Fire spalling of concrete,as studied by NMR

The moisture transport in concrete subjected to fire is one of the most important processes with respect to fire spalling. The research on fire spalling of concrete is currently lacking experimental information of the moisture transport processes.We present combined moisture content and temperature profiles of one-sided heated concrete samples measured with our dedicated NMR setup. The concrete samples were equilibrated at different moisture contents ranging from 97 to 50% RH. The moisture content can be measured quantitatively and non-destructively while heating up the sample one-sided to 500 °C.We present the first experimental proof for the build up of a moisture peak in concrete, and the formation of a saturated layer. The temperatures measured at the boiling front indicate a vapour pressure in the order of 1.8 MPa. A simple vapour transport model was successfully used to describe the speed of the boiling front.     

Synergistic effect of combined fibers for spalling protection of concrete in fire

This study demonstrates the synergistic effect of some particular combination of fibers that can provide significantly better spalling protection of concrete in a fire than single fiber by themselves at the same fiber content level. Various combinations of polypropylene, polyvinyl alcohol, cellulose and nylon fibers were investigated. Fire tests were conducted in accordance with ISO-834. The combination of nylon (9 mm length) and polypropylene (19 mm length) fibers found to provide the most optimum results. By combining these two fibers, the same level of spalling protection was achieved by three times less fiber content than the single type of 0.10% polypropylene fiber commonly prescribed. A “fiber effectiveness parameter” is proposed which is a function of total number of fibers per unit volume and length of fiber. This parameter is useful in providing quantitative explanations of various fiber additions and their spalling results in fire.     

Post-fire residual mechanical properties of concrete made with recycled concrete coarse aggregates

This paper presents results of an experimental study on the residual mechanical performance of concrete produced with recycled coarse aggregates, after being subjected to high temperatures. Four different concrete compositions were prepared: a reference concrete made with natural coarse aggregates and three concrete mixes with replacement rates of 20%, 50% and 100% of natural coarse aggregates by recycled concrete coarse aggregates. Specimens were exposed for a period of 1 h to temperatures of 400 °C, 600 °C and 800 °C, after being heated in accordance with ISO 834 time–temperature curve. After cooling down to ambient temperature, the following basic mechanical properties were then evaluated and compared with reference values obtained prior to thermal exposure: (i) compressive strength; (ii) tensile splitting strength; and (iii) elasticity modulus. Results obtained show that there are no significant differences in the thermal response and post-fire mechanical behaviour of concrete made with recycled coarse aggregates, when compared to conventional concrete.     

Experimental and numerical study of electrochemical chloride removal from brick and concrete specimens

The electrochemical technique for chloride extraction (desalination) was applied in galvanostatic mode to cylindrical brick and concrete specimens with a steel bar as reinforcement placed in the centre. The specimens were initially contaminated by immersion in a solution of 35 g/l NaCl. Based on the Nernst-Planck equations, a numerical model was developed considering the interactions between the various ionic species in the pore solution. The model makes it possible to predict the evolution of the chloride profile with time. The numerical and experimental results are compared and the model parameters discussed.     

Influence of the nature of aggregates on the behaviour of concrete subjected to elevated temperature

An experimental study is carried out on concretes composed of three different types of aggregates: semi crushed silico-calcareous, crushed calcareous and rolled siliceous. For each aggregate type, two water/cement ratios (W/C), 0.6 and 0.3 are studied. Aggregates and concrete specimens were subjected to 300, 600 and 750 °C heating–cooling cycles. We analyse the evolution of thermal, physical and mechanical properties of concrete in terms of behaviour and physical characteristic evolutions of aggregates with temperature. The study of thermal behaviour of aggregates showed the importance of initial moisture state for the flints. The crystallisation and microstructure of quartz play an important role in the thermal stability of siliceous aggregates. The residual mechanical behaviour of concrete varies depending on the aggregate and the influence of aggregates is also dependent on paste composition. This study allowed to better understand the influence of chemical and mineralogical characteristics of aggregates on the thermomechanical behaviour of concrete.     

