Report of RILEM TC 267-TRM phase 3

RILEM TC 267 TRM– “Tests for Reactivity of Supplementary Cementitious Materials” recommends the Rapid Reliable Relevant (R3) test as a method for determining the chemical reactivity of supplementary cementitious materials (SCMs) in Portland cement blends. In this paper, the R3 test was applied to 52 materials from a wide range of conventional and alternative SCMs with the aim to validate such test. An excellent correlation was found between the cumulative heat release and the bound water determined following the R3 test method. Comparison of the R3 test results to mortar compressive strength development showed that all conventional SCMs (e.g. blast furnace slag and fly ashes) followed the same trend, with the notable exception of very reactive calcined kaolinitic clays. It is discussed, through an in-depth statistical regression analysis of the R3 reactivity test results and the 28 days relative compressive strengths, how reactivity threshold values for classification of the chemical reactivity of SCMs could be proposed based on the R3 test results

Use of steel slag for the synthesis of belite-sulfoaluminate clinker

Belite-sulfoaluminate (BCSA) cements are low-carbon mineral binders, which require low energy consumption and allow the incorporation of various secondary raw materials in the clinker raw meal. In this study two types of unprocessed steel slags, coming from stainless steel production, were incorporated in the BCSA clinkers. The clinker phase composition, clinker reactivity, and the compressive strength of the cement were studied to evaluate the possible use of the slag in BCSA clinkers. The cement clinkers were synthesized by using natural raw materials, white titanogypsum, mill scale, as well as two different steel slags: (i) EAF S slag, which is a by-product of melting the recycled steel scrap in an electric arc furnace, and (ii) la dle slag as a by-product of the processes of secondary metallurgy, in various quantities. Raw mixtures with two different targeted phase compositions varying in belite, calcium sulfoaluminate and ferrite phases were sintered at 1250 °C. Clinker phases were determined by Rietveld quantitative phase analysis, while their distribution, morphology and incorporation of foreign ions in the phases were studied by SEM/EDS analysis. The clinker reactivity was determined by isothermal calorimetry. BCSA cements were prepared by adding titanogypsum. The compressive strength of the cement pastes was determined after 7 days of hydration. The presence of a predicted major clinker phases was confirmed by Rietveld analysis, however periclase was also detected. Microscopy revealed subhedral grains of belite and euhedral grains of calcium sulfoaluminate phases, while ferrite occurred as an interstitial phase. The results showed differences in the microstructure and reactivity of the clinker and cement, which can be attributed to varying amounts of ettringite due to different slag type

Upotreba letećeg pepela u industriji građevinskog materijala

In this study, fly ash (FA) from the active and passive cassette TENT A (Nikola Tesla power plant, Obrenovac) is characterized from physicochemical and radiological aspects.Samples of FA consisted of amorphous phase followed by quartz, mullite, plagioclase, K-feldspar, hematite and calcite. As indicated by laser granulometry, the fraction D50 of investigated samples are about 80μm, so based on the above, they belong to coarse ashes.Very important parameter which defines chemical composition of the fly ash as precursor material of clinker or alkali activated materialsis presence of organic matter which is expressed by total organic content (TOC).Assessment of radiation exposure during coal combustion depends on the concentration of radioactive elements in the coal and in the resulting fly ash. Fly ash as industrial waste contains certain concentrations of natural radionuclides that are considered naturally occurring radioactive materials (NORM). The results showed that fly ash has satisfactory radiological properties and can be used as an addition to clinkers, but also as a potential precursor of a new class of alkaline activated materials that can be used in the construction sector.Procena izloženosti zračenju pri sagorevanju uglja zavisi od koncentracije radioaktivnih elemenata u uglju i u letećem pepelu koji nastaje. Uzorci letećeg pepela se sastoje od amorfne faze praćene kvarcom, mulitom, plagioklasom, K-feldspatom, hematinom, kalcitom. Kao rezultat laserske granulometrije, frakcija D50 za ispitivane uzorke je približno 80 μm, tako da na osnovu navedenog, leteći pepeli predstavljaju pepele krupnih čestica. Veoma važan parametar je prisustvo organske materije koje se izražava ukupnim organskim sadržajem. Leteći pepeli kao industrijski ostaci sadrže određene koncentracije prirodnih radionuklida koji se smatraju prirodnim radioaktivnim materijalima (NORM). U ovojm istraživanju, leteći pepeo iz aktivne i pasivne kasete TENT A (termoelektrana Nikola Tesla, Obrenovac) karakteriše se sa radiološkog i fizičko-hemijskog aspekta. Rezultati su pokazali da leteći pepeo ima zadovoljavajuća radiološka svojstva i da se može koristiti kao dodatak klinkerima, ali i kao potencijalni precursor nove klase alkalno aktiviranih materijala koji se mogu primeniti u građevinskom sektoru.XXXII Simpozijum Društva za zaštitu od zračenja Srbije i Crne Gore, 4-6. oktobar 2023; Budva, Crna GoraProceedings: [https://vinar.vin.bg.ac.rs/handle/123456789/11602

