Durability of Magnesium Potassium Phosphate Cements (MKPCs) under Chemical Attack.

Magnesium phosphate cements (MPCs), also known as chemically bonded ceramics, represent a class of inorganic cements that have garnered considerable interest in recent years for their exceptional properties and diverse applications in the construction and engineering sectors. However, the development of these cements is relatively recent (they emerged at the beginning of the 20th century), so there are still certain aspects relating to their durability that need to be evaluated. The present work analyses the chemical durability of magnesium potassium phosphate cements (MKPCs) during 1 year of immersion in three leaching media: seawater, a Na2SO4 solution (4% by mass) and deionized water. For this, pastes of prismatic specimens of MKPC, prepared with different M/P ratio (2 and 3), were submitted to the different chemical attacks. At different ages, the changes on the mechanical strengths, microstructure (BSEM, MIP) and mineralogy (XRD, FTIR, TG/DTG) were evaluated. The results obtained indicate that, in general terms, MKPC systems show good behavior in the three media, with the more resistant system being the one prepared with a M/P molar ratio of 3.

MgO/KH2PO4 and Curing Moisture Content in MKPC Matrices to Optimize the Immobilization of Pure Al and Al-Mg Alloys.

Magnesium Potassium Phosphate Cements (MKPCs) are considered a good alternative for the immobilization of aluminium radioactive waste. MKPC composition and moisture curing conditions are relevant issues to be evaluated. The corrosion of pure aluminium (A1050) and AlMg alloys (AA5754) with 3.5% of Mg is studied in MKPC systems prepared with different MgO/KH2PO4 (M/P) molar ratios (1, 2, and 3M) and moisture curing conditions (100% Relative Humidity (RH) and isolated in plastic containers (endogenous curing)). The Al corrosion potential (Ecorr) and corrosion kinetic (icorr and Vcorr) are evaluated over 90 days. Additionally, the pore ion evolution, the matrix electrical resistance, the pore structure, and compressive strength are analysed. The corrosion process of Al alloy is affected by the pH and ion content in the pore solution. The pore pH increases from near neutral for the 1M M/P ratio to 9 and 10 for the 2 and 3M M/P ratio, increasing in the same way the corrosion of pure Al (AA1050) and AlMg alloys (AA5754). The effect of Mg content in the alloy (AA5754) becomes more relevant with the increase in the M/P ratio. The presence of phosphate ions in the pore solution inhibits the corrosion process in both Al alloys. The MKPC physicochemical stability improved with the increase in the M/P ratio, higher mechanical strength, and more refined pore structure.

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.

Smart Inhibition Action of Amino Acid-Modified Layered Double Hydroxide and Its Application on Carbon Steel.

Surface impregnation of concrete structures with a migrating corrosion inhibitor is a promising and non-invasive technique for increasing the lifetime of existing structures that already show signs of corrosion attack. The main requirement for inhibitors is their ability to diffuse the rebar at a sufficient rate to protect steel. The use of smart nanocontainers such as layered double hydroxides (LDH) to store corrosion inhibitors significantly increases efficiency by providing an active protection from chloride-induced corrosion. The addition of LDH to reinforced mortar can also improve the compactness and mechanical properties of this matrix. Here, we report the synthesis of a magnesium-aluminum LDH storing glutamine amino acid as a green inhibitor (labeled as Mg-Al-Gln), which can be used as a migrating inhibitor on mortar specimens. The corrosion behavior of the specimens was determined via electrochemical techniques based on measurements of corrosion potential and electrochemical impedance spectroscopy. A cell containing a 3.5% NaCl solution was applied to the mortar surface to promote the corrosion of embedded rebars. The specimens treated with Mg-Al-Gln presented an improved corrosion protection performance, exhibiting an increase in polarization resistance (Rp) compared to the reference specimens without an inhibitor (NO INH). This effect is a consequence of a double mechanism of protection/stimuli-responsive release of glutamine and the removal of corrosive chloride species from the medium.

Evaluation of Fillers for Magnesium Potassium Phosphate Cement (MKPC) for the Encapsulation of Low and Intermediate Level Metallic Radioactive Wastes.

This study investigates the effect of coal fly ash (FA), wollastonite (WO), pumice (PM), and metakaolin (MK) as filler materials in the rheological, mechanical, chemical, and mineralogical properties of a magnesium potassium phosphate cement (MKPC), designed for the encapsulation of low and intermediate level radioactive wastes containing reactive metals. Workability, compression strength, dimensional stability, pH, chemical composition, and mineralogical properties were studied in different pastes and mortars of MKPC with a fixed molar ratio of MgO/KH2PO4 = 1. No new mineral phases were found with the addition of the fillers, denoting their low chemical impact on the MKPC system. Moreover, all formulations with a water/cement mass ratio of <0.65 presented compressive strengths higher than 30 MPa after 90 days, and pH values lower than 8.5, corresponding to the passivation zone of aluminum corrosion.

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.

Influence of Accelerating Admixtures on the Reactivity of Synthetic Aluminosilicate Glasses.

This research aims at gaining a further understanding of the impact of accelerating admixtures on the reactivity of supplementary cementitious materials (SCMs), which are widely used as a clinker replacement in blended cements. This was done on synthetic glasses with controlled composition and structure that mimic two types of real SCMs (slag and calcium-rich fly ash). The effects of DEIPA, TIPA, NaSCN and Na2S2O3 on the glass dissolution, hydration kinetics and reaction products were investigated. The obtained results concluded that the pH of the NaOH solution and the composition of the synthetic glass play a key role on the effect of the admixtures. In 0.1 M NaOH (pH = 13.0), all the studied admixtures inhibited the dissolution of slag-like glasses while they enhanced the dissolution of Ca-rich fly ash-like glasses, being Na2S2O3 the admixture that led to the highest increase of the dissolution rate of the Ca-rich fly ash-type glasses. In 1 M NaOH solutions (pH = 13.8), only the alkali admixtures (NaSCN and Na2S2O3) enhanced the degree of reaction of both glasses. In slag-type glasses pastes mixed with 1 M NaOH, the addition of 2% Na2S2O3 induced the highest increase of their reactivity as inferred by the total heat release and the amount of bound water. This is related to the formation of a high amount of S(II)-AFm, in addition to C-A-S-H, that would increase the aluminium undersaturation of the pore solution and consequently the further dissolution of the glass.

ZnO Nanoparticles for Photocatalytic Application in Alkali-Activated Materials.

This paper reports an Alkali-Activated Materials (AAM) using two different precursors, metakaolin and a metallurgical slag with photocatalytic zinc oxide nanoparticles, as novel photocatalytic composites. The photodegradation performance of the composites using methylene blue (MB) dye as a wastewater model was investigated by ultraviolet radiations (UV-vis) spectroscopy. Adsorption in dark conditions and photodegradation under UV irradiation are the mechanisms for removing MB dye. The pseudo-first-order kinetic and pseudo-second-order kinetic models were employed, and the experimental data agreed with the pseudo-second-order model in both cases with UV and without UV irradiations. As new photocatalytic materials, these composites offer an alternative for environmental applications.

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.