Relation of the aged gels microstructure on the zeolite a particulate properties.

The microstructure of the starting hydrogel has extremely important role in the synthesis of the microporous materials. Due to the fact that very limited number of experimental methods (techniques) can be used for gel analysis, there are still a lot of missing informations about the processes on molecular level, which occur before and during the nuclei formation. In this paper, various methods were used in characterization of pretreated (aged) hydrogel before the process of its hydrothermal transformation to zeolite A. Results show the changes in chemical composition and in microstructure of the solid phase (FTIR, PALS, BET, DTG), indicating that the structure of the ordered phase (potential nuclei) within gel matrix (completely amorphous according to PXRD patterns) is rather of different structural units typical for FAU and SOD (or their mixture) than the final product (LTA) only!

Complexation of gallic acid with calcium: electrochemical, potentiometric, and UV-VIS studies.

Gallic acid and its metal complexes are good antioxidants that could be used to increase the body's immune system against degenerative and viral diseases. Therefore, such complexes could be used as a good alternative to supplementary medicines and may have potential significance in clinical trials. Differential pulse voltammetry, UV/VIS spectroscopy, and potentiometry were used to analyse the complexation of gallic acid with calcium in this study. The metal : ligand ratio was determined using Job's continuous variation method and was found to be 2 : 1. The stability constant of calcium gallate was determined with potentiometric titration with a calcium electrode, which amounted to K° = 4.83 × 106 (log K° = 6.7). The combination of the results obtained in this study gives a deeper insight into the complexation of gallic acid with calcium and determines the stability constant of calcium gallate.

Microplastics encapsulation in aragonite: efficiency, detection and insight into potential environmental impacts.

Plastic pollution in aquatic ecosystems has become a significant problem especially microplastics which can encapsulate into the skeletons of organisms that produce calcium carbonates, such as foraminifera, molluscs and corals. The encapsulation of microplastics into precipitated aragonite, which in nature builds the coral skeleton, has not yet been studied. It is also not known how the dissolved organic matter, to which microplastics are constantly exposed in aquatic ecosystems, affects the encapsulation of microplastics into aragonite and how such microplastics affect the mechanical properties of aragonite. We performed aragonite precipitation experiments in artificial seawater in the presence of polystyrene (PS) and polyethylene (PE) microspheres, untreated and treated with humic acid (HA). The results showed that the efficiency of encapsulating PE and PE-HA microspheres in aragonite was higher than that for PS and PS-HA microspheres. The mechanical properties of resulting aragonite changed after the encapsulation of microplastic particles. A decrease in the hardness and indentation modulus of the aragonite samples was observed, and the most substantial effect occurred in the case of PE-HA microspheres encapsulation. These findings raise concerns about possible changes in the mechanical properties of the exoskeleton and endoskeleton of calcifying marine organisms such as corals and molluscs due to the incorporation of pristine microplastics and microplastics exposed to dissolved organic matter.

Precipitation at Room Temperature as a Fast and Versatile Method for Calcium Phosphate/TiO2 Nanocomposites Synthesis.

The constantly growing need for advanced bone regeneration materials has motivated the development of calcium phosphates (CaPs) composites with a different metal or metal-oxide nanomaterials and their economical and environmentally friendly production. Here, two procedures for the synthesis of CaPs composites with TiO2 nanoplates (TiNPl) and nanowires (TiNWs) were tested, with the immersion of TiO2 nanomaterials (TiNMs) in corrected simulated body fluid (c-SBF) and precipitation of CaP in the presence of TiNMs. The materials obtained were analyzed by powder X-ray diffraction, spectroscopic and microscopic techniques, Brunauer-Emmett-Teller surface area analysis, thermogravimetric analysis, dynamic and electrophoretic light scattering, and their hemocompatibility and ability to induce reactive oxygen species were evaluated. After 28 days of immersion in c-SBF, no significant CaP coating was formed on TiNMs. However, the composites with calcium-deficient apatite (CaDHA) were obtained after one hour in the spontaneous precipitation system. In the absence of TiNMs, CaDHA was also formed, indicating that control of the CaP phase formed can be accomplished by fine-tuning conditions in the precipitation system. Although the morphology and size of crystalline domains of CaDHA obtained on the different nanomaterials differed, no significant difference was detected in their local structure. Composites showed low reactive oxygen species (ROS) production and did not induce hemolysis. The results obtained indicate that precipitation is a suitable and fast method for the preparation of CaPs/TiNMs nanocomposites which shows great potential for biomedical applications.

Kinetics of struvite to newberyite transformation in the precipitation system MgCl2-NH4H2PO4NaOH-H2O.

The influence of the initial reactant concentrations on the composition of the solid phases formed in the precipitation system MgCl(2)-NH(4)H(2)PO(4)-NaOH-H(2)O was investigated. The precipitation diagram constructed shows the approximate concentration regions within which struvite, newberyite, and their mixtures exist at 25 degrees C and an aging time of 60 min. It was found that immediately after mixing the reactant solutions, struvite (MgNH(4)PO(4).6H(2)O) precipitated in nearly the whole concentration area, while newberyite (MgHPO(4).3H(2)O) appeared mostly within the region of the excess of magnesium concentration. It was also found that after aging time of 60 min the precipitation domain of struvite alone is much broader than that of newberyite or the domain of their coexistence, and shows that struvite is more abundant in the systems in which the initial concentration of ammonium phosphate is higher than that of magnesium. The kinetics of struvite to newberyite transformation (conversion) was systematically studied under the conditions of different initial reactant concentrations and different initial pH in the systems in which a mixture of both phases precipitated spontaneously. The struvite to newberyite conversion period was found to be strongly related to the ratio of initial supersaturations, S(N)/S(S), rather than to the any particular physical quantity that can describe and predict the behavior of the precipitation system. Experimental data suggest a solution-mediated process as a most possible transformation mechanism. Along with a continuous monitoring of the changes in the liquid phase, the content of struvite in the solid phase was estimated by means of a Fourier transform infrared (FT-IR) method, developed for this particular precipitation system.

