X-ray microtomography (microCT) of the progression of sulfate attack of cement paste

High-resolution X-ray computed tomography (i.e., microCT or microtomography) was used to study the sulfate attack of cylinders of Type I cement paste cast with water-cement (w/c) ratios of 0.45, 0.50 and 0.60. Damage levels in samples exposed to a Na₂SO₄ solution with 10,000 ppm sulfate ion concentration were qualitatively rated from 0 (no damage) to 4 (extreme damage) based upon visual examination of the samples' exteriors and microtomography of the samples' interiors. The greater the w/c ratio, the more rapid the onset of sulfate damage. The corners of the cylinders appeared to be particularly susceptible to spalling, and damage may have continued into the cement paste by formation of subsurface cracks.     

The influence of calcium lignosulphonate-sodium bicarbonate on the status of ettringite crystallization in fly ash cement paste

Calcium lignosulphonate (CL)-sodium bicarbonate (SB) (a total of 0.7% by weight of cement and CL to SB ratio of 1:1.8) will cause the fluidity of fly ash cement paste to decrease rapidly. It is the variation of the status of ettringite crystallization that causes this phenomenon. Experimental results show that CL-SB affects the liquid-phase composition of fly ash cement paste remarkably. As a result, ettringite crystallizes out in the shape of needles from the solution. These needle-like crystal particles are distributed in the solution at a certain distance from the surface of clinker particles. At the initial hydration stage, the crystallization of ettringite is stronger in fly ash cement with calcined gypsum than in fly ash cement with gypsum.     

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.     

Damage monitoring of cement paste by electrical resistance measurement

Electrical resistance measurement is effective for monitoring damage (due to damage infliction and subsequent microcrack opening) and healing (due to microcrack closing) of cement pastes (plain, with silica-fume, and with latex) in real time during repeated compressive loading. Damage causes the resistance to increase; healing causes the resistance to decrease.     

Effects of gypsum formation on the performance of cement mortars during external sulfate attack

Sodium sulfate attack was studied on C₃S mortars, along with ASTM Type I Portland cement (PC) mortars, in an attempt to independently evaluate the effect of gypsum formation on the performance. The quantity of gypsum and ettringite, as measured by differential scanning calorimetry (DSC), increased with the time of immersion in the sulfate solution. An increase in length of the mortar specimens was also registered along with the increase in the quantity of gypsum. This result suggests that the formation of gypsum could be expansive. Indeed, considerable expansion, although delayed compared to PC mortars, was observed in the C₃S mortars. Thus, it can be concluded that the expansion of the PC mortars occurred due to the combined effect of gypsum and ettringite formation, while the expansion of C₃S mortars occurred as a result of gypsum formation.Thaumasite formation as small inclusions was also detected in both the C₃S and the PC mortars, especially in regions of high gypsum deposition. The formation of thaumasite, despite the absence of carbonate bearing minerals and low temperatures, could be because of the carbonation of the surface zones of the mortars. However, it would be speculative to attribute any expansion to the formation of thaumasite, since it was detected only in minute amounts in the microstructural investigation.     

Magnesium sulfate attack on hardened blended cement pastes under different circumstances

This paper describes the sulfate resistance of some hardened blended Portland cement pastes. The blending materials used were silica fume (SF), slag, and calcium carbonate (CaCO₃, CC?). The blended cement pastes were prepared by using W/S ratio of 0.3. The effects of immersion in 10% MgSO₄ solution under different conditions (room temperature, 60 °C, and drying-immersion cycles at 60 °C) on the compressive strength of the various hardened blended cement pastes were studied. Slag and CC? improve the sulfate resistance of ordinary Portland cement (OPC) paste. Mass change of the different mixes immersed in sulfate solution at 60 °C with drying-immersion cycles was determined. The drying-immersion cyclic process at 60 °C accelerates sulfate attacks. This process can be considered an accelerated method to evaluate sulfate resistance of hardened cement pastes, mortars, and concretes.     

