Synthesis and characterisation of nanophase hydroxyapatite co-substituted with strontium and zinc

In order to develop new bioactive calcium phosphate (CaP) materials to repair bone defects, it is important to ensure these materials more closely mimic the non-stoichiometric nature of biological hydroxyapatite (HA). Typically, biological HA combines various CaP phases with different impurity ions, which substitute within the HA lattice, including strontium (Sr²⁺), zinc (Zn²⁺), magnesium (Mg²⁺), carbonate (CO₃^2-) and fluoride (F^-), but to name a few. In addition to this biological HA have dimensions in the nanometre (nm) range, usually 60?nm in length by 5–20?nm wide. Both the effects of ion substitution and the nano-size crystals are seen as important factors for enhancing their potential biofunctionality. The driving hypothesis was to successfully synthesise nanoscale hydroxyapatite (nHA), co-substituted with strontium (Sr²⁺) and zinc (Zn²⁺) ions in varying concentrations using an aqueous precipitation method and to understand their chemical and physical properties. The materials were characterised using Fourier Transform Infrared Spectroscopy (FTIR), X-Ray Diffraction (XRD), X-Ray Photoelectron Spectroscopy (XPS) and Transmission Electron Microscopy (TEM) techniques. The FTIR, XRD and XPS results confirmed that the nHA was successfully co-substituted with Sr²⁺ and Zn²⁺, replacing Ca²⁺ within the nHA lattice at varying concentrations. The FTIR results confirmed that all of the samples were carbonated, with a significant loss of hydroxylation as a consequence of the incorporation of Sr²⁺ and Zn²⁺ into the nHA lattice. The TEM results showed that each sample produced was nano-sized, with the Sr/Zn-10%nHA having the smallest sized crystals approximately 17.6 ± 3.3?nm long and 10.2 ± 1.4?nm wide. None of the materials synthesised here in this study contained any other impurity CaP phases. Therefore, this study has shown that co-substituted nHA can be prepared, and that the degree of substitution (and the substituting ion) can have a profound effect on the attendant materials’ properties.     

Effects of Sr2+/Zn2+ co-substitution on crystal structure and properties of nano-β-tricalcium phosphate

The incorporation of therapeutic ions like Sr²⁺, Si⁴⁺, Zn²⁺ and Li⁺ into biomaterials has become a promising approach to promote bone regeneration. However, the effects of Sr²⁺ and Zn²⁺ co-substitution on the crystal structure and properties of β-tricalcium phosphate (β-TCP) have not been elucidated well. In this study, Sr²⁺/Zn²⁺ co-substituted β-tricalcium phosphate (SrZnTCP) nano-powders with different extents of substitution (0–4.8 mol%) were synthesized by poly(ethylene glycol)-assisted co-precipitation and subsequent heat treatment. The as-synthesized SrZnTCP nano-powders were characterized by x-ray diffraction, Fourier transform infrared spectroscopy, elemental analysis, Rietveld refinement and differential scanning calorimetry. The results showed that the conversion of calcium-deficient apatite to β-TCP was achieved after heat-treatment above 800 °C. The a-axis and c-axis lattice parameters gradually decreased with increasing level of Sr²⁺/Zn²⁺ co-substitution in β-TCP lattice. Sr²⁺ and Zn²⁺ preferentially occupied the ninefold coordinated Ca (4) sites and the sixfold coordinated Ca (5) sites, respectively. The co-substitution of Sr²⁺ and Zn²⁺ for Ca²⁺ significantly improved the thermal stability of β-TCP. The release rate of Zn²⁺ from SrZnTCP depended on Ca²⁺ concentration over 63-day immersion in PBS solution while that of Sr²⁺ was not affected by Ca²⁺ concentration. The amount of Sr²⁺ released increased with increasing Sr²⁺ content in SrZnTCP. Collectively, SrZnTCP showed great promise as a Sr²⁺/Zn²⁺-releasing biomaterial for bone repair, although no obvious mineralization was observed on β-TCP and SrZnTCP disc samples during 56 days of immersion in simulated body fluid.     

