Valorisation of "La Palma" Volcanic Ash for Making Portland-Blended, Alkaline and Hybrid Portland-Alkaline Cements.

The present work evaluates the feasibility of using volcanic fly ash (VFA) generated by the eruption of the Tajogaite volcano on the island of La Palma (Spain) in 2021, as a precursor in the preparation of cementitious materials with different Portland cement (PC) replacement levels (0%, 30%, 70% and 100%), in the absence (Blended Cement, BC) and presence of an alkaline activator (Hybrid Alkaline Cement, HAC, and Alkaline Cements, AC). Hydration kinetics (isothermal conduction calorimetry), paste mechanical strengths and reaction products were characterised by XRD, FTIR, TG/DTG and BSEM/EDX. The results obtained indicate that the strengths developed by the hybrid alkaline cements (HAC) are higher than those of the blended cements (BC), especially at the age of 2 days, where 25 MPa were obtained with the replacement of 70% PC by VFA. Alkaline cements (AC, 100% VFA) that were prepared with 8 M NaOH solution as the activator reached 40 MPa after 2 days. It was observed that in all the binders, depending on the initial composition of the binder mixture and the percentage of replacement and/or activator, VFA reacts to form cementitious gels, C-A-S-H and N-A-S-H type, which supports its use as a mineral addition to blended cement or as a precursor in the preparation of alkaline and hybrid alkaline cements.

Effect of Na versus Ca Sulfate Salts on the Hydration of Calcium Sulfoaluminate Clinker.

This paper examined how the amount (5% or 20%) and type (CaSO4 or Na2SO4) of sulphate salt affect the hydration of calcium sulphoaluminate clinker (KCSA). The mechanical behavior of the pastes was determined at 1, 3, 28, and 90 days, the heat flow and total heat were measured with isothermal conduction calorimetry, and the reaction products were characterized using X-ray diffraction (XRD), differential thermal analysis/thermogravimetry (DTA/TG) and scanning electron microscopy (SEM). The results obtained indicated that both the amount of sulphate salt (5% or 20%) and its type (CaSO4 or Na2SO4) affect the hydration kinetics, type of reaction products formed, and development of mechanical strength. The incorporation of CaSO4 has a positive effect on the development of the mechanical strength of KCSA. However, Na2SO4 can also produce adverse side effects at older ages. The presence of Na2SO4 increases pH values, which partly destabilizes the ettringite formed, thereby favoring carbonation and thenardite precipitation, which can cause the specimens to crack and break.

Alkali-Activated Binary Binders with Carbonate-Rich Illitic Clay.

This work deals with the investigation of alkaline binders obtained from binary mixtures of carbonate-rich illitic clay from deposits in southern Italy and two industrial by-products with very different total composition and calcium content, i.e., blast furnace slag and type F fly ash, respectively. To improve the reactivity, the selected clay was ground in a ball miller and heated to 700 °C. The binary mixtures were alkali activated with NaOH solution at 4 M and 8 M, and the activated pastes were cured at room temperature and relative humidity >90% in a climatic chamber. Heat flow, total heat and compressive strength (2, 7 and 28 days) were determined. The hardened pastes were characterized by X-ray powder diffraction (XRPD), Fourier-transform infrared spectroscopy (FTIR) and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDX). Results show that the main reaction product in all samples is a gel or mixture of C-A-S-H/(N, C)-A-S-H type gel depending on the calcium content in the precursors. The paste, made up of a 1:1 weight proportion of carbonate-rich illitic clay and blast furnace slag, showed the formation of a more compact matrix than that observed in each individually activated component, achieving the considerable mechanical strength value of 45 MPa after 28 days, which suggests a very positive interaction between the two calcium-rich solid precursors. The binary mixture of carbonate-rich illitic clay and F fly ash showed relatively low compressive strength (below 15 MPa), which has been related to the poor reaction potential of fly ash regarding the alkali activation at room temperature. The modification of curing parameters is expected to improve the reaction of carbonate-rich illitic clay/fly ash blend. The clay activation method used in this study has been demonstrated to be suitable for larger scale industrial pre-treatment set-ups.

Report of RILEM TC 281-CCC: outcomes of a round robin on the resistance to accelerated carbonation of Portland, Portland-fly ash and blast-furnace blended cements.

