Composition and Properties of Crystals Growing in the Ca2+–Mg2+–HPO2- 4–HCO- 3 System in the Presence of Na+, K+, Cl–, and SO2- 4 Ions

Data are presented on crystallization processes in aqueous solutions in the Ca²⁺–Mg²⁺–HPO^2- ₄–HCO^- ₃ system in the presence of Na⁺, K⁺, Cl^–, and SO^2- ₄ ions for molar ratios of the ions similar to those in human blood plasma. The solution concentration is shown to have a significant effect on the chemical composition and physicochemical properties of the forming precipitates.     

Interface between zinc phosphate-deposited steel fibres and cement paste

In an attempt to protect steel fibre reinforcements from corrosion and improve their adherence to cement pastes, we deposited a zinc phosphate (ZnPh) conversion coating on the surface of the fibres. At the interfacial contact zones between the cement paste and ZnPh, alkali-induced dissolution caused the dissociation of abundant PO ₄ ^3– ions from the ZnPh. The interaction of PO ₄ ^3– ions with Ca²⁺ ions from the pastes led to the formation of hydroxyapatite and brushite in the vicinity of the dissolved ZnPh surface. Such intermediate calcium phosphate compounds played important roles in (1) improving the cement-fibre interfacial bonds, and (2) repairing the damage of the ZnPh surfaces dissolved by alkali. These processes protected the steel fibre from corrosion.     

Reactivity of biological and synthetic hydroxyapatite towards Zn(II) ion, solid-liquid investigations

The reaction of biological and synthetic hydroxyapatite Ca₅(PO₄)₃OH (HAP) with Zn²⁺ ions is investigated as a function of Zn²⁺/Ca²⁺ molar ratio, time, temperature and electrolyte type (NaCl, NaHCO₃, Na₂HPO₄) by means of pH, pZn, pCa measurements, in aqueous solution. Biological powdered HAP invariably affords an almost quantitative reaction, while Zn²⁺ precipitated only partially by reaction with cubelets of biological HAP. Using powdered biological HAP and synthetic HAP (dried at 100 °C), the reaction with Zn²⁺ ion is fast and takes place without addition of precipitating anion; synthetic HAP (dried at 1000 °C) reacts if free phosphate ions are present. The solid phases separated after different reaction times are investigated by means of X-ray diffraction (XRD), IR, SEM techniques and elemental analysis (C,H,N). The solid phases contain Zn₃(PO₄)₂ { 4H₂O (Hopeite) at the beginning of reaction and CaZn₂(PO_{4 2} { 2H₂O (Scholzite) at the equilibrium.     

Hydrothermal precipitation of hydroxyapatite on anodic titanium oxide films containing Ca and P

Highly-crystallized hydroxyapatite (HA) can be precipitated during heat treatment in high-pressure steam at 300 °C on an anodic titanium oxide film containing Ca and P (AOFCP), which has been electrochemically formed on a titanium substrate prior to the hydrothermal treatment. Factors affecting the precipitation, such as a percentage of distilled water in the autoclave and additives in the AOFCP, were evaluated by scanning electron microscopy. Ca²⁺ and PO^3– ₄ ions were leached from the AOFCP into a water layer covering the film surface, and nucleate HA heterogeneously on the porous TiO₂ matrix of the AOFCP which was made by the ion leaching. The morphology of the precipitated crystals was significantly affected by the water volume ratio because the concentrations of the Ca²⁺ and PO₄ ^3– ions varied depending on the thickness of the water layer. The amount of the precipitation decreased on the AOFCP which was formed in the solution containing a small amount of Mg²⁺ ions or formed on Ti-6Al-4V alloy instead of titanium.     