Stress relaxation of foamed high-alumina cement paste

A series of stress relaxation tests on foamed high-alumina cement pastes with different relative densities under various temperatures and imposed fixed strains were conducted to study the effects of relative density and imposed strain on the stress relaxation rates of foamed high-alumina cement pastes. At the same time, the activation energy for stress relaxation of foamed high-alumina cement paste was determined from experimental results. Experimental results on the stress relaxation rates of foamed high-alumina cement pastes are also compared to a theoretical expression obtained from a cell-edge relaxation-bending model. Consequently, the microstructural coefficients included in the theoretical expression for describing the stress relaxation rates of foamed high-alumina cement pastes are found. Furthermore, the stress relaxation rates of foamed high-alumina cement pastes can be predicted from the theoretical expression once their relative density and the imposed strain are known.     

Micro-spectroscopic investigation of Al and S speciation in hardened cement paste

Synchrotron-based micro X-ray fluorescence (micro-XRF) and micro X-ray absorption near edge spectroscopy (micro-XANES) have been used to determine the spatial distribution of Al and S and to identify the Al- and S-bearing species in compact hardened cement paste hydrated at 50 °C. The contribution of the S-bearing cement phases to the composed S K-edge XANES spectra collected in ten S-rich regions was determined using least-squares fitting. Ettringite and calcium monosulfoaluminate were identified as the main S-bearing species in the selected regions. Factor analysis was employed to determine the contribution of the various Al-bearing cement minerals to the composed Al K-edge XANES collected in different Al-rich regions of the cement matrix. Principal component analysis revealed that all spectra could be fitted using three components. Target transformation further suggested that the two Al-bearing clinker phases (aluminate, ferrite) and secondary phases of the hydrate assemblage (ettringite, AFm phases, hydrotalcite) contributed to the set of components that made up the experimental spectra. Least-squares fitting allowed the relative contribution of each reference compound to be determined. Aluminate and/or ferrite were detected in all Al-rich regions. AFm phases were identified in six out of the ten regions studied, while ettringite was detected in only two regions. The study confirmed that AFm phases are important cement minerals in hardened cement paste hydrated at 50 °C.     

Rheological properties of cement paste: Thixotropic behavior and structural breakdown

In this work, a new material model is presented to simulate rheological behavior of cement paste. This material model is among others based on combined concepts by Hattori and Izumi and by Tattersall and Banfill. More precisely, coagulation, dispersion and re-coagulation of the cement particles (giving a true thixotropic behavior) in combination with the breaking of certain chemically formed linkages between the particles (giving a so-called structural breakdown behavior) are assumed to play an important role in generating the overall time-dependent behavior of the cement paste. The model evaluation is done by comparing experimental data with model prediction.     

Model of piezoresistivity in carbon fiber cement

Piezoresistivity in carbon fiber cement allows strain sensing. It was first reported in 1993, but this paper provides the first theoretical model for this phenomenon. The model is based on the concept that the piezoresistivity is due to the slight pull-out of crack-bridging fibers during crack opening and the consequent increase in the contact electrical resistivity of the fiber-matrix interface. Good agreement is found between theory and experimental results obtained under tension/compression.     

X-ray absorption study of drying cement paste and mortar

X-ray absorption was used to observe water evaporation with hydration time in paste and mortar specimens, with the aim of studying the influence of water/cement (w/c) ratio, presence of aggregates, curing conditions on drying during early hydration. For the samples subjected to surface drying immediately after mixing, there exists a moisture gradient within the internal part of the specimen. However, obvious top-down drying only occurs within a small zone near the surface for early age cement pastes and mortars. The evaporation rate of water is very high in the first day after casting and is drastically reduced afterwards due to the formation of a microstructure that greatly improves specimens resistance to moisture loss. Mortars reveal a slightly lower evaporation rate since the aggregate increases the length of the transport route because of a larger tortuosity. However, the effect of sealed curing is much more important than the tortuosity effect of the aggregates.     

