Ivona Janković-Častvan

Surface Properties of HAp Particles Obtained by Hydrothermal Decomposition of Urea and Calcium-EDTA Chelates

In this paper surface properties of calcium-hydroxyapatite, synthes ized by modified hydrothermal reaction of urea and Ca(EDTA) 2– in phosphate solutions, as well as the dependence of calcium hydroxyapatite dispersion stability on pH were determined. T he specific surface area of calcium-hydroxyapatite was experimentally found to be 67 m /g. The point of zero charge (PZC) of indifferent KCl electrolyte of 6.8 ± 0.1 was determined by the batch equilibration method. From the dependence of surface charge density on pH and electrolyte concentrati on, the intrinsic equilibrium constant of surface groups p a2 K was determined to be 8.3 ± 0.1, while p int a1 K , calculated from the p int a2 K and point of zero charge values, is 5.3 ± 0.1. Hy droxyapatite suspension stability was investigated, in the pH range from 7 to12, it was r evealed that the most stable dispersion at pH 10. Introduction Hydroxyapatite is one of the main constituent compo unds of bones and teeth. Knowledge of the hydroxyapatite surface chemistry is very important from the point of view not only of bone tissue formation but also of HAP solubility, due to its in teraction with the surrounding fluid. Solubility of apatites is directly connected with various illness es uch as decalcination of bones (osteoporosis) and dental caries[1-2]. Behavior of the aqueous dispersion of hydroxyapatit e depends on the interfacial chemistry of the solid phase and dispersive medium. Surface charge o f hydroxyapatite in aqueous systems plays one of the main roles in determination of its colloidal and sorption properties [3]. The studies of the point of zero charge (pH PZC) and surface charge characteristics of apatites in dicate that H + and OH are potential-determinig ions and that the surface charge development at the apatite-water interface could be described by amphoteric dissociation react ions of surface functional groups [4,5]. In this paper, behavior and surface properties such as specific surface area, presence of particular surface groups, point of zero charge, surface charg e density, and intrinsic equilibrium constants of carbonate HAP obtained by hydrothermal decompositio n of urea and Ca-chelate, were reported. Methods and Materials Synthesis of carbonate hydroxyapatite was performed by a modified method of Fujishiro et al.[6-8], and was described earlier [9]. Specific surface area of HAP was determined by the B.E.T. (Brunauer – Emett – Teller) method, the sample was previously degassed in vacuum for 2 hour s at 150°C. The point of zero charge of HAP was determined by t he batch equilibration method described by one of the authors[10]. The adopted technique is as follows: KCl of different ionic strengths, 0.1 and 0.01 mol/ dm, was used as an electrolyte. First set of measurements included 12 samples with 25 cm 3 KCl of 0.1 mol/dm ionic strength. The initial pH (pHi) values, from 3 to 10, were adjusted by adding sm all volumes of 0.1 mol/dm 3 HCl or KOH to Key Engineering Materials Online: 2003-05-15 ISSN: 1662-9795, Vols. 240-242, pp 437-440 doi:10.4028/www.scientific.net/KEM.240-242.437

Kinetics, thermodynamics, and structural investigations on the removal of Pb2+, Cd2+, and Zn2+ from multicomponent solutions onto natural and Fe(III)-modified zeolites

The adsorption of Pb2+, Cd2+, and Zn2+ from equimolar multicomponent solutions onto natural and Fe(III)-modified zeolites was studied by batch experiments in order to determine the influence of the competitive effect on the efficiency ions removal at different initial concentrations and different temperatures. Kinetic and equilibrium studies showed that affinity of both zeolites was the highest for Pb2+ and much lower for Zn2+ and Cd2+. The competitive effect was negligible at lower concentrations, while Zn2+ and especially Cd2+ ions adsorption was suppressed as the concentrations were increased. Affinity of natural zeolite toward the ions was lower than that of the modified zeolite, as was shown for adsorption from single-component solutions. External film diffusion was the rate-controlling step at lower concentrations and for ions of higher affinity for the adsorbent, while intraparticle diffusion was dominant at higher concentrations and for ions of lower affinity for the adsorbent. The increasing spontaneity of the adsorption process with increasing temperature and the positive values of enthalpy of adsorption indicated the endothermic nature of the adsorption process. Structural investigations of the adsorbents loaded with Pb2+, Cd2+, and Zn2+ ions by X-ray photoelectron spectroscopy (XPS) confirmed the higher content of the ions in the surface and subsurface regions of the Fe(III)-modified than of the natural zeolite. XPS depth profiles of the loaded Fe(III)-modified zeolite showed that surface mechanisms of adsorption were dominant in the case of lead and cadmium, while zinc loading on the zeolite sample was governed mainly by an ion-exchange process.

Sintering Behaviour of Nanosized HAP Powder

The influences of temperature and time on sintering behaviour of nanosized HAP powder were investigate in this paper. The calcium hydroxyapatite powder, with the average crystallite size of 34 ± 1 nm, was uniaxially pressed at a pressure of 500 MPa. Obtained green compacts were sintered at temperature ranging from 1000°C to 1200°C in air atmosphere at various times. According to the results of scanning electron microscopy, X-ray and FTIR analyses, it is shown that HAP compacts with dense microstructure and average grain size below 250 nm is obtained.

