硅-矿渣-水泥复合胶凝材料在不同温度下均具有优异的抗硫酸盐侵蚀能力,随着纳米二氧化硅掺量的增加,抗蚀性能增强;随着温度的降低,试件的侵蚀速率加快,270d的抗蚀系数及抗折强度逐渐降低。养护温度的改变导致腐蚀产物的成分发生变化,5℃养护条件下腐蚀产物中钙矾石及碳硫硅钙石均存在,但以后者为主。     

硫铝酸盐水泥增强建筑石膏的力学性能与耐水性能机理

石膏基胶凝材料的力学性能低、耐水性能差是限制其应用的主要原因.本工作通过复掺硫铝酸盐水泥,研究其对建筑石膏水化硬化进程及石膏硬化体力学性能与耐水性能的影响.结果表明,随着硫铝酸盐水泥掺量的增加,建筑石膏标准稠度需水量小幅降低,水化进程加速;10％水泥掺量时,石膏硬化体2 h与3 d的绝干抗折、抗压强度均大幅提升,2 h增幅高达34.8％、29.0％,3 d增幅高达28.8％、34.7％;同时饱水抗折强度由2.35 MPa提升至3.38 MPa,增幅高达43.8％,吸水率相应降低.XRD、SEM、MIP微观结构分析表明:硫铝酸盐水泥与建筑石膏复掺,水化生成针尖状的钙矾石(AFt)与无定形铝凝胶(AH3),AFt与针棒状二水石膏(DH)交织、穿插生长,在晶体之间发挥架桥、连接作用,同时AH3紧密填充在孔隙之间形成致密的晶胶结构中,石膏硬化体孔隙率降低,孔径明显细化,力学性能与耐水性能得到显著改善.     

复合盐浸下多元外掺剂-混凝土抗干湿-冻融循环性能

通过对粉煤灰、硅灰、矿渣、膨胀剂、引气减水剂（Air-Entrained Water Reduce Agent,AEWRA）和水泥基自愈合防水材料（Cementitious Capillary Crystalline Waterproofing Material,CCCWM）等多元外掺剂进行组合搭配掺入混凝土中,设计了5组混凝土配比。分析了复合盐（氯盐、硫酸盐和碳酸盐）浸-干湿-冻融循环等多种因素共同作用下多元外掺剂-混凝土的腐蚀破坏现象、质量损失率、相对动弹性模量衰减规律和抗侵蚀系数变化规律。采用SEM、EDS和XRD,研究了多元外掺剂-混凝土腐蚀的微观结构变化规律。研究结果表明,双掺粉煤灰和硅灰混凝土提高混凝土的抗侵蚀性能作用有限;在双掺粉煤灰和硅灰基础上加入适量的膨胀剂能够较大幅度提高混凝土的抗侵蚀性能,经11次复合盐浸-干湿-冻融循环后,其相对动弹性模量仍然在80%以上,抗侵蚀系数在0.9以上;CCCWM作为一种外掺剂加入混凝土会降低混凝土的耐侵蚀性,经4次复合盐浸-干湿-冻融循环后,相对动弹性模量就降到了60%以下,抗侵蚀系数从1.0降到了0.3。微观机制研究也表明,在复合盐浸-干湿-冻融循环作用下,腐蚀产物钙矾石和方解石共同作用会加速混凝土的腐蚀破坏。     

环境极性对水泥基材料抗低温硫酸盐侵蚀性能的影响

通过分析甘油对水泥-石灰石粉胶凝材料在低温(5℃)、5%硫酸钠溶液中侵蚀的影响,研究了环境极性对水泥基材料抗低温硫酸盐侵蚀性能的影响。结果表明,水泥-石灰石粉试件腐蚀程度随时间增加而加重,腐蚀产物主要为碳硫硅钙石,未掺甘油的试件棱角发生明显脱落;掺甘油降低了腐蚀产物中碳硫硅钙石的生成量,随甘油掺量增加腐蚀产物中碳硫硅钙石的生成量减少,腐蚀程度减轻。甘油可以抑制水泥基材料中碳硫硅钙石的生成,降低环境极性能提高水泥基材料抗低温硫酸盐侵蚀性能。     