Luminescence and structural properties of Gd2SiO5:Eu3+ phosphors synthesized from the modified solid state method

This paper reports the preparation of Eu³⁺ doped Gadolinium oxyorthosilicate (Gd₂SiO₅:Eu³⁺) phosphor with different concentration of Eu³⁺(0.1–2.5 mol%) using the modified solid state reaction method. The synthesis procedure of the Gd₂SiO₅:Eu³⁺phosphor using inorganic materials such as Gd₂O₃, silicon dioxide (SiO₂), europium oxide (Eu₂O₃) and boric acid (H₃BO₃) as flux is discussed in detail. The prepared phosphor samples were characterized by using X-Ray Diffraction (XRD), Field Emission Gun Scanning Electron Microscopy (FEGSEM), Transmission Electron Microscopy (TEM), Fourier Transform Infrared Spectroscopy (FTIR), Photoluminescence (PL) and Thermoluminescence (TL). The Commission Internationale de l′Eclairage(CIE) coordinates were also calculated. The PL emission was observed in the 350–630 nm range for the Gd₂SiO₅:Eu³⁺ phosphor. PL excitation peaks were observed at 266, 275, 312 and 395 nm while the emission peaks were observed at 380, 416, 437, 545, 579, 589, 607, 615 and 628 nm. The emission peak at 615 nm was the most intense peak for all the different Eu³⁺ concentration samples. From the XRD data, using the Scherrer's formula, the average crystallite size of the Gd₂SiO₅:Eu³⁺ phosphor was calculated to be 33 nm. TL was carried out for the phosphor after both UV and gamma irradiation. The TL response of the Gd₂SiO₅:Eu³⁺ phosphor for the two different radiations was compared and studied in detail. It was found that the present phosphor can acts as a single host for red emission (1.5 mol%) for display devices and light emitting diode (LED) and white light emission for Eu³⁺(0.1 mol%) and it might be used as a TL dosimetric material for gamma dose detection.     

Luminescence properties of Eu2+ and Mn2+ doped Sr1.7Mg0.3SiO4 phosphors

Eu²⁺, Mn²⁺ doped Sr_1.7Mg_0.3SiO₄ phosphors were prepared by high temperature solid-state reaction method. Their luminescence properties were studied. The emission spectra of Eu²⁺ singly doped Sr_1.7Mg_0.3SiO₄ consist of a blue band (455 nm) and a green band (550 nm). The relative intensities of two emissions varied with Eu²⁺ concentration. Eu²⁺ and Mn²⁺ co-doped Sr_1.7Mg_0.3SiO₄ phosphors emit three color lights and present whitish color. The blue (455 nm) and green (550 nm) emissions are attributed to the transitions of Eu²⁺, while the red (670 nm) emission is originated from the transition of Mn²⁺ ion. The results indicate the energy transfer from Eu²⁺ to Mn²⁺. The mechanism of the energy transfer is resonance-type energy transfer due to the spectral overlap between the emission of Eu²⁺and the absorption of Mn²⁺.     

Tunable single-phased white-emitting Sr3Y(PO4)3:Dy3+ phosphors for near-ultraviolet white light-emitting diodes

Single-component white-emitting Sr₃Y(PO₄)₃:Dy³⁺ phosphors were synthesized by a high-energy deformation process. X-ray diffraction patterns showed the resulting crystallized phase to be of cubic structure, space group I-43d (no. 220). The broad-band excitation spectra between 250 and 500 nm were observed by monitoring the emission wavelength at 576 nm, which matches well with commercial near-UV or blue LED chips. Under a 352 nm excitation, the emission peaks were observed at 483 nm (blue), 576 nm (yellow), and 666 nm (red), corresponding to the ⁴F_9/2 → ⁶H_15/2, ⁴F_9/2 → ⁶H_13/2, and ⁴F_9/2 → ⁶H_11/2 transitions of Dy³⁺ ions. The optimized doping concentration of Dy³⁺ ion was 8 mol%. By controlling the Dy³⁺ ion concentration, tunable colors from white to yellow were obtained in Sr₃Y(PO₄)₃:Dy³⁺ phosphors. These results reveal that studied materials may be a promising candidate for white LED applications.     

Feasibility of producing geopolymer binder based on a brick clay mixture

A brick clay mixture from a company localized in the north west of France is used for this study. The feasibility of producing geopolymer materials from a clay mixture was investigated. The final aim is to find a new application for this aluminosilicate material. One metakaolin (for a reference), the brick clay mixture, and the clay mixture calcined at two temperatures were compared after reaction with each of three alkaline solutions with different reactivity (the reactivity of each is defined). Physical, chemical, structural (FTIR and XRD) and thermal characterization (DTA) were first performed on the raw materials. Then, the structural evolution of the formed geopolymers was investigated using FTIR spectroscopy and XRD. Thus, this study demonstrates the feasibility of producing consolidated materials from a calcined brick clay (containing calcium oxides), which exhibits higher reactivity than brick clay. Plus, from a mixture of 25 wt% of less reactive materials such as ground