Hydrolysis of tetracalcium phosphate in H3PO4 and KH2PO4

The activity product of tetracalcium phosphate (TTCP, Ca₄(PO₄)₂O), was determined at 37°C, and the hydrolysis of TTCP was investigated in 0.01–0.1 mol l^–1 H₃PO₄ and KH₂PO₄ solutions by means of calcium and phosphorus analyses, X-ray diffraction and infrared analysis. The activity product, defined as K _sp=(Ca²⁺)⁴ (PO ₄ ^3– )² (OH^–)², was 37.36 as pK _sp, which was smaller than that previously reported (42.4). TTCP easily hydrolysed to form calcium-deficient apatite (Ca-def OHAp, Ca_5–x (HPO₄) _x (PO₄)_3–x (OH)_1–x ), or dicalcium phosphate dihydrate (DCPD, CaHPO₄2H₂O), depending on the initial phosphate concentration. With 0.1 mol l^–1 H₃PO₄, TTCP hydrolysed to form DCPD within several minutes. In 0.025 mol l^–1 H₃PO₄ and 0.1 mol l^–1 KH₂PO₄, TTCP hydrolysed to form Ca-def OHAp through DCPD. In the latter solution, a small amount of octacalcium phosphate (OCP, Ca₈(H₂PO₄)₂(PO₄)₄5H₂O), was detected as an intermediate product. In 0.025 mol l^–1 KH₂PO₄, TTCP hydrolysed directly to form Ca-def OHAp. In 0.01 mol l^–1 H₃PO₄, hydrolysis of TTCP was not completed, although Ca-def OHAp was only a product. Thus the final product and the degree of hydrolysis depended on the pH and the overall Ca/P ratio in the reaction system. The rate of Ca-def OHAp formation seemed to be controlled by the dissolution rate of TTCP rather than the crystallization rate of the OHAp.     

Solubility characteristics of synthetic silicate sulphate apatites

Isomorphic substitution of (Si, S) for phosphorus in apatite (Ca₅(PO)₃F) was investigated in the solid solution series from P-apatite to (Si, S)-apatite utilizing compositions of Ca₅(PO₄)_3–x (SiO₄) _x/2(SO₄)_x/2F with x=0, 0.75, 1.5, 2, 2.25, 3. Study of the solubility characteristics of these apatites showed an increased weight loss in water with progression from the P-apatite end member to the (Si, S)-apatite end member. Experimentally determined pK _sp decreased from 60.62 for the fluorapatite (Ca₅(PO₄)₃F) to 31.65 for fluorellestadite (Ca₅(SiO₄)_1.5(SO₄)_1.5F). The free energy of formation calculated from the solubility product became less negative from –6755 kJ mol ^–1 for fluorapatite to –5760 kJ mol ^–1 for fluorellestadite.     

Fast Li+ ion conduction in Li2O–(Al2O3 Ga22O3)–TiO2–P2O5 glass–ceramics

Fast lithium ionic conducting glass-ceramics have been obtained by heat-treatment of glasses in the systems Li₂O–M₂O₃–TiO₂–P₂O₅ (M = Al and Ga). The glass–ceramics were mainly composed of LiTi₂(PO₄)₃ in which Ti⁴⁺ ions were partially replaced by M³⁺ ions. Considerable enhancement of the conductivity with the substitution of M³⁺ ions for Ti⁴⁺ ions was observed. The maximum conductivity obtained at room temperature was 1.3 × 10^–3 S cm^–1 for the aluminium system and 9 × 10^–4 S cm^–1 for the gallium system.     

The nonstoichiometry and physical properties of the Nd1−x Ca1+x FeO4−y system

The solid solutions of the Nd_1–x Ca_1+x FeO_4–y system for compositions ofx=0.000,0.125, 0.250,0.375, and 0.500 are prepared by drip pyrolysis. XRD analysis shows all the solid solutions are tetragonal I_4/mmm. The Fe⁴⁺ ratio to the total Fe ions or value has a maximum for the compositionx=0.375. From the X-ray powder diffraction analysis and the Mössbauer spectroscopy, the distortion and symmetry change of oxygen octahedra of Fe ions are observed. The structural change of oxygen octahedra of Fe ions strongly affects the physical properties. The solid solution whenx=0.000 shows a weak ferromagnetic behaviour due to the spin canting of the distorted octahedra. The other solid solutions withx=0.125, 0.250, 0.375, and 0.500 show a paramagnetic behaviour over room temperature. The decrease of the magnetic transition temperature is due to the distortion of oxygen octahedra of Fe ions and the existence of the Fe⁴⁺ ion. The formation site of oxygen vacancies plays an important role in the conductivity of the Nd_1–x Ca_1+x FeO_4–y system. Although the oxygen vacancies in [Nd, Ca]-O layer have little effect on conductivity, the oxygen vacancies in the FeO₂ plane of the perovskite layer act as electron trapping sites and thus increase the activation energy.     