低温环境下赤泥地聚合物抗硫酸盐侵蚀机理研究

通过将内掺不同质量分数硫酸镁和硫酸钠的赤泥地聚合物和普通硅酸盐水泥试件在(5±1)℃的条件下长期浸泡,定期观测试件外观变化,并对长期浸泡后的试件取样进行XRD衍射和FT-IR光谱分析,研究了内掺不同种类和不同质量分数硫酸盐对赤泥地聚合物的侵蚀破坏过程与作用机理,并与同等条件下普通硅酸盐水泥抗硫酸盐侵蚀性能及机理进行了对比。结果表明:当试件内掺硫酸镁和硫酸钠时,赤泥地聚合物发生了石膏型硫酸盐膨胀破坏,而普通硅酸盐水泥则分别发生了TSA型硫酸盐侵蚀破坏和石膏型硫酸盐膨胀破坏。赤泥地聚合物内部孔隙液pH值高,水化产物中C-S-H凝胶钙硅比低和水化生成的铝硅酸盐类物质化学性质稳定是其在长期低温硫酸盐侵蚀环境下未发生TSA型硫酸盐侵蚀破坏的主要原因。     

Thaumasite formation in concrete and mortars containing fly ash

Due to recent reports on deterioration of concrete structures, the thaumasite form of sulfate attack has become a subject of study and close investigation. This paper investigates the formation of thaumasite in concrete and mortars containing fly ash. The results show that thaumasite formation can occur within 84 days of exposure to sulfate solutions. High volumes of fly ash can limit or promote thaumasite formation depending on the type of cement used. Thaumasite and ettringite were found among the deterioration products. However, the thaumasite formation in the specimen prepared from sulfate resisting Portland cement was not accompanied by deterioration, except by 50% fly ash addition. The mixtures of Portland limestone cement with 40% fly ash exhibited a very limited thaumasite formation while the mixtures with 50% had no thaumasite at all. It is concluded that thaumasite can also be formed in mixtures incorporating fly ash.     

Synthesis of low-temperature calcium sulfoaluminate-belite cements from industrial wastes and their hydration: Comparative studies between lignite fly ash and bottom ash

The aim of this research was to study the production of calcium sulfoaluminate-belite (CŜAB) cement from industrial waste materials via hydrothermal-calcination process. Lignite fly ash and bottom ash were used as starting materials for comparison. Other waste materials viz., Al-rich sludge and flue gas desulfurization gypsum were also key players in raw mixes for the synthesis of CŜAB cement. For lignite fly ash as a starting material, mixed phases between ye'elimite and larnite were obtained, whereas for lignite bottom ash as starting material, only ye'elimite was obtained The hydration reaction was studied in terms of heat evolution, setting time, compressive strength and hydration product formation with various gypsum contents. The results showed a rapid formation of ettringite as a main hydration product mixed with calcium silicate hydrate, monosulfate and strätlingite phases as minority, with a fast final setting time of 24–26 min and high early compressive strength of 16.0 and 18.0 MPa in 1 day for CŜAB cements made of fly ash and bottom ash, respectively.     

The microstructure and sulfate resistance mechanism of high-performance concrete containing CNI

It is found from previous studies that the incorporation of calcium nitrite inhibitor (CNI) together with mineral admixtures could weaken the resistance of mixtures to sulfate attack. To better understand the mechanism of this phenomenon, the influence of CNI on the microstructure of cement-based materials is studied by means of quantitative X-ray diffraction, mercury intrusion porosimetry, and scanning electronic microscopy technique. The test results demonstrate that the incorporation of CNI accelerates the formation of calcium hydroxide and ettringite crystals, and weakens the pore refinement effect caused by the secondary hydration reaction of fly ash and microsilica. At the age up to one year, the relative crystal quantity in mixture containing CNI is always higher than that in control mixture without CNI. The reasons for the degradation in sulfate resistance of mixtures may be attributed to the increase of the calcium hydroxide and ettringite crystals formed, the increase of micropore size and the degradation of secondary hydration reaction. Based on the experimental results, conclusion can be drawn that NCI should be used cautiously in practical engineering when high resistance to sulfate attack is required.     

改性磷石膏的强度与孔结构的研究

本工作研究了矿物掺合料(矿渣、粉煤灰)和激发剂(熟石灰和水泥)对磷石膏强度的影响,并且探索了水泥对磷石膏耐水系数的影响。此外对磷石膏改性处理后的微观形貌和孔结构进行了分析。研究结果表明:矿渣和粉煤灰均能提高磷石膏的强度,且矿渣对磷石膏强度的增强作用更明显;但两者对磷石膏耐水性的增强作用并不明显,矿渣掺量过多时会由于延迟钙矾石的形成而导致石膏开裂。水泥和熟石灰作为激发剂时可以增强磷石膏的强度,熟石灰的增强作用更明显。水泥对磷石膏的耐水性能有一定的增强作用。磷石膏的水胶比、养护龄期和矿物掺合料可以改变其孔隙率,但不会改变其孔径分布;粉煤灰可以提高石膏的孔隙率,并且改变其孔径分布;水泥会降低石膏的孔隙率并改变其孔结构。     

Identification of concrete deteriorating minerals by polarizing and scanning electron microscopy

