New Discovery of Natural Zeolite-Rich Tuff on the Northern Margin of the Los Frailes Caldera: A Study to Determine Its Performance as a Supplementary Cementitious Material.

The release of Neogene volcanism in the southeastern part of the Iberian Peninsula produced a series of volcanic structures in the form of stratovolcanoes and calderas; however, other materials also accumulated such as large amounts of pyroclastic materials such as cinerites, ashes, and lapilli, which were later altered to form deposits of zeolites and bentonites. This work has focused on an area located on the northern flank of the San José-Los Escullos zeolite deposit, the only one of its kind with industrial capacity in Spain. The main objective of this research is to characterize the zeolite (SZ) of this new area from the mineral, chemical, and technical points of view and establish its possible use as a natural pozzolan. In the first stage, a study of the mineralogical and chemical composition of the selected samples was carried out using X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray fluorescence (XRF), and thermogravimetric analysis (TGA); in the second stage, chemical-qualitative and pozzolanicity technical tests were carried out at 8 and 15 days. In addition, a chemical analysis was performed using XRF on the specimens of mortars made with a standardized mixture of Portland cement (PC: 75%) and natural zeolite (SZ: 25%) at the ages of 7, 28, and 90 days. The results of the mineralogical analyses indicated that the samples are made up mainly of mordenite and subordinately by smectite, plagioclase, quartz, halloysite, illite, and muscovite. Qualitative chemical assays indicated a high percentage of reactive silica and reactive CaO and also negligible contents of insoluble residues. The results of the pozzolanicity test indicate that all the samples analyzed behave like natural pozzolans of good quality, increasing their pozzolanic reactivity from 8 to 15 days of testing. Chemical analyses of PC/SZ composite mortar specimens showed how a significant part of SiO2 and Al2O3 are released by zeolite while it absorbs a large part of the SO3 contained in the cement. The results presented in this research could be of great practical and scientific importance as they indicate the continuation of zeolitic mineralization beyond the limits of the San José-Los Escullos deposit, which would result in an increase in geological reserves and the extension of the useful life of the deposit, which is of vital importance to the local mining industry.

Diatomites from the Iberian Peninsula as Pozzolans.

The object of this work is to study and characterize diatomites from the southeast of the Iberian Peninsula to establish their character and quality as natural pozzolans. This research carried out a morphological and chemical characterization study of the samples using SEM and XRF. Subsequently, the physical properties of the samples were determined, including thermic treatment, Blaine particle finesse, real density and apparent density, porosity, volume stability, and the initial and final setting times. Finally, a detailed study was conducted to establish the technical properties of the samples through chemical analysis of technological quality, chemical analysis of pozzolanicity, mechanical compressive strength tests at 7, 28, and 90 days, and a non-destructive ultrasonic pulse test. The results using SEM and XRF show that the samples are composed entirely of colonies of diatoms whose bodies are formed by silica between 83.8 and 89.99% and CaO between 5.2 and 5.8%. Likewise, this indicates a remarkable reactivity of the SiO2 present in both natural diatomite (~99.4%) and calcined diatomite (~99.2%), respectively. Sulfates and chlorides are absent, while the insoluble residue portion for natural diatomite is 1.54% and 1.92% for calcined diatomite, values comparatively lower than the standardized 3%. On the other hand, the results of the chemical analysis of pozzolanicity show that the samples studied behave efficiently as natural pozzolans, both in a natural and calcined state. The mechanical tests establish that the mechanical strength of the mixed Portland cement and natural diatomite specimens (52.5 MPa) with 10% PC substitution exceeds the reference specimen (51.9 MPa) after 28 days of curing. In the case of the specimens made with Portland cement and calcined diatomite (10%), the compressive strength values increase even more and exceed the reference specimen at both 28 days (54 MPa) and 90 days (64.5 MPa) of curing. The results obtained in this research confirm that the diatomites studied are pozzolanic, which is of vital importance because they could be used to improve cements, mortars, and concrete, which translates to a positive advantage in the care of the environment.

Ignimbrites Related to Neogene Volcanism in the Southeast of the Iberian Peninsula: An Experimental Study to Establish Their Pozzolanic Character.