Many (inter)national standards exist to evaluate the resistance of mortar and concrete to carbonation. When a carbonation coefficient is used for performance comparison of mixtures or service life prediction, the applied boundary conditions during curing, preconditioning and carbonation play a crucial role, specifically when using latent hydraulic or pozzolanic supplementary cementitious materials (SCMs). An extensive interlaboratory test (ILT) with twenty two participating laboratories was set up in the framework of RILEM TC 281-CCC 'Carbonation of Concrete with SCMs'. The carbonation depths and coefficients determined by following several (inter)national standards for three cement types (CEM I, CEM II/B-V, CEM III/B) both on mortar and concrete scale were statistically compared. The outcomes of this study showed that the carbonation rate based on the carbonation depths after 91 days exposure, compared to 56 days or less exposure duration, best approximates the slope of the linear regression and those 91 days carbonation depths can therefore be considered as a good estimate of the potential resistance to carbonation. All standards evaluated in this study ranked the three cement types in the same order of carbonation resistance. Unfortunately, large variations within and between laboratories complicate to draw clear conclusions regarding the effect of sample pre-conditioning and carbonation exposure conditions on the carbonation performance of the specimens tested. Nevertheless, it was identified that fresh and hardened state properties alone cannot be used to infer carbonation resistance of the mortars or concretes tested. It was also found that sealed curing results in larger carbonation depths compared to water curing. However, when water curing was reduced from 28 to 3 or 7 days, higher carbonation depths compared to sealed curing were observed. This increase is more pronounced for CEM I compared to CEM III mixes. The variation between laboratories is larger than the potential effect of raising the CO2 concentration from 1 to 4%. Finally, concrete, for which the aggregate-to-cement factor was increased by 1.79 in comparison with mortar, had a carbonation coefficient 1.18 times the one of mortar. Supplementary Information: The online version contains supplementary material available at 10.1617/s11527-022-01927-7.

Effect of Alkaline Salts on Calcium Sulfoaluminate Cement Hydration.

This work analyzes the effect of the presence of 5 wt.% of solid sodium salts (Na2SO4, Na2CO3, and Na2SiO3) on calcium sulfoaluminate cement (CSA) hydration, addresses hydration kinetics; 2-, 28-, and 90-d mechanical strength, and reaction product microstructure (with X-ray diffraction (XRD), and Fourier transform infrared spectroscopy, (FTIR). The findings show that the anions affect primarily the reactions involved. Ettringite and AH3, are the majority hydration products, while monosulfates are absent in all of the samples. All three salts hasten CSA hydration and raise the amount of ettringite formed. Na2SO4 induces cracking in the ≥28-d pastes due to post-hardening gypsum and ettringite formation from the excess SO42- present. Anhydrite dissolves more rapidly in the presence of Na2CO3, prompting carbonation. Na2SiO3 raises compressive strength and exhibits strätlingite as one of its reaction products.

Supersulfated Cement Applied to Produce Lightweight Concrete.

The physical and mechanical characteristics of expanded-clay lightweight concrete based on a supersulfated binder in comparison with lightweight concrete based on ordinary Portland cement were studied. In replacing CEM 32.5 with a supersulfated binder of 6000 cm2/g specific surface, one can increase the tensile strength in bending up to 20% and can increase the ratio of the tensile strength in bending to the compressive strength that indicates the crack resistance increase of concrete. Compressive strengths at the age of 28 days were equal to 17.0 MPa and 16.6 MPa for the supersulfated binder of 3500 cm2/g specific surface and CEM 32.5, respectively. Shrinkage deformation of hardening concrete, indicators of fracture toughness, frost resistance, and thermal conductivity were determined during the experimental works. The coefficient of thermal conductivity decreased up to 12% compared to the use of CEM 32.5. An enhancement in concrete properties was associated with the increase of supersulfated binder fineness.

Hydration of Hybrid Alkaline Cement Containing a Very Large Proportion of Fly Ash: A Descriptive Model.

In hybrid alkaline fly ash cements, a new generation of binders, hydration, is characterized by features found in both ordinary portland cement (OPC) hydration and the alkali activation of fly ash (AAFA). Hybrid alkaline fly ash cements typically have a high fly ash (70 wt % to 80 wt %) and low clinker (20 wt % to 30 wt %) content. The clinker component favors curing at ambient temperature. A hydration mechanism is proposed based on the authors' research on these hybrid binders over the last five years. The mechanisms for OPC hydration and FA alkaline activation are summarized by way of reference. In hybrid systems, fly ash activity is visible at very early ages, when two types of gel are formed: C-S-H from the OPC and N-A-S-H from the fly ash. In their mutual presence, these gels tend to evolve, respectively, into C-A-S-H and (N,C)-A-S-H. The use of activators with different degrees of alkalinity has a direct impact on reaction kinetics but does not modify the main final products, a mixture of C-A-S-H and (N,C)-A-S-H gels. The proportion of each gel in the mix does, however, depend on the alkalinity generated in the medium.

An assessment of Mercury immobilisation in alkali activated fly ash (AAFA) cements.

This paper presents total and soluble Mercury contents for three coal fly ashes and alkali-activated fly ash (AAFA) cements consisting of 100% fly ash as starting material. To evaluate the potential of the AAFA cement matrix to immobilise Hg from an external source, another batch of cements, doped with 5000 mg/kg Hg as highly soluble HgCl(2), was prepared. The ashes and control AAFA cements complied with Mercury leaching criteria for non-hazardous wastes according to both TCLP and EN 12457 tests. Fly ash activated cements doped with 5000 mg/kg Hg and aged for 2 days immobilised 98.8-99.6% and 97.3-98.8% of Hg according to TCLP and EN 12457 tests respectively. Evidence from SEM-EDX suggests that Hg was immobilised by precipitation as highly insoluble HgS or Hg(2)S, although partial precipitation as less insoluble HgO or Hg silicates could not be entirely ruled out based on data presented. The results for Hg-doped cements contribute to the growing body of evidence that shows AAFA cement as a useful material for immobilizing elevated concentrations of toxic and hazardous elements.