Specimens size,aggregate size,and aggregate type effect on spalling of concrete in fire

This paper attempted to isolate variables that govern concrete spalling when exposed to a hydrocarbon fire. The influence of specimen size was investigated by studying 4 specimen sizes consisting of cylinders, columns, and panels. Three aggregate sizes, 7 mm, 14 mm, and 20 mm were used in the concrete mixes to determine their effect on concrete spalling. Influence of aggregate type on concrete spalling was also investigated. Forty‐two different specimens were considered in this investigation. Concrete spalling was quantified as nominal spalling depth, which has been presented as a new way of quantifying the degree of concrete spalling. The results indicated that specimen size did have an effect on the spalling of concrete under hydrocarbon fire exposure and that nominal spalling depth of concrete increases as the specimen size increases. Aggregate size effect was evident when the maximum aggregate size increased from 7 mm to 20 mm, and explosive spalling was more severe for specimens with small size aggregates. Specimens with 14‐mm aggregate size showed inconsistent results and the spalling behavior witnessed was more random and sporadic. The type of aggregate used has no clear bearing on concrete spalling given both aggregates had similar linear expansion profiles.     

Measurement methods of carbonation profiles in concrete: Thermogravimetry, chemical analysis and gammadensimetry

This paper deals with two experimental methods to determine carbonation profiles in concrete. Gammadensimetry is a non-destructive test method able to measure the total penetrated CO₂ and to monitor the carbonation process during laboratory accelerated tests. The second method is thermogravimetric analysis (TGA) supplemented with chemical analysis (CA): as TGA is performed on a small mortar sample not representative of the whole tested concrete, CA is needed to proportion the sample cement content, the sand content and to correct the TGA results becoming thus representative of the concrete mix. Consequently, TGA-CA gives accurate quantitative profiles in carbonated cementitious materials. Results are reported for an ordinary Portland cement paste, and three concrete mixes, containing siliceous or calcareous aggregates. The CO₂ mass loss due to carbonation occurs from 530 to 950 °C, which overlaps the temperature range of the calcareous aggregate dissociation. To solve the problem, the origin of CaCO₃ is carefully analyzed. Calcium carbonate ensuing from C-S-H carbonation dissociates in a lower temperature range than the more stable one ensuing from portlandite carbonation and from limestone, which enables C-S-H carbonation to be distinguished from calcareous aggregates. Therefore, TGA-CA allows the CaCO₃ ensuing from C-S-H carbonation to be measured and to calculate the portlandite degraded by carbonation. Thus, the total calcium carbonates profiles can be deduced even when calcareous aggregates is present in the concrete mix.     

Aluminosilicate concretes bonded with water glass

Summary A composition was developed for aluminosilicate concrete with a water-glass bond with a density of 1.25–1.30 g/cm³ and with a setting accelerator-Portland cement.By reducing the density of the glass and eliminating the addition of sodium silicofluoride, the RUL is increased by 300° C compared with ordinary concrete used at present. The concrete possesses a high strength over the entire temperature range, a high abrasion resistance and excellent spalling resistance.The technical properties of the fireclay concrete suggest that this material can be used at up to 1300° C, and the aluminous at up to 1450° C in place of piece aluminosilicate goods.To solve the problem of the reliable and mass use of the recommended concretes in heat exchangers and in other parts of rotary cement furnaces it is necessary to carry out extra tests with the concretes on a bigger scale.     