Formation and morphology of struvite and newberyite in aqueous solutions at 25 and 37 degrees C.

The influence of the initial reactant concentrations (c(i)(Mg)tot = 5.0 x 10(6) to 5.0 x 10(-1) mol dm(-3), c(i)(P)tot = c(i)(NH4)tot = 1.0 x 10(-3) to 5.0 x 10(-1) mol dm(-3)) and temperature (25 and 37 degrees C) on the composition and morphology of the precipitates formed in the system MgCl2-NH4H2PO4-NaOH-H2O at initial pHi = 7.40 has been investigated. Precipitation diagrams are presented showing the concentration regions within which different morphologies of solid phase have been formed. The solid phases aged for 24 hours were characterized by means of optical microscopy, FT-IR spectrophotometry, X-ray diffractometry and thermogravimetry. It was found that struvite was a predominant phase formed within the concentration region examined and newberyite was obtained only in the region where pH(24h) < 6.5. The influence of the initial pH on the formation and transformation of these two compounds were studied in the region 5.0 < or = pHi < or = 9.0 and the results are discussed.

Metabolic evaluation of urolithiasis patients from eastern Croatia.

Metabolic parameters were determined in fasting blood serum, fasting first morning urine, and 24-hour urine of male patients with recurrent calcium oxalate stones (N = 26, age 39.1 +/- 6.2 years) as well as in male healthy controls (N = 18, age 35.0 +/- 7.1 years), recruited from the eastern part of Croatia. The 24-hour urinary calcium excretion was significantly higher (p < 0.01) for patients (5.6 +/- 2.5 mmol) than for controls (3.7 +/- 1.9 mmol), but potassium excretion was higher (p < 0.01) for controls (74.5 +/- 33.8 mmol) than for patients (49.2 +/- 15.7 mmol). The mean ionic activity product of calcium and oxalate ions, IAP(CaOx), calculated from the fasting first morning urine parameters, was 25% higher for patients than for controls, but the difference was not statistically significant (p > 0.05). Very strong correlation (r = 0.97) was obtained between IAP(CaOx) values and calculated Ogawa indices that were recommended for estimating the potential risk for calcium oxalate stone formation.

Precipitation of different calcite crystal morphologies in the presence of sodium stearate.

The influence of sodium stearate (NaSt) on the precipitation of calcium carbonate during the semicontinuous process of slaked lime carbonation was studied in the systems in which process parameters, like concentration of total dissolved calcium, temperature, CO(2) flow rate and initial addition rate of slaked lime, were controlled. It was found that calcite was the only calcium carbonate polymorph that appeared under the investigated experimental conditions, while FT-IR spectroscopy and thermogravimetric analysis of samples confirmed the presence of stearate on the surface of precipitated calcium carbonate (PCC). Specific surface area of PCC increased with increasing stearate content: the highest value, s = 52.8 m(2) g(-1), was obtained at t = 20 degrees C, c(tot) = 17.0 mmol dm(-3) and the stearate content of m(NaSt)/m(CaO) = 0.03. It was also found that hydrophobic calcite crystals in the form of rhombohedral and scalenohedral morphology can be produced at m(NaSt)/m(CaO) > 0.01. The exception is the case of nanosized PCC production, when much higher concentration of NaSt is needed, m(NaSt)/m(CaO) = 0.22. Minimal amount of stearate necessary to build up the monolayer and corresponding cross sectional area of one stearate molecule were estimated for the obtained calcite morphologies.

Effect of inorganic anions on the morphology and structure of magnesium calcite.

Calcium carbonate was precipitated from calcium hydroxide and carbonic acid solutions at 25 degrees C, with and without addition of different magnesium (MgSO(4), Mg(NO(3))(2) and MgCl(2)) and sodium salts (Na(2)SO(4), NaNO(3) and NaCl) of identical anions, in order to study the mode of incorporation of magnesium and inorganic anions and their effect on the morphology of calcite crystals over a range of initial reactant concentrations and limited c(i)(Mg(2+))/c(i)(Ca(2+)) molar ratios. The morphology, crystal size distribution, composition, structure, and specific surface area of the precipitated crystals, as well as the mode of cation and anion incorporation into the calcite crystal lattice, were studied by a combination of optical and scanning electron microscopy (SEM), electronic counting, a multiple BET method, thermogravimetry, FT-IR spectroscopy, X-ray diffraction (XRD), and electron paramagnetic resonance (EPR) spectroscopy. In the systems of high initial relative supersaturation, precipitation of an amorphous precursor phase preceded the formation of calcite, whereas in those of lower supersaturation calcite was the first and only polymorphic modification of calcium carbonate that appeared in the system. The magnesium content in calcite increased with the magnesium concentration in solution and was correlated with the type of magnesium salt used. Mg incorporation caused the formation of crystals elongated along the calcite c axis and, in some cases, the appearance of new [011] faces. Polycrystalline aggregates were formed when the c(i)(Mg(2+))/c(i)(Ca(2+)) molar ratios in solution were increased. Addition of sulfate ions, alone, caused formation of spherical calcite polycrystalline aggregates.