The advanced tendencies in building materials development are related to the design of cement composites with a reduced amount of Portland cement, contributing to reduced CO₂ emissions, sustainable development of used non-renewal raw materials, and decreased energy consumption. This work deals with water cured for 28 and 120 days cement composites: Sample A—reference (white Portland cement + sand + water); Sample B—white Portland cement + marble powder + water; and Sample C white Portland cement + marble powder + polycarboxylate-based water reducer + water. By powder X-ray diffraction and FTIR spectroscopy, the redistribution of CO₃²⁻, SO₄²⁻, SiO₄⁴⁻, AlO₄⁵⁻, and OH⁻ (as O-H bond in structural OH⁻ anions and O-H bond belonging to crystal bonded water molecules) from raw minerals to newly formed minerals have been studied, and the scheme of samples hydration has been defined. By thermal analysis, the ranges of the sample’s decomposition mechanisms were distinct: dehydration, dehydroxylation, decarbonation, and desulphuration. Using mass spectroscopic analysis of evolving gases during thermal analysis, the reaction mechanism of samples thermal decomposition has been determined. These results have both practical (architecture and construction) and fundamental (study of archaeological artifacts as ancient mortars) applications.

Cadmium exchange on clinoptilolite is performed and structurally studied for different durations of the ion exchange process (2 h, 24 h, 72 h, 168 h, 12 days, 22 days) at room temperature and 90 °C. The distribution of Cd²⁺ ions in all samples is elucidated after exchange on clinoptilolite using powder XRD data processed by Rietveld structural software. Clinoptilolite is not selective for cadmium cations, but at 90 °C the exchange is ~2.5 cations per unit cell. At RT it reaches ~1.25 cations per unit cell being twice as low. The obtained maximum exchanged sample for 22 days 90 °C was structurally refined in order to find the cadmium positions in the clinoptilolite voids. The structural refinements of the occupations of the incoming and outgoing cations give an idea of how the intracrystalline diffusion is processed. A good correlation between results obtained by structural refinement of the Cd-exchanged samples and the data of the EDS measurements was achieved.

The structural features and the thermal behavior of natural, Na-, Ca-, K-, Mg-, and Cd-exchanged clinoptilolite from the Beli Plast deposit (Bulgaria) were studied. Purified clinoptilolite sample was preliminary prepared and ion-exchanged at 100 °C for six days. DSC-TG analyses were performed for all studied forms. The effects in the DSC curves show differences with temperature due to release of weakly bound H₂O molecules and strongly bound ones. The endotherm minima temperatures were between 78 and 115 °C decreasing in the sequence K- < Na- < Natural- < Ca- ≤ Mg- < Cd-clinoptilolite. The hydrate complexes around the exchanged cations also influenced the DSC curves. The cation-coordinating H₂O molecules and the non-coordinating ones were determined by XRD structural refinement for all exchanged samples. The H₂O molecules of the cation–hydrate complexes are released at higher temperatures than weakly bound ones and affected the DSC curves differently. The structural adjustments made by the Rietveld method, as well as the applied EDS analyzes for the chemical composition of the samples, allowed us to correlate these data to the thermal characteristics of the studied clinoptilolite samples.

The Rietveld method using X-ray powder diffraction data was applied to selected skarn samples for quantitative determination of the present minerals. The specimens include garnet, clinopyroxene–garnet, plagioclase–clinopyroxene–wollastonite–garnet, plagioclase–clinopyroxene–wollastonite, plagioclase–clinopyroxene–wollastonite–epidote, and plagioclase–clinopyroxene skarns. The rocks are coarse- to fine-grained and characterized by an uneven distribution of the constituent minerals. The traditional methods for quantitative analysis (point-counting and norm calculations) are not applicable for such inhomogeneous samples containing minerals with highly variable chemical compositions. Up to eight individual mineral phases have been measured in each sample. To obtain the mineral quantities in the skarn rocks preliminary optical microscopy and chemical investigation by electron probe microanalysis (EPMA) were performed for the identification of some starting components for the Rietveld analysis and to make comparison with the Rietveld X-ray powder diffraction results. All of the refinements are acceptable, as can be judged by the standard indices of agreement and by the visual fits of the observed and calculated diffraction profiles. A good correlation between the refined mineral compositions and the data of the EPMA measurements was achieved.

Partial and almost complete barium exchange on clinoptilolite is performed and structurally studied for different durations (2 h, 24 h, 72 h, 168 h, 12 d, 22 d) at room temperature and 90 °C of the ion exchange process. Continuing ion exchange up to the 22nd day is proved by EDS analyses data and powder XRD (intensity changes of 020 and 200 peaks). Rietveld structure refinement was first performed on the maximum Ba exchanged clinoptilolite at 90 °C for 22 days (3.04 atoms per unit cell). Four barium positions and 9 H₂O sites were refined. The split positions Ba2 and BaK (around M3 site in channel C) were found mostly occupied by 2.23 atoms per unit cell. The rest of refined samples showed different occupations of the positions of incoming Ba²⁺ and outgoing cations (Na⁺, Ca²⁺, K⁺, Mg²⁺) during ion exchange, describing extra-framework cationic movements, which are released easily without preferable directions. The exchanges at 90 °C and room temperature were found proceeding similarly up to the 2nd hour, but then at room temperature the process is slowed and at 22nd day 1.64 barium atoms per unit cell are structurally refined.