Performance characteristics of concrete based on a ternary calcium sulfoaluminate–anhydrite–fly ash cement

This paper reports an assessment of the performance of concrete based on a calcium sulfoaluminate–anhydrite–fly ash cement combination. Concretes were prepared at three different w/c ratios and the properties were compared to those of Portland cement and blast-furnace cement concretes. The assessment involved determination of mechanical and durability properties. The results suggest that an advantageous synergistic effect between and ettringite and fly ash (Ioannou et al., 2014) was reflected in the concrete’s low water absorption rates, high sulfate resistance, and low chloride diffusion coefficients. However, carbonation depths, considering the dense ettringite-rich microstructure developed, were higher than those observed in Portland cement concretes at a given w/c ratio. It was concluded that the amount of alkali hydroxides present in the pore solution is as important factor as the w/c ratio when performance of this type of concrete is addressed.     

钙矾石膨胀机理的SEM研究

本文利用扫描电镜观察了在具有不同矿物组成的系统中生成的钙矾石的形成与膨胀机理。发现能够产生膨胀的钙矾石是由局部化学反应所生成；它们在未水化的铝酸盐矿物表面原地结晶，呈放射状生长。通过溶解，沉淀生成的钙矾石不能凝结，没有膨胀性。     

Microstructural changes in concretes with sulfate exposure

In prior papers the responses of concretes to 50,000 ppm MgSO₄ exposure depending on cement type, w/cm and the presence of slag were described. The present paper completes this analysis by examining the effects of immersion of concretes produced using slag blended cements, in solutions containing 50,000 ppm of sodium sulfate. The spatial evolution of microstructure associated with carbonation and sulfate attack show differences which can be related to the nature of the cation associated with the sulfate, the cement type, and the w/cm ratio.     

Long-term performance of cement paste during combined calcium leaching-sulfate attack: kinetics and size effect

This paper presents experimental results obtained on cement paste samples (water/cement ratio of 0.4) subjected to a low-concentration (15 mmol/l) external sulfate attack during several weeks. Chemical and microstructural analyses include the continuous monitoring of calcium loss and sulfate consumption within the cement paste, periodic layer by layer X-ray diffraction (XRD)/energy-dispersive spectrometer (EDS) analyses of the solid constituents of the cement matrix (ettringite, portlandite, gypsum) within the calcium-depleted part of the samples. Scanning electron microscopy (SEM) and visual observations are used to follow the crack pattern evolution during the external sulfate attack. The relation between the size of the specimen and crack initiation/development is investigated experimentally by performing tests on samples with different thickness/diameter ratios.     

Internal deterioration of concrete by the oxidation of pyrrhotitic aggregates

This paper presents research results on the causes of a severe concrete deterioration, which occurred in many building foundations approximately 2 years after construction. Concrete samples were investigated with X-ray diffraction (XRD) analysis, a scanning electron microscope (SEM) and a petrographic examination performed with a stereomicroscope. It was found that the early cracking of concrete stemmed from the oxidation of the pyrrhotite found in the anorthosite aggregates used to produce the concrete. The oxidation process led to the precipitation of iron hydroxides having a higher volume than the original pyrrhotite does. The presence of micas (biotite) close to the pyrrhotite seemed to promote and accelerate the oxidation process.     

The C-S-H gel of Portland cement mortars: Part I. The interpretation of energy-dispersive X-ray microanalyses from scanning electron microscopy, with some observations on C-S-H, AFm and AFt phase compositions

Scanning electron microscopy (SEM) microanalyses of the calcium-silicate-hydrate (C-S-H) gel in Portland cement pastes rarely represent single phases. Essential experimental requirements are summarised and new procedures for interpreting the data are described. These include, notably, plots of Si/Ca against other atom ratios, 3D plots to allow three such ratios to be correlated and solution of linear simultaneous equations to test and quantify hypotheses regarding the phases contributing to individual microanalyses. Application of these methods to the C-S-H gel of a 1-day-old mortar identified a phase with Al/Ca=0.67 and S/Ca=0.33, which we consider to be a highly substituted ettringite of probable composition C₆A₂S?₂H₃₄ or {Ca₆[Al(OH)₆]₂·24H₂O}(SO₄)₂[Al(OH)₄]₂. If this is true for Portland cements in general, it might explain observed discrepancies between observed and calculated aluminate concentrations in the pore solution. The C-S-H gel of a similar mortar aged 600 days contained unsubstituted ettringite and an AFm phase with S/Ca=0.125.     