Effect of the addition of Ca2+ on the structure, microstructure and ferroelectric properties of (Pb1 − y Ca y )(Zr0.8Ti0.2)O3 system with y = 0.0, 0.02, 0.05 and 0.1

This work studies the relationship between ferroelectric properties and structural features of the (Pb_{1 – y} Ca _y )(Zr_0.8Ti_0.2)O₃ system with y = 0.0, 0.02, 0.05 and 0.1. All of the samples were prepared by hot-pressing of PZT calcined powder, prepared by conventional ceramic route. Single phase compositions of rhombohedral (RH) structure were observed for the whole series of the samples studied in this work. However, a linear decrease of RH lattice constant a _p is seen with increasing the Ca²⁺ concentration with a subsequent decrease of lattice strain expressed by (90 – _p). Further, a sharp decline is also observed in the magnitudes of saturation polarization (P _s) of the samples doped with 2 mol% Ca²⁺. However, the rate of decrease slows down for Ca²⁺ concentrations above this level. A diffuse phase transition was observed in the case of 10 mol% Ca²⁺-doped PZT(0.8) which is believed to be possibly due to the distribution in coupling strengths created from a random compositional fluctuations of Ca²⁺ and Pb^2– ions on A-sites. The results are interpreted on crystal-chemical grounds. It is proposed that the long range coupling of (Zr/Ti)O₆ coordination octahedra and Pb²⁺ ions, due to the covalency of the Pb–O bond, is interrupted by the incorporation of Ca²⁺. By considering the effect of calcium on coupling strength and coupling distribution, the observed dielectric response for the above compositions is qualitatively explained.     

Hydrothermal synthesis of calcium hydroxyapatite nanorods in the presence of PVP

Calcium hydroxyphosphate (Ca₁₀(PO₄)₆(OH)₂, HAP) nanorods have been successfully synthesized by a simple and mild hydrothermal treatment in the presence of polyvinylpyrrolidone (PVP). A complex of calcium nitrate (Ca(NO₃)₂) and Na₂HPO₄ was used to supply the calcium and phosphate ions during the reactions. The synthesis of pure HAP nanorods was under near neutral condition. The morphology and structure of the samples were characterized by transmission electron microscope (TEM), scanning electron microscope (SEM), X-ray diffraction (XRD), and Fourier transform infrared (FT-IR) spectroscopy analysis. The nanorods were uniform with diameter of 20–25 nm and length ranging from several hundreds of nanometers to several micrometers. The influence of different experiment conditions, i.e., the PVP concentration, molar ratio of Ca²⁺ to HPO₄ ²⁻, reaction time, and temperature, on the morphology of the nanorods was investigated. The formation mechanism of rod-like HAP and effects of PVP on the crystal nucleation and growth have also been discussed.     