Nanoscale zerovalent iron (nZVI) supported by natural and acid-activated sepiolites: the effect of the nZVI/support ratio on the composite properties and Cd 2+ adsorption

Natural (SEP) and partially acid-activated (AAS) sepiolites were used to prepare composites with nanoscale zerovalent iron (nZVI) at different (SEP or AAS)/nZVI ratios in order to achieve the best nZVI dispersibility and the highest adsorption capacity for Cd2+. Despite the higher surface area and pore volume of AAS, better nZVI dispersibility was achieved by using SEP as the support. On the other hand, a lower oxidation degree was achieved during the synthesis using AAS. X-ray photoelectron spectroscopy (XPS) analysis of the composite with the best nZVI dispersibility, before and after Cd2+ adsorption, confirmed that the surface of the nZVI was composed of oxidized iron species. Metallic iron was not present on the surface, but it was detected in the subsurface region after sputtering. The content of zerovalent iron decreased after Cd2+ adsorption as a result of iron oxidation during Cd2+ adsorption. The XPS depth profile showed that cadmium was present not only at the surface of the composite but also in the subsurface region. The adsorption isotherms for Cd2+ confirmed that the presence of SEP and AAS decreased the agglomeration of the nZVI particles in comparison to the pure nZVI, which provided a higher adsorption capacity. The results showed that the prevention of both aggregation and oxidation during the synthesis was necessary for obtaining an SEP/AAS–nZVI composite with a high adsorption capacity, but oxidation during adsorption was beneficial for Cd2+ removal. The formation of strong bonds between Cd2+ and the adsorbents sites of different energy until monolayer formation was proposed according to modeling of the adsorption isotherms.

Simultaneous enhancement of natural sunlight- and artificial UV-driven photocatalytic activity of a mechanically activated ZnO/SnO2 composite

Mechanical milling of commercial ZnO and SnO2 was used to produce a ZnO/SnO2 composite with a high density of surface defects; in particular, zinc interstitials (Zni) and oxygen vacancies (VO). To determine the impact of surface defects on photocatalytic activity, the relative concentration ratio of bulk defects to surface defects was modified by annealing at 400 and 700 °C. The possible application of the ZnO/SnO2 composite as a natural sunlight and UV-light driven photocatalyst was revealed via de-colorization of methylene blue. In both cases the ZnO/SnO2 composite exhibited enhanced photocatalytic activity as compared to the pristine ZnO. In order to investigate the origin of the enhancement, the pristine metal oxides and composites were characterized using a variety of techniques, including X-ray diffraction (XRD), Raman and Fourier transform infrared (FTIR) spectroscopy, field emission scanning electron microscopy (FESEM), laser diffraction particle size analysis, Brunauer–Emmett–Teller, UV-Vis diffuse reflectance and photoluminescence spectroscopy. High-resolution transmission electron microscopy (HRTEM) and elemental mapping analyses were used to reveal the presence of SnO2 nanocrystallites on the surface of larger ZnO particles. The enhanced photocatalytic activity of the composite can be attributed to the synergetic effect of the surface defects and the ZnO/SnO2 heterojunction particles, which facilitated charge separation, thereby hindering the recombination of photogenerated carriers. This study draws attention to mechanical activation as an inexpensive and environmentally friendly technique for the large-scale production of the composite with an enhanced photocatalytic activity under illumination of either UV or sunlight.

PVB/sepiolite nanocomposites as reinforcement agents for paper

In order to improve the mechanical properties of paper, 1, 3 and 5 wt. % of sepiolite were dispersed in a poly(vinyl butyral) (PVB) matrix and coated onto the surface of schrenz (110 g m-2). Deagglomerated sepiolite nanofibers in the PVB matrix on the paper surface were observed by scanning electron microscopy. The glass transition temperature of schrenz with PVB/sepiolite coatings was not changed with increasing content of sepiolite. Two different methods were used to evaluate the mechanical properties of the paper sample reinforced with PVB/sepiolite nanocomposites: tensile testing and nanoindentation. The values of breaking force and tensile energy absorption of the reinforced paper samples obtained by tensile testing were increased by up 10 %. The values of the reduced elastic modulus and hardness obtained by nanoindentation were increased by up to 78 %. The best improvement of the mechanical properties was shown by the paper sample coated with PVB/3 wt. % sepiolite nanocomposite.

Preparation of α-TCP Cements from Calcium Deficient Hydroxyapatite Obtained by Hydrothermal Method

In this paper the synthesis of bioactive cement based on α-Ca3(PO4)2 (α-TCP) and calcium deficient hydroxyapatite (CDHAp), obtained by hydrothermal method from CaCl2, EDTA, NaH2PO4·12H2O and urea at 160oC, was described. According to the results of DTA, SEM, X-ray and FTIR analyses performed in this investigation, it is shown that CDHAp is transformed to β- TCP at 780oC, and to α-TCP at 1400oC. The hardening of the samples, prepared from the mixture of α-TCP and 2.5 % solution of Na2HPO4, in simulated body fluid at 37oC, was followed by the microstructure changes.

Sepiolite functionalized with N-[3-(trimethoxysilyl)propyl]ethylenediamine triacetic acid trisodium salt. Part II: Sorption of Ni2+ ions from water

Abstract: The sorption of Ni 2+ on the sepiolite functionalized by covalent grafting of N -[3-(trimethoxysilyl)propyl]ethylenediamine triacetic acid trisodium salt, MSEAS, was studied in batch experiments as a function of the initial metal concentration, the equilibration time, pH value, and temperature. The modification of sepiolite resulted in an enhanced Ni 2+ retention with a capacity of 0.261 mmol/g at 298 K. The retention of Ni 2+ ions occurred dominantly by specific sorption and exchange of Mg 2+ ions from the sepiolite structure. The sorption process followed pseudo-second-order kinetics. The sorption equilibrium results were best described by the non-linear form of the Langmuir Sorption Equation. The values of the thermodynamic parameters (enthalpy, free energy and entropy) were calculated from temperature dependent sorption isotherms and these values showed that the sorption of Ni 2+ onto modified sepiolite was endothermic.