The speed at which climate change is happening is leading to a demand for new pozzolanic materials that improve the quality of cements and, at the same time, limit the emission of greenhouse gases into the atmosphere. The main objective of this work is the detailed characterization of an ignimbrite sample (IGNS) to demonstrate its effectiveness as a natural pozzolan. To meet this objective, a series of tests were carried out. In the first stage, mineral and chemical analyses were performed, such as petrographic analysis by thin section (TSP), X-ray diffraction (XRD), oriented aggregate (OA), scanning electron microscopy (SEM) and X-ray fluorescence (XRF). In the second stage, the following technical tests were carried out: chemical quality analysis (QCA), pozzolanicity test (PT) and mechanical compressive strength (MS) at 7, 28 and 90 days, using mortar specimens with ignimbrite/cement formulation (IGNS/PC): 10, 25 and 40% to establish the pozzolanic nature of the ignimbrite. The results of the mineral and chemical analyses showed that the sample has a complex mineralogical constitution, consisting of biotite mica, potassium feldspar, plagioclase, smectite (montmorillonite), quartz, volcanic glass, iron, titanium and manganese oxides, chlorite and chlorapatite. On the other hand, the technological tests revealed the pozzolanic nature of the sample, as well as visible increases in the mechanical compressive strengths in the three proportions, the most effective being IGNS/PC:10% and IGNS/PC:25% at 7, 28 and 90 days of setting. The results obtained could be applied in the formulation of new pozzolanic cements with ignimbrite as a natural pozzolanic aggregate.

Effects of a Natural Mordenite as Pozzolan Material in the Evolution of Mortar Settings.

This paper shows the results of a study focused on the evolution and properties of mortars made with a mixture of portland cement (PC) and natural mordenite (Mor). To begin, samples of mordenite, cement and sand were studied with X-ray diffraction (XRD), X-ray fluorescence (XRF) and granulometric analysis (GA). Next, mortars with a ratio of 75% PC and 25% mordenite were prepared to determine their initial and final setting times, consistency and density. Continuing, the density, weight and compressive strength of the specimens were determined at 2, 7, 28, 90 and 365 days. Finally, the specimens were studied using SEM, XRD and XRF. The results of the study of the mordenite sample showed a complex constitution where the major mineral component is mordenite, and to a lesser degree smectite (montmorillonite), halloysite, illite, mica, quartz, plagioclase and feldspar, in addition to altered volcanic glass. Tests with fresh cement/mordenite mortar (CMM) showed an initial setting time of 320 min and a final setting time of 420 min, much longer than the 212-310 min of portland cement mortar (PCM). It was established that the consistency of the cement/mordenite mortar (CMM) was greater than that of the PCM. The results of the density study showed that the CMM has a lower density than the PCM. On the other hand, the density of cement/mordenite specimens (CMS) was lower than that of portland cement specimens (PCS). The CMS compressive strength studies showed a significant increase from 18.2 MPa, at 2 days, to 72 MPa, at 365 days, with better strength than PCS at 28 and 365 days, respectively. XRD, XRF and SEM studies conducted on CMS showed a good development of primary and secondary tobermorite, the latter formed at the expense of portlandite; also, ettringite developed normally. This work proves that the partial replacement of PC by mordenite does not have a negative effect on the increase in the mechanical strength of CMS. It indicates that the presence of mordenite inhibits the spontaneous hydration of C3A and controls the anomalous formation of ettringite (Ett). All this, together with the mechanical strength reported, indicates that mordenite has a deep and positive influence on the evolution of the mortar setting and is an efficient pozzolan, meaning it can be used in the manufacture of mortars and highly resistant pozzolanic cement, with low hydration heat, low density, stability in extremely aggressive places and a low impact on the environment.

Natural Mordenite from Spain as Pozzolana.

This work deals with anomalous concentrations of natural mordenite in the southeast of Spain. The X-ray diffraction (XRD) and scanning electron microscopy (SEM) studies evidenced that the samples contain mainly monomineral zeolitic phase of mordenite (70% to 74%), usually accompanied by smectite (montmorillonite), the principal component of bentonite. A study of the applicability of these zeolites is presented to establish the potential use as pozzolanic cements. For comparative purposes, synthetic commercial mordenite is also characterized and tested. The initial mixtures were prepared using cement and mordenite at a 75:25 ratio. Chemical analysis and a pozzolanicity test showed the high pozzolanic character. These mixtures were further added to sand and water, yielding the cement specimens to be used as concrete. Mechanical test results showed that the mechanical compression at 7 and 28 days fall into the range of 19.23 to 43.05 MegaPascals (MPa) for the cement specimens built with natural mordenites. The obtained results fall in the same range of cement specimens prepared with natural clinoptilolite, using mixtures within the European requirement for commercial concretes. Thus, these results and the low cost of natural mordenite of San José de los Escullos deposit supports the potential use of natural mordenite as pozzolanic cement.