Change in pore structure and composition of hardened cement paste during the process of dissolution

An understanding about the dissolution phenomena of cement hydrates is important to assess changes in the long-term performance of radioactive waste disposal facilities. To investigate the alteration associated with dissolution, dissolution tests of ordinary Portland cement (OPC) hydrates were performed.Through observation of the samples after leaching, it was confirmed that ettringite precipitation increased as the dissolution of the portlandite and the C-S-H gel progressed. EPMA performed on cross-sections of the solid phase showed a clear difference between the altered and unaltered parts. The boundary between the two parts was termed the portlandite (CH) dissolution front. As the leaching period became longer, the CH dissolution front shifted toward the inner part of the sample. A linear relationship was derived by plotting the distance moved by the CH dissolution front against the square root of the leaching time. This indicated Ca ion movement by diffusion.     

Modeling the effects of solution temperature and concentration during sulfate attack on cement mortars

Simple chemistry-based empirical models have been developed to assess the role of temperature and concentration of the sulfate solution in the process of expansion of cement mortars that are subjected to external sulfate attack. ASTM Type I PC mortars, prepared according to ASTM C-109, were immersed in sodium and magnesium sulfate solutions at five different concentrations and four different temperatures. For both solutions, the trends in the measured expansion suggested the use of a simple rate law to analyze the effect of concentration. For the effect of temperature, an Arrhenius relationship was developed to determine the activation energy required to initiate expansion in sodium sulfate solution. Regression-based statistical models were found to be sufficient to explain the effect of temperature of magnesium sulfate solution on the expansion. Implications of using these models for developing potential test methods, as well as to enable interpretation of data from nonstandard test methods, are discussed.     

The effect of liquid push out of the material capillaries under sulfate ion diffusion in cement composites

The paper treats complex phenomena that accompany the diffusion of sulfate ions into cement paste or systems. The ion distribution within the material was studied by designing a specific diffusion model. The model accounts for two phenomena: capillary filling with products of the chemical reactions and the subsequent liquid push out of the capillary. The approach allows to quantify the concentration of free ions having penetrated the cement stone and that of chemically reacted ions, and to assess the liquid push out. Experimental data are also presented.     

Physical and microstructural aspects of sulfate attack on ordinary and limestone blended Portland cements

The consequences of external sulfate attack were investigated by traditional test methods, i.e. length and mass change, as well as by a newly developed, surface sensitive ultrasonic method, using Leaky Rayleigh waves (1 MHz). The macroscopic changes are discussed and compared with thermodynamic calculations and microstructural findings (SEM/EDS). The results show that the main impact of limestone additions on resistance to sulfate degradation are physical — i.e. addition of a few percent in Portland cement reduces the porosity and increases the resistance of Portland cement systems to sulfate; but higher addition of 25% increase porosity and lower resistance to sulfate. The kinetics of degradation were dramatically affected by the solution concentration (4 or 44 g Na₂SO₄/l) and the higher concentration also resulted in the formation of gypsum, which did not occur at the low concentration. However the pattern of cracking was similar in both cases and it appears that gypsum precipitates opportunistically in pre-formed cracks so it is not considered as making a significant contribution to the degradation. At 8 °C limited formation of thaumasite occurred in the surface region of the samples made from cement with limestone additions. This thaumasite formation led to loss of cohesion of the paste and loss of material from the surface of the samples. However thaumasite formation was always preceded by expansion and cracking of the samples due to ettringite formation and given the very slow kinetics of thaumasite formation it was probably facilitated by the opening up of the structure due to ettringite induced cracking.The expansion of the samples showed a steady stage, followed by a rapidly accelerating stage, with destruction of the samples. The onset of the rapidly accelerating stage occurred when the thickness of the cracked surface layer reached about 1–1.5 mm–10–15% of the total specimen thickness (10 mm).     

Autogenous shrinkage in high-performance cement paste: An evaluation of basic mechanisms

In this paper, various mechanisms suggested to cause autogenous shrinkage are presented. The mechanisms are evaluated from the point of view of their soundness and applicability to quantitative modeling of autogenous shrinkage. The capillary tension approach is advantageous, because it has a sound mechanical and thermodynamical basis. Furthermore, this mechanism is easily applicable in a numerical model when dealing with a continuously changing microstructure. In order to test the numerical model, autogenous deformation and internal relative humidity (RH) of a Portland cement paste were measured during the first week of hardening. The isothermal heat evolution was also recorded to monitor the progress of hydration and the elastic modulus in compression was measured. RH change, degree of hydration and elastic modulus were used as input data for the calculation of autogenous deformation based on the capillary tension approach. Because a part of the RH drop in the cement paste is due to dissolved salts in the pore solution, a method is suggested to separate this effect from self-desiccation and to calculate the actual stress in the pore fluid associated with menisci formation.     

