Spatially resolved analysis of complex multi-phase systems can be validated through different analytical methods. This study compares investigations by scanning electron microscopy coupled with energy dispersive X-ray fluorescence analysis and high resolution X-ray diffraction. The studied sulfate attacked cement paste containing fly ashes consists of different interacting crystalline and amorphous phases. The complementary methods revealed in detail changes in phase composition due to the chemical attack. The advantages and disadvantages of both methods are discussed and suggestions are given for combining them with additional methods to maximize the information content.
Cementitious materials, in particular concrete, are durable materials if prepared appropriately and the Service life of concrete structures is now often required to last 120 years or more. Concrete durability depends strongly on intrinsic (e.g. composition, porosity) and exterior factors (e.g. moisture condition and composition, frost cycles, load pattem). Deleterious actions leading to concrete degradation are often created by the environment. Extemal sulfate attack is one of the more spectacular damage scenarios for concrete structures caused by the ingress of sulfate ions into the pore System of the material and successive formation of expanding phases. Though in recent years well studied there are still many questions remaining conceming the mechanisms of sulfate attack. In particular over the last ten years, with the increased utilization of blended cements, new questions arose concerning the sulfate resistance of those binder Systems. In the presented study therefore a method was developed to analyze the changes of the phase composition within the micro structure due to sulfate attack. The analytical method was based on pX-Ray diffraction (pXRD) using Synchrotron radiation in Debye-Scherrer (transmission) geometry. The spatial resolution of the method is ca. 10 pm and allows the characterization of phase transformations in the wake of damaging processes in more detail compared to other techniques. Furthermore, the experimental setup provides the possibility for analyzing the phase assemblage of a given sample without destroying the micro structure. This is possible because the specimens for phase analysis consists of thick sections, which can be used for further microscopic analysis of the micro structure and micro chemistry (e.g. by SEM-EDX). Samples containing supplementary cementitious materials were measured in comparison and to reconstruct the influence of the degradation process in detail. Additionally, reaction ffonts within the samples were localized by micro x-ray fluorescence analysis (MXRF).
Mechanisms of degradation of concrete by external sufate ions under laboratory and field conditions
(2011)
The durability of concrete is a major challenge for the construction, which devotes one third to one half of its annual investment to building maintenance. The lack of fieid data regarding concrete durability, especially in the case of exposure to Sulfate ions (“sulfate attack”) makes it dijficult to determine the appropriate fest methods andperformance criteria. Additionally, the increased use of sustainable blends (cement with mineral admixtures, typically slag from the iron industiy) suffers from a lack of experience regarding their long-term performance. Most results for sulfate resistance are derived from accelerated laboratoiy tests xvhere performance criteria are based only on macroscopic properties, especially expansion. To fill this gap and better widerstand the mechanisms of sulfate attack under real conditions, a parallel study of laboratoiy micro-concrete and fieid concrete samples under sulfate exposure was undertaken, focussing on microstructural changes in addition to the conventional macroscopic characterisation.
Four exposure regimes were designed in the laboratoiy: full immersion (ponding), pH-control, semi-immersion and wet/diy cycles. Pure Portland blends and slag blends witli high level of slag replacement (70 wt.-%) were investigated.
The exposure regime has been found to play a major role in the damage process. In ponding conditions, the damage process takes place in three stages characterised by a first period of induction, followed by surface damage thatfinally extends to the bulle of the material. Paradoxically, the w/c-ratio does not seem to have much impact on the ionic transport phenomena but might be more decisive in the microstructure mechanical strength against local stresses. The slag blends, considered as sulfate resistant in ponding exposure, revealed badperformances under wet/diy cycles. This beliaviour was attributed to poor proper physical resistance of the slag hydrates against diying.
The fieid concretes selected for the comparison with the laboratoiy cases were partially buried in a sulfate-enriched soil in Argentina. A pure Portland blend and a slag blends with high level of slag replacement (80 wt.-%) were investigated. The submerged part of the samples could be compared to the laboratoiy ponding exposure, wliile the upper layer of the samples subjected to weathering could be compared to the laboratoiy wet/diy cycles exposure. The fieid obsen’ations tend to confirm the laboratoiy results and validate the fest settings.
It has been underlined that a direct relationship between damage (e.g.; cracking/expansion) andphase assemblage was not evident. However, the study highlights that sulfate combination with the hydrates of the cement (e.g.; C-S-H) and with those of the slag would play a rote in the initiation of the expansion, which would be attributed to a swelling of the hydrates or to the precipitation offine ettringite after the Saturation level in sulfate of the hydrates has been reached.