Technical and radiological characterisation of fly ash and bottom ash from thermal power plant

Huge quantities of fly ash and bottom ash are generated from thermal power plants and it presents great concern for country, mainly due to the environmental effects. In this study, fly ashes and bottom ash were characterized from technical and radiological aspects. Health effect due to the activity of radionuclides 226Ra, 232Th and 40K was estimated via radium equivalent activity (Raeq), external hazards index (Hex), the external absorbed dose rate (D) and annual effective dose rate (EDR). The specific surface area (40.25 m2 g−1), particle density (1.88 g cm−3) and LOI (23.49%) were typical for bottom ash. Siliceous fly ash contained 32% reactive silica. The annual effective dose rate for all ashes is ≤ 0.2 mSv y−1. Both, fly ash and bottom ash present potential secondary raw materials to be used for building purposes as result of their technological and radiological assessment

Phase development and hydration kinetics of belite-calcium sulfoaluminate cements at different curing temperatures

The influence of different curing temperatures on the hydration of belite-calcium sulfoaluminate cement was investigated at 20, 40 and 60 °C. The hydration kinetics and the hydrated phase assemblages were studied by isothermal calorimetry, X-ray powder diffraction, differential thermal analysis and thermogravimetric analysis, as well as field emission scanning electron microscopy. The compressive strength development of the cement pastes was also determined. Results showed that, at early ages, hydration was faster and early compressive strength was higher at elevated temperatures than at ambient temperature. On the other hand, at late ages in cement pastes cured at 60 °C, the amount of ettringite decreased, leading to lower compressive strength, indicating that the degree of hydration was lower at higher temperatures. Moreover, at elevated temperatures prismatic ettringite crystals became smaller due to faster hydration. Other hydration products present were aluminium hydroxide, which is formed together with ettringite from the hydration of calcium sulfoaluminate and gypsum, and C–S–H which precipitates as a main hydration product of belite. Belite hydrated in a lesser amount, especially at 60 °C, when the lowest amount of C–S–H was observed

Report of RILEM TC 267-TRM phase 2

The results of phase 1 of an interlaboratory test, coordinated by the RILEM TC 267-TRM “Tests for Reactivity of Supplementary Cementitious Materials” showed that the R3 (rapid, relevant, reliable) test method, by measurement of heat release or bound water, provided the most reliable and relevant determination of the chemical reactivity of supplementary cementitious materials (SCMs), compared to other test methods. The phase 2 work, described in this paper aimed to improve the robustness of the test procedure and to develop precision statements for the consolidated test procedure. The effect of the pre-mixing and mixing conditions, and the impact of the mix design on the test method robustness were assessed and fixed for optimal conditions to carry out the R3 heat release test. The effect of the drying step was evaluated to define the R3 bound water test procedure in more detail. Finally, the robustness of the consolidated final test methods was determined by an interlaboratory study to define the precision statements

Quantitative in situ X-ray diffraction analysis of early hydration of belite-calcium sulfoaluminate cement at various defined temperatures

The influence of temperature on the early hydration of belite-calcium sulfoaluminate cements with two different calcium sulfate to calcium sulfoaluminate molar ratios was investigated. The phase composition and phase assemblage development of cements prepared using molar ratios of 1 and 2.5 were studied at 25, 40 and 60 ◦C by in situ X-ray powder diffraction. The Rietveld refinement method was used for quantification. The degree of hydration after 24 h was highest at ambient temperatures, but early hydration was significantly accelerated at elevated temperatures. These differences were more noticeable when we increased the temperature from 25 ◦C to 40 ◦C, than it was increased from 40 ◦C to 60 ◦C. The amount of calcium sulfate added controls the amount of the precipitated ettringite, namely, the amount of ettringite increased in the cement with a higher molar ratio. The results showed that temperature also affects full width at half maximum of ettringite peaks, which indicates a decrease in crystallite size of ettringite at elevated temperatures due to faster precipitation of ettringite. When using a calcium sulfate to calcium sulfoaluminate molar ratio of 1, higher d-values of ettringite peaks were observed at elevated temperatures, suggesting that more ions were released from the cement clinker at elevated temperatures, allowing a higher ion uptake in the ettringite structure. At a molar ratio of 2.5, less clinker is available in the cement, therefore these differences were not observed