Experimental study of gas diffusion in cement paste

This paper presents an experimental study of gas diffusion in binary mixtures of hydrogen-nitrogen and xenon-nitrogen through cement pastes (CEM I and CEM V) of different water/cement ratios (0.35 and 0.45). First, the impact of water saturation on gas diffusion is investigated by performing tests on samples pre-conditioned in specific atmospheric conditions (dry, 55, 70, 82, 93 and 100% RH) by means of saline solutions. The comparison of the results obtained for the CEM I and the CEM V samples (w/c ratio of 0.45) demonstrate the importance of pore size distribution/connectivity on gas diffusion. Second, diffusion tests at different total pressures and using two different mixtures (hydrogen-nitrogen, xenon-nitrogen) are performed to study the nature of gas diffusion in cement paste. Results demonstrate that gas diffusion in cement paste is controlled by Knudsen and ordinary diffusion at pressures greater than 100 kPa and mainly by Knudsen diffusion at pressures less than 100 kPa.     

Carbonation around near aggregate regions of old hardened concrete cement paste

Analogous with most modern cities, waste disposal is a pressing issue due to limited landfill and public filling (land reclamation) areas in Hong Kong in which construction and demolition (C&D) waste forms the major source. Concrete, apportioning the largest portion of C&D waste, has the greatest potential for recycling. However, the knowledge on micro-structural behavior of concrete waste is immature to give adequate details on the macro-behavior of concrete waste. This paper attempts to examine the problems of recycling old concrete by investigating the microstructure and phase transformation of the concrete samples collected from buildings with 46 and 37 years of services. From the results of Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM) examination, it is found that there are a lot of pores at the near layers of aggregate where carbonation of the hardened cement paste (HCP) is high. The pores may be generated as a result of poor workmanship such as insufficient concrete mixing time, trapping of air voids beneath coarse aggregate, inappropriate water to cement ratio, and the microclimate conditions such as humidity that affects the demand on water from the aggregate during mixing.     

Transport of a surface-applied corrosion inhibitor in cement paste and concrete

Surface-applied corrosion inhibitors are a kind of repair material and usually contain an aminoalcohol and a component forming a salt with the aminoalcohol. According to the manufacturers, this type of inhibitor penetrates very rapidly into concrete; however, the transport mechanisms have not been sufficiently investigated so far. The major part of the study therefore focused on the transport of the ingredients of an inhibitor in cement paste and concrete, which contained an aminoalcohol and a phosphorous compound. It has been shown that the latter forms an insoluble calcium salt in the environment of cement and precipitates quantitatively. It is thus unable to penetrate from the outside into the alkaline concrete zone and cannot develop its inhibiting effect there. The aminoalcohol, on the other hand, is not bound by cement, but remains largely dissolved in the pore liquid, thus providing optimal conditions for high mobility. The analysis of the transport mechanisms involved has revealed that diffusion in the dissolved state is by far the most efficient transport mechanism. While basically the transport of the aminoalcohol via the gaseous phase is possible, it does play an inferior role only. Surprisingly, the substance had hardly been absorbed by concrete by capillary suction, but at first remained close to the concrete surface.     

Effect of polysaccharides on the hydration of cement paste at early ages

This work deals with the relative efficiency of polysaccharides and their influence on cement hydration. Several parameters such as the structure, concentration, average molecular weight, and soluble fraction value of polysaccharides were examined. Cement hydration was monitored by isothermal calorimetry, thermogravimetry (TGA), and Fourier transform infrared (FTIR) spectroscopy. Results clearly show that retardation increases with higher polysaccharide-to-cement weight ratio (P/C). Low-molecular-weight starch showed enhanced retarding effect on the hydration of cement. The retardation effect of polysaccharides is also dependent on the composition of cement.