Effect of high temperatures on high performance steel fibre reinforced concrete

After being subjected to different elevated heating temperatures, ranging between 105 °C and 1200 °C, the compressive strength, flexural strength, elastic modulus and porosity of concrete reinforced with 1% steel fibre (SFRC) and changes of colour to the heated concrete have been investigated.The results show a loss of concrete strength with increased maximum heating temperature and with increased initial saturation percentage before firing. For maximum exposure temperatures below 400 °C, the loss in compressive strength was relatively small. Significant further reductions in compressive strength are observed, as maximum temperature increases, for all concretes heated to temperatures exceeding 400 °C. High performance concretes (HPC) start to suffer a greater compressive strength loss than normal strength concrete (NSC) at maximum exposure temperatures of 600 °C. It is suggested that HPC suffers both chemical decomposition and pore-structure coarsening of the hardened cement paste when C-S-H starts to decompose at this high temperature. Strengths for all mixes reached minimum values at 1000 or 1100 °C. No evidence of spalling was encountered. When steel fibres are incorporated, at 1%, an improvement of fire resistance and crack [F.M. Lea, Cement research: retrospect and prospect. Proc. 4th Int. Symp. On the Chemistry of Cement, pp. 5-8 (Washington, DC, 1960).] resistance as characterized by the residual strengths were observed. Mechanical strength results indicated that SFRC performs better than non-SFRC for maximum exposure temperatures below 1000 °C, even though the residual strength was very low for all mixes at this high temperature. The variations with colour, which occured, are associated with maximum temperatures of exposure.     

Phase and porosity changes in a calcium aluminate cement and alumina system under hydrothermal conditions

When refractory castables are dried, hydrothermal conditions may result inside the bodies if the H₂O cannot escape from the material. Under such high-pressure conditions, problems such as explosive spalling can arise. As different curing temperatures during the hydration of calcium aluminate cement (CAC)-bound castables lead to the formation of different hydrate phases, different microstructures can develop in the hardened material. This study presents the changes in porosity and in the mineralogical composition of a refractory castable model system under hydrothermal conditions depending on the curing temperature (5, 23 and 40 °C).Quantitative X-ray diffraction (QXRD) measurements show that different hydrate phases are formed during curing, while C₃AH₆ and boehmite are formed in the same quantities after hydrothermal treatment in an autoclave at ～11 bar/180 °C. Although the mineralogical composition after autoclaving is not different, the three samples differ in their microstructure. Mercury intrusion porosimetry measurements reveal that although the total porosity after autoclaving is the same, the 40 °C samples have a higher proportion of large pores. SEM images also show that the appearance of C₃AH₆ in the 40 °C autoclaved samples varies, which originates from the starting phase composition and microstructure after curing.     

On the mathematics of time-dependent apparent chloride diffusion coefficient in concrete

This paper provides an improved mathematical analysis of chloride penetration into concrete employing a time-dependent diffusion coefficient for the solution of Fick's second law of diffusion. In the paper the possible errors caused by the application of oversimplified mathematical expressions used in some models for the evaluation of service life of reinforced concrete structures are discussed. The results from this mathematical analysis demonstrate that some models based on the oversimplified error function complement (ERFC) solutions may easily overestimate the service life by orders of magnitude, especially when the age factor is high. Some chloride profiles after up to 10 years' field exposure were used to compare the oversimplified with the improved models. The results show that both the oversimplified and the improved models fairly well predict the 10 years' chloride ingress in Portland cement concrete, but the oversimplified ERFC model significantly underestimates the chloride ingress in concrete with fly ash.     

Permeability measurement on high strength concrete without and with polypropylene fibers at elevated temperatures using a new test setup

A new test setup for permeability measurement at room and high temperature is presented. The experimental results obtained by employing the new setup are reported and validated. The experiments are performed on high performance concrete, without and with addition of polypropylene fibers under temperatures ranging from 20 °C to 300 °C as well as after cooling of previously heated specimens to the room temperature. The results show that plain concrete exhibits steady increase in permeability with increasing temperature, whereas concrete with fibers exhibit a sudden increase of permeability at temperatures between 80 °C and 130 °C. The results confirm the governing role of permeability on explosive spalling and suggest the existence of mechanisms of pressure relief other than just melting of fibers. The microstructure of concrete with fibers is investigated using SEM before and after exposure to high temperature. It is observed that the melted polypropylene flows only into the micro-cracks and does not penetrate into cement paste.     