Substitution of manganese and iron into hydroxyapatite: Core/shell nanoparticles

The bioceramics, hydroxyapatite (HAP), is a material which is biocompatible to the human body and is well suited to be used in hyperthermia applications for the treatment of bone cancer. We investigate the substitution of iron and manganese into the hydroxyapatite to yield ceramics having the empirical formula Ca_9.4Fe_0.4Mn_0.2(PO₄)₆(OH)₂. The samples were prepared by the co-precipitation method. The formation of the nanocrystallites in the HAP structure as the heating temperatures were raised to obtain a glass–ceramic system are confirmed by X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM), electron diffraction (ED) and electron spin resonance (ESR). TEM images show the core/shell structure of the nanoparticles, with the core being formed by the ferrites and the shell by the hydroxyapatite. The ED patterns indicate the nanoparticles formed at 500 °C have an amorphous structure while the nanoparticles formed at 1000 °C are crystalline. ESR spectroscopy indicated that the Fe³⁺ ions have a g-factor of 4.23 and the Mn²⁺ ions have a g-factor of 2.01. The values of the parameters in the spin Hamiltonian which describes the interaction between the transition metal ions and the Ca²⁺ ions, indicate that the Mn²⁺ ion substitute into the Ca²⁺ sites which are ninefold coordinated, i.e., the Ca(1) sites.     

Precipitation of carbonate crystal on surface active glasses

Anions, such as CO₃ ^2– and SO₄ ^2– ions, in industrial wastewater can cause serious scale problem in drainage pipes and vessels, when combined with other metal ions in the water. In this study, it was attempted to remove CO₃ ^2– ions from an aqueous solution by using surface active glasses. Glasses with various compositions of SiO₂-Na₂O-B₂O₃-RO (R = Mg, Ca, Sr, Ba) system were reacted in a CO₃ ^2– ion-containing solution with various pH, then the glass surfaces were analyzed by XRD and SEM, and CO₃ ^2– ions in the reacted solution were also measured. CO₃ ^2– ions in the solution were combined with alkaline earth metal ions, which were leached out of the glass, and were precipitated on the glass surface as carbonate crystals. In this way, the carbonate ions could be removed from the solution. The removal capacity of CO₃ ^2– ions is closely related to the surface reactivity of the glass and solubility product constants of the newly formed carbonate crystals. Glass containing either SrO or BaO showed a strong uptake capacity of CO₃ ^2– ions from the solution.     

Red long-lasting phosphorescence (LLP) in β-TCP type Ca9.5Mn(PO4)7 compounds

Mn-ion doped calcium phosphates namely Ca₅(PO₄)₃(OH) hydroxyapatite (HAP), β-Ca₃(PO₄)₂ (β-TCP) as well as Ca_9.5Mn(PO₄)₇ whitlockite were synthesized and the optical properties of the Mn²⁺ cations were investigated. Annealing under reducing atmosphere enhances the emission of the divalent manganese species. Electron paramagnetic resonance (EPR) and optical spectroscopies confirm that Mn²⁺ ions are the active species. Orange and red emissions occur respectively for the Mn:HAP and Mn:TCP. For this latter, long-lasting phosphorescence (LLP) coming from the Mn²⁺ emission (⁴T₁ → ⁶A₁ transition) is observed at 640 nm but it appears that the traps depths are either two shallow or too deep to lead to an efficient long-lasting emission.     

Fabrication and optical properties of NUV-emitting SiO2–SrB4O7:Eu glass–ceramic thin films

SiO₂–SrB₄O₇:Eu²⁺ glass–ceramic thin films were fabricated for possible application in near ultraviolet (NUV) emitting devices. Nano-sized SrB₄O₇:Eu²⁺ powders were prepared by a Pechini-type sol–gel method and a subsequent ball-milling treatment. The powders showed NUV emissions centered at 367 nm, upon irradiation with UV of shorter wavelengths, due to an allowed 4f⁶5d¹ → 4f⁷ electronic transition of Eu²⁺ ions. The glass–ceramic thin films were prepared by dip-coating of tetraethylorthosilicate (TEOS) solutions dispersed with the nano-sized SrB₄O₇:Eu²⁺ powders and a subsequent heat-treatment. It was found that the glass–ceramic thin films had relatively high thermal stability up to 800 °C in terms of the Eu²⁺ emissions. SiO₂ layers surrounding SrB₄O₇:Eu²⁺ appeared to be effective for the surface passivation of the phosphor particles.     