The deterioration of concrete represents one of the most serious problems of civil engineering worldwide. Besides other processes, deterioration of concrete consists of sulfate attack and carbonation. Sulfate attack results in the formation of gypsum, ettringite and thaumasite in hardened concrete.Products of sulfate attack may cause a loss of material strength and a risk of collapse of the concrete constructions. The authors focused especially on the microscopical research of sulfate attack. Concrete samples were taken from the Charles Bridge in Prague, Czech Republic. A succession of degrading mineral formation was suggested. Microscope methods represent a new approach to solving the deterioration problems. They enable evaluation of the state of concrete constructions and in cooperation with hydro-geochemistry, mathematics and statistics permit prediction of the durability of a structure. Considering the number of concrete constructions and their age, research of concrete deterioration has an increasing importance. The results obtained can also be useful for future construction, because they identify the risk factors associated with formation of minerals known to degrade structures.     

聚乙烯醇纤维增强水泥基复合材料在长期浸泡作用下抗硫酸盐侵蚀性能

为了研究纤维和粉煤灰对长期浸泡作用下聚乙烯醇纤维增强水泥基复合材料（PVA纤维/水泥复合材料）抗硫酸钠侵蚀的影响,对多次试验周期后的试件表观形貌变化、质量变化、体积变化、抗压强度和微观结构进行分析研究。试验结果表明,纤维的掺入及良好的分散,在水泥基体中形成了良好的网络分布结构,使PVA纤维/水泥复合材料在硫酸钠溶液中的侵蚀速度减缓,但纤维掺量有一个最佳值;粉煤灰的掺入在一定程度上密实了PVA纤维/水泥复合材料,使其抗硫酸钠侵蚀性能得到改善,质量分数在50%之内时随着掺量的增加而更加明显。     

The co-existence of thaumasite and ettringite in concrete exposed to magnesium sulfate at room temperature and the influence of blast-furnace slag substitution on sulfate resistance

The effects of Type I Portland cement replacement by 45% or 72% blast-furnace slag on the sulfate resistance of laboratory concretes were analyzed by microstructural investigation. The concretes investigated were stored in water or in magnesium sulfate solutions for 23 years under laboratory conditions. For those stored in water only surface layers of carbonation and decalcification were observed. Concretes exposed to sulfate solutions formed brucite, ettringite and thaumasite. Thus, thaumasite was observed to form in concretes stored under laboratory conditions. In all cases both ettringite and thaumasite were found to co-exist in the damaged zones. However, the thaumasite appears to be moving in from the exterior after initial formation of ettringite, and has not resulted in the massive destruction of the hydrated matrix as has been found elsewhere at lower temperature exposures. Slag replacement was observed to be an effective means of conferring resistance to sulfate attack. Although the concretes studied were prepared at a W/cm (water-to-cementitious materials) ratio of 0.50, the depths of attack observed were comparable to those observed in concrete prepared at w/c=0.45 using ASTM Type V (SRPC) cement alone.     

Calcium sulphate anhydrite based composite binders; effect of Portland cement and four pozzolans on the hydration and strength

The strength, hydration products, microstructure and heat of early hydration were investigated on alternative hydraulic green cements based on calcium sulphate anhydrite partially blended with Portland cement and pozzolans. Four pozzolans of different physical and chemical nature, namely a geothermal waste, silica fume, metakaolin and pulverized fuel ash were characterized. The composite binders showed hydraulic behavior. The use of Portland cement favoured the strength, which was also higher with the incorporation of siliceous nanometric pozzolans compared to the micrometric silicoaluminate pozzolans. The nanoparticles enhanced the early hydration and changed the gypsum morphology promoting denser matrices of hydration products. The geothermal waste pozzolan was the most effective, while one of the composites with metakaolin showed formation of ettringite and strength losses. The heat of hydration of the composites was considerably lower than that of the neat Portland cement.     

Preparation of alinite cement from municipal solid waste incineration fly ash

The feasibility of partially substituting ordinary raw materials with municipal solid waste incineration (MSWI) fly ash in alinite cement production was investigated by X-ray diffraction (XRD), X-ray fluorescence spectrometry (XRF) and scanning electron microscopy (SEM). The physical properties and leaching behavior of the produced cement were also evaluated. Experimental results show that good quality clinkers can be obtained by firing the raw mixes, in which the replacement of MSWI fly ash reaches to 30%, at 1200 °C for 2 h. Alinite cements have higher early strengths at all gypsum additions, while the best result having acceptable early and 28-day strengths is obtained at 5% of gypsum addition. Results also show that the leaching toxicity of heavy metals is far lower than that of the regulatory limit at all testing ages. Based on this study, MSWI fly ash is viable as an effective, alternative raw material in alinite cement production.