Real-time measurements of temperature,pressure and moisture profiles in High-Performance Concrete exposed to high temperatures during neutron radiography imaging

High-Performance Concrete (HPC) is particularly prone to explosive spalling when exposed to high temperature. Although the exact causes that lead to spalling are still being debated, moisture transport during heating plays an important role in all proposed mechanisms. In this study, slabs made of high-performance, low water-to-binder ratio mortars with addition of superabsorbent polymers (SAP) and polypropylene fibers (PP) were heated from one side on a temperature-controlled plate up to 550 °C. A combination of measurements was performed simultaneously on the same sample: moisture profiles via neutron radiography, temperature profiles with embedded thermocouples and pore pressure evolution with embedded pressure sensors. Spalling occurred in the sample with SAP, where sharp profiles of moisture and temperature were observed. No spalling occurred when PP-fibers were introduced in addition to SAP. The experimental procedure described here is essential for developing and verifying numerical models and studying measures against fire spalling risk in HPC.     

Effect of short fibers on residual permeability and mechanical properties of hybrid fibre reinforced high strength concrete after heat exposition

Mechanical and permeability performance of fibre reinforced high strength concrete after heat exposition were evaluated in the experimental study. Cylindrical concrete specimens were exposed to heat with the rate of 10 °C/min of up to 400 °C. In order to study the effect of short fibres on residual performance of heated high strength concrete, polypropylene and steel fibres had been added into the concrete mix. The melting and vaporization of its fibre constituents were found to be responsible for the significant reduction in residual properties of polypropylene fibre reinforced high strength concrete. In terms of non-destructive measurement, UPV test was proposed as a promising initial inspection method for fire damaged concrete structure. Furthermore, the effect of hybrid fibre on the residual properties of heated fibre reinforced high strength concrete was also presented.     

Effect of entrained air voids on the microstructure and mass transport properties of concrete

The effects of entrained air on microstructure and transport properties of concrete with up to 11.5% air at different w/c ratios, curing and conditioning regimes were investigated. It was found that air voids disrupt the packing of cement and increase the heterogeneity of the microstructure. The width of the affected interface is around 30 μm. Gaseous diffusivity and permeability are increased by up to a factor of 2–3 at the highest air contents. This effect is similar to that due to increasing w/c ratio from 0.35 to 0.50 when samples are conditioned at 52% r.h or 50 °C. The effect on sorptivity is less consistent, while the effect on electrical conductivity is influenced by the moisture condition of the air voids. It is estimated that every 1% increase in air content increases transport by 10% or decreases it by 4%, depending on whether the air voids act as conductors or insulators.     

Isothermal corrosion testing of frit furnace refractories

In this paper, the corrosion behaviour of aluminosilicate type refractories in frit melts is studied in an isothermal corrosion test setup. A refractory brick of largely andalusite and sillimanite composition was compared to another refractory brick of mullite and sillimanite composition, both of which were made by different manufacturers for use in different frit furnaces. The industrial frit used for corrosion tests was a commercial product used in a wall tile glaze formulation. Corrosion tests conducted under isothermal conditions provide quantitative and reproducible data about the corrosion performance of refractories. In this study, tests were performed by partially immersing a 15 mm × 15 mm × 115 mm refractory specimen into a frit melt at temperatures between 1404 and 1504 °C. The effects of temperature, duration of exposure and the refractory brick type were investigated using a statistically designed set of experiments. The ANOVA (analysis of variance) table indicated that temperature and test duration were the most important factor effects, as expected. Increasing both temperature and exposure duration led to an increased amount of corrosion as measured by the cross-sectional area loss of the corroded refractory specimen. Postmortem microstructural analysis was also done on the specimens, with extensive amount of ZnO·Al₂O₃ precipitation observed along the frit–refractory interface, where crystals of mullite and alumina were also found to precipitate. Increasing the amount of exposure time and temperature produced more ZnO·Al₂O₃ precipitation. As identified by SEM-EDS analysis, mullite crystals were in the needle-like morphology, while alumina crystals were generally cubic. Additional experiments were conducted by rotating the specimens in the melt at 50 rpm of rotational speed. Due to the reduction of boundary layer thickness, more dissolution was observed from the rotated specimens. In all specimens, corrosion was more pronounced in the bond phase than through the large filler grains of mullite and andalusite.     

The effect of permeability enhancement on dry-out behavior of CA- and microsilica gel-bonded castables as determined by NMR

This investigation deals with refractory monolithic materials that are broadly used in thermal treatment facilities as they are necessary e.g. for iron and steel, glass and cement production, thereby withstanding temperatures between 600 and 2000 °C. In the special case of hydraulic bond refractory castables, the components must be mixed with water for two reasons: firstly, to obtain a mouldable suspension; and secondly, to achieve a green strength via the hydraulic reaction of calcium aluminate cement that is high enough to enable a secure refractoriness of the concrete formwork. Prior to their first use in production, castables must have their pore water and hydraulic bond water carefully removed in order to avoid explosive spalling that can cause severe damages inside the furnaces.In this study, we investigate the one-dimensional drying behavior of two specific refractory castable compositions, a microsilica-containing low- and a no-cement castable (LCC/NCC) during first heat-up in the temperature regime between 20 and 300 °C. First results were already presented in a prior publication that demonstrate a specialized high-temperature Nuclear Magnetic Resonance (NMR) setup capable of continuously measuring moisture and temperature profiles on 74 mm-long cylindrical samples, without touching or moving the sample [1].In this paper we explore how the use of permeability-enhancing agents (fibers and MIPORE 20) beneficially affects the drying behavior and consequently allows higher heating rates. We also demonstrate that the NMR technique as applied here is sensitive enough to resolve differences in the dry-out behavior if said additives are used in the castable formulations.Our results demonstrate that incorporation of fiber and MIPORE 20 significantly alters the dry-out behavior. In particular, it can be resolved that as the fibers begin to melt, there is a noticeable increase in permeability that results in faster drying, as well as a decrease of the drying front temperature and therefore the generated maximum pressure.     

Pore pressure development in hybrid fibre-reinforced high strength concrete at elevated temperatures

The present experimental work investigates the build-up of pore pressure at different depths of High Strength Concrete (HSC) and Hybrid-Fibre-Reinforced High Strength Concrete (HFRHSC) when exposed to different heating rates. First, the effect of the measurement technique on maximum pore pressures measured was evaluated. The pressure measurement technique which utilised a sintered metal and silicon oil was found to be the most effective technique for pore pressure measurement. Pore pressure measurements carried out showed that addition of polypropylene fibres is very effective in mitigation of spalling and build-up of pore pressure inside heated HSC. Addition of steel fibres plays some role in pore pressure reduction at relatively higher pressures in deeper regions of concrete during fast heating. Pore pressure development is highly influenced by the rate of heating with fast heating leading to higher pore pressures in the deeper regions of concrete compared to slow heating.     

Modelling chemical degradation of concrete during leaching with rain and soil water types

Percolation of external water through concrete results in the degradation of cement and changes the concrete pore water and solid phase composition. The assessment of long-term degradation of concrete is possible by means of model simulation. This paper describes simulations of chemical degradation of cement for different types of rain and soil water at an ambient earth surface temperature (10 °C). Rain and soil water types were derived using generic equations and measurement of atmospheric boundary conditions representative for North-Belgium. An up-to-date and consistent thermodynamic model is used to calculate the geochemical changes during chemical degradation of the concrete. A general pattern of four degradation stages was simulated with the third stage being the geochemically most complex stage involving reactions with calcium-silicate hydrates, AFm and AFt phases. Whereas the sequence of the dissolution reactions was relatively insensitive to the composition of the percolating water, the duration of the different reactions depends strongly on the percolating water composition. Major identified factors influencing the velocity of cement degradation are the effect of dry deposition and biological activity increasing the partial pressure of CO_2(g) in the soil air phase (and thus increasing the inorganic carbon content in the percolating water). Soil weathering processes have only a minor impact, at least for the relatively inert sandy material considered in this study.