Physico-chemical aspects of calcium vanadate apatite

By appropriate modifications of existing precipitation methods, a sample of calcium vanadate apatite, Ca₁₀(VO₄)₆(OH)₂ was prepared at 110°C. It was characterized through X-ray, electron microscopic, infrared and thermoanalytical analyses in addition to chemical analysis. Equilibrating the sample in buffered aqueous media at 37° C, the solubility was measured using microanalytical techniques of Ca²⁺ and VO₄ ^3– present in the saturated solutions after separating the colloidal component of the solute. Duration of equilibration for the attainment of saturation of the solution of the sample was obtained from a study on its dissolution kinetics. The pK _ip of calcium vanadate apatite was found to be 107.09. The investigation showed that pK _ip was independent of the presence of the common ions.     

Photo-induced formation of hydroxyapatite on TiO2 synthesized by a chemical–hydrothermal treatment

The formation of hydroxyapatite (HAp) on TiO₂ surfaces under continuous ultraviolet (UV) irradiation was investigated. Pure Ti substrates were chemically treated with H₂O₂/HNO₃ at 353 K for 20 min to form a TiO₂ gel layer. The specimens were then hydrothermally treated with an aqueous NH₃ solution in an autoclave at 453 K for 12 h. An adhesive and sufficiently crystallized anatase-type TiO₂ film could be synthesized on the Ti surface. The specimens were immersed in simulated body fluid in darkness or under UV irradiation with a centered wavelength of λ = 365 nm. Under dark conditions, a thin homogeneous HAp film was formed, with just a few spherical clusters of HAp. The UV illumination promoted the formation of HAp clusters, which may be due to the generation of functional Ti–OH or Ti–O groups on the TiO₂ surface. On the other hand, the UV light produced electron-hole pairs in the TiO₂, and the photogenerated holes that migrated to the surface repelled the Ca²⁺ ions in the solution. As a consequence, the UV irradiation suppressed the formation of a HAp thin film.     

Development and characterisation of novel Ce‐doped hydroxyapatite–Fe3 O4 nanocomposites and their in vitro biological evaluations for biomedical applications

Hydroxyapatite (HAP: Ca₁₀ (PO₄)₆ (OH)₂) is extensively used in biomedical field because of its biocompatibility, osteoconductivity and non‐toxicity properties. However, HAP exhibits poor mechanical strength and bacterial restriction behavior. To overcome these drawbacks, various metal ions such as Ag⁺, Zn²⁺, Cu²⁺, Ti⁴⁺ and Ce^4+/3+ are incorporated in HAP matrix to increase the mechanical and biological properties. Among these, Cerium (Ce) is selected as antibacterial agent due to its high thermal stability and its applications in dental fillings, bone healing and catheters. Fe₃ O₄ nanoparticles were used in hyperthermia treatment, magnetic fluid recordings and catalysis. In this present study, we have synthesized nanocomposites consisting of 1.25% Ce doped HAP with various concentrations of Fe₃ O₄ NPs as 90:10 (C‐1), 70:30 (C‐2) and 50:50 wt% (C‐3) using ball milling technique. The obtained Ce@HAP‐Fe₃ O₄ nanocomposites were characterized by ATR‐FTIR, XRD, VSM, SEM‐EDAX and TEM analysis. Further, the fabricated Ce@HAP‐Fe₃ O₄ nanocomposites were tested for its antibacterial activity towards Staphylococcus aureus (S. aureus) and Escherichia coli (E.coli), where C‐3 composites exhibit the excellent pathogen inhibition towards E.coli. In addition, the cytotoxicity evaluation on C‐3 nanocomposites by in vitro biocompatibility study using MG‐63 cells shows the prominent viable cell enhancement up to 400µg/mL concentrations.Inspec keywords: nanocomposites, iron compounds, calcium compounds, cerium, mechanical strength, antibacterial activity, biomedical materials, dentistry, bone, nanoparticles, nanofabrication, ball milling, Fourier transform infrared spectra, attenuated total reflection, X‐ray diffraction, magnetometry, scanning electron microscopy, transmission electron microscopy, microorganisms, cellular biophysics, nanomedicineOther keywords: Ce‐doped HAP–Fe3O4 nanocomposite, hydroxyapatite, in vitro biological evaluation, mechanical strength, bacterial restriction behaviour, metal ion, silver ion, zinc ion, copper ion, titanium ion, cerium ion, HAP matrix, antibacterial agent, thermal stability, dental filling, bone healing, catheter, Fe3O4 nanoparticle, hyperthermia treatment, magnetic fluid recording, catalysis, ball milling technique, Fourier transform infrared spectroscopy, attenuated total reflectance spectroscopy, X‐ray diffraction, vibrating sample magnetometry, scanning electron microscopy, SEM‐energy dispersive spectroscopy, transmission electron microscopy, TEM analysis, antibacterial activity, Staphylococcus aureus, Escherichia coli, pathogen inhibition, in vitro biocompatibility, MG‐63 osteoblast cell, cell enhancement, Ca₅ (PO₄)₃ (OH):Ce, Fe₃ O₄      