The influence of calcium sulfate content on the hydration of belite-calcium sulfoaluminate cements with different clinker phase compositions

The influence of different amounts of gypsum on the hydration of a belite-rich and a yeʼelimite-rich belite-calcium sulfoaluminate clinker (BCSA) was investigated. The hydration kinetics, phase assemblages and compressive strength development of cements prepared using yeʼelimite/ calcium sulfate molar ratios of 1, 1.5 and 2 were studied. Besides ettringite and monosulfate, aluminium hydroxide, strätlingite, C-S-H, iron-containing siliceous hydrogarnet and hydrotalcite were present as hydration products. Increasing the amount of gypsum increased the ratio of ettringite to monosulfate formed in the cement paste, lowered the amount of pore solution, delayed the dissolution of belite and ferrite, decreased the formation of strätlingite and, in the case of the yeʼelimite-rich BCSA, led to an increase in compressive strength. Increased amounts of belite in the clinker led to the formation of higher quantities of C-S-H, at the expense of straätlingite and a lower compressive strength, as belite has a lower degree of reaction than yeʼelimite and due to the formation of more C-S-H and stratlingite compared to the more space-filling ettringite. The thermodynamic model established for BCSA cement hydration agrees well with the experimental data. Compressive strength directly correlated with bound water from thermogravimetric analyses and inversely correlated with the porosity calculated from thermodynamic modelling

The Incorporation of steel slag into belite-sulfoaluminate cement clinkers

The potential use of steel slag from treated steel slag in belite-sulfoaluminate cements was investigated in this study. Cement clinkers with two phase compositions were synthesized, allowing the incorporation of different amounts of steel slag. The phase composition and microstructure of cement clinkers at three different sintering temperatures were studied by X-ray powder diffraction and the Rietveld method, as well as scanning electron microscopy with energy dispersive spectrometry. The results showed that the targeted phase composition of clinkers was achieved at a sintering temperature of 1250%C. However, a higher amount of perovskite instead of ferrite was detected in the clinker with a higher content of Ti-bearing bauxite. Apart from the main phases, such asbelite, calcium sulfoaluminate, and ferrite, several minor phases were identified, including mayenite, perovskite, periclase, and alkali sulfates. In both clinker mixtures, a higher content of MgO in the steelslags resulted in the formation of periclase. Furthermore, the hydration kinetics and compressive strength at 7 and 28 days were studied in two cements prepared from clinkers sintered at 1250%C. As evidenced by the results of isothermal calorimetry, the hydration kinetics were also influenced by the minor clinker phases. Cement with a higher content of calcium sulfoaluminate phase developed a higher compressive strength

Experimental study and thermodynamic modelling of the temperature effect on the hydration of belite-ye’elimite-ferrite cements

This study focuses on the kinetics of hydration, phase assemblage, microstructure and mechanical properties after various hydration times of two different BCSA cements at 5, 20, 40 and 60 ◦C and compares experimental data with thermodynamic modelling. Different curing temperatures change the type of hydrates and their amounts. Ye’elimite and gypsum in belite-ye’elimite-ferrite cements are almost fully reacted after 24 h of hy- dration at 20, 40 and 60 ◦C, while not at 5 ◦C. The hydration of belite is slower than the one of ye’elimite, but reaches a high degree of hydration after 150 days which is increasing with temperature. Less ettringite is present at elevated temperatures due to its increasing solubility, while more monosulfate is observed. Furthermore, with increasing temperature siliceous hydrogarnet forms at the expenses of str¨atlingite as well as more C S H is found as more belite reacts resulting in higher compressive strength. Dense and homogenous microstructure is observed at 5 ◦C, while it is more heterogeneous at higher temperatures. The presence of more ye’elimite resulted in higher ettringite and str¨atlingite formation and a higher compressive strength, while more belite yields more C S H in the hydrates and lower compressive strength