Differentiating seawater and groundwater sulfate attack in Portland cement mortars

The study reported in this article deals with understanding the physical, chemical and microstructural differences in sulfate attack from seawater and groundwater. Portland cement mortars were completely immersed in solutions of seawater and groundwater. Physical properties such as length, mass, and compressive strength were monitored periodically. Thermal analysis was used to study the relative amounts of phases such as ettringite, gypsum, and calcium hydroxide, and microstructural studies were conducted by scanning electron microscopy. Portland cement mortars performed better in seawater solution compared to groundwater solution. The difference in performance could be attributed to the reduction in the quantity of the expansive attack products (gypsum and ettringite). The high Cl concentration of seawater could have played an important role by binding the C₃A to form chloroaluminate compounds, such as Friedel's salt (detected in the microstructural studies), and also by lowering the expansive potential of ettringite. Furthermore, the thicker layer of brucite forming on the specimens in seawater could have afforded better protection against ingress of the solution than in groundwater.     

A hydration study of various calcium sulfoaluminate cements

The present work studies the hydration process and microstructural features of five calcium sulfoaluminate (CSA) cements and a ternary mixture including also ordinary Portland cement (OPC). The pastes were studied with simultaneous differential thermal-thermogravimetric (DTA-TG) analysis, mercury intrusion porosimetry (MIP), scanning electron microscopy (SEM), and expansion/shrinkage tests. The DTA-TG analysis confirmed the role of the hydration reactions involving the main CSA clinker constituent, tetracalcium trialuminate sulfate, which produced (i) ettringite when combined with lime and calcium sulfate, (ii) ettringite and aluminum hydroxide in the presence of calcium sulfate alone, and (iii) monosulfate and aluminum hydroxide in the absence of both lime and calcium sulfate. The MIP and SEM were able to discriminate between expansive (ternary mixture and CSA cement containing 50% gypsum) and non-expansive cements. Expansive cement pastes had (i) a nearly unimodal pore size distribution shifted toward higher radii and (ii) ettringite crystals smaller in size during the first day of curing. In a SEM image of a hardened paste of the CSA cement containing 50% gypsum, a stellate ettringite cluster was observed.     

Effect of NaOH activation on sulphate resistance of GGBFS and binary blend pastes

This paper presents an investigation into the observed enhanced performance that alkali activated ground granulated blast furnace slag (GGBFS) and binary blends offer against sulphate attack. X-ray diffraction (XRD) was carried out to identify and quantify the crystalline phases formed in a wide range of GGBFS and GGBFS-OPC (ordinary Portland cement) blends. Furthermore, specimens were exposed to a sulphate solution to examine the evolution of compressive strength along with identification of activation and/or hydration products. XRD demonstrated that ettringite was completely decomposed into its constituents in the presence of NaOH while quantification ascertained the formation of considerable amounts of hydrotalcite in the activated GGBFS and binary blends. Alkali activated GGBFS and binary blends specimens with higher GGBFS content offered enhanced resistance against aggressive sulphate ions and no significant degradation products were observed in these specimens after 6 months of exposure to sulphate solution. The results demonstrated that hydrotalcite formation may be a major reason for the improved sulphate resistance of alkali activated GGBFS and binary blend pastes with higher GGBFS content.     

Immobilization of heavy metals by calcium sulfoaluminate cement

Two types of calcium sulfoaluminate cement containing 20% and 30% phosphogypsum, respectively, were investigated for their ability in hazardous waste stabilization. Fourteen series of pastes were prepared, each containing the following soluble salt: Na₂CrO₄·4H₂O; Na₂Cr₂O₇·2H₂O; CrCl₃·6H₂O; Pb(NO₃)₂; Zn(NO₃)₂·6H₂O; ZnSO₄·7H₂O; and CdCl₂·5H2O. The level of pollution was 0.069 mol of heavy metal per Kg of cement.

The study has been carried out by means of X-ray diffraction, thermal analysis, scanning electron microscopy, mercury intrusion porosimetry, electrical conductivity, and leaching tests. Very good retention of lead, cadmium, zinc and trivalent chromium is observed. The retention of hexavalent chromium depends upon the nature of the binder: the cement containing 20% gypsum develops the best behaviour. This is explained by the microstructure of the hydrated paste: in the paste containing 30% gypsum, delayed ettringite precipitates and damages the hardened paste.