Synthesis and cytocompatibility of manganese (II) and iron (III) substituted hydroxyapatite nanoparticles

Manganese (II) and iron (III) substituted hydroxyapatite (HA, Ca₁₀(PO₄)₆(OH)₂) nanoparticles were synthesized using wet chemical method. All samples were single-phase, non-stoichiometric and B-type carbonated hydroxyapatite. Compared with pure HA, Mn²⁺ substituted (MnHA) and Fe³⁺ doped HA (FeHA) did not demonstrate significant structure deviation. Since ion exchange mechanism was applied for the synthesis process, the morphology and particle size were not significantly affected: all samples were elongated spheroids of around 70 nm. The presence of Fe and Mn was confirmed by energy dispersive X-ray spectroscopy (EDX) while the concentrations were quantified by inductively coupled plasma (ICP). Fe³⁺ ions were more active than Mn²⁺ ions in replacing Ca²⁺ ions in HA lattice structure. The magnetic property of HA was modified by substitution with Fe. The Fe5 (Fe_added/Ca_added = 5% by molar ratio) was paramagnetic while pure HA was diamagnetic. Results of extraction assay from cells cultured in extracted medium for 72 h suggested that both MnHA and FeHA were non-cytotoxic to osteoblast cells. Meanwhile, the presence of Fe³⁺ ions in HA demonstrated significant positive effect on osteoblast cells, where the cell number on Fe5 pellets was twice that of pure HA and MnHA samples.     

Preparation of spherical zirconium salt particles by homogeneous precipitation

Spherical basic zirconium sulphate particles were prepared by homogeneous precipitation in mixed solutions of zirconium sulphate and urea. Values of [SO ₄ ^2– ]/[Zr⁴⁺] and [urea]/[Zr⁴⁺] in starting mixed solutions and cooling rate may affect the formation of spherical particles. Complexes such as [Zr(OH)_n]^4–n could prevent the formation and thus lead to gel precipitation. In addition, spherical particles could only be obtained in the presence of SO ₄ ^2– ; for NO^3– and Cl^–, only gel precipitation occurred.     

X-ray diffraction study of calcium nitrate tetrahydrate melt at 328 K

The hydration structure of calcium nitrate tetrahydrate, Ca(NO₃)₂ · 4.1 H₂O, melt at 328 K has been investigated by X-ray scattering and correlation method. Analysis of the radial distribution function and model fitting revealed that in the hydrate melt, a Ca²⁺ ion is surrounded by about six oxygen atoms, 4.1 of which come from water molecules at the average distance of 0.241 nm, 2.0 coming from the nitrate ions at the average distance of 0.254 nm. In the first coordination shell of the melt, the formation of a direct Ca²⁺-NO ₃ ^– correlation, such as contact ion pairs, was suggested. The hydration structure of the melt analysed was compared with that of Ca(NO₃)₂ · 3.5H₂O melt previously reported, and the decrease from nine of the reported melt to six in this melt was observed in the number of the nearest neighbour oxygen atoms around a Ca²⁺ ion. This implies that in the highly concentrated aqueous solution, the structure of the first coordination shell around the cation changes markedly with a small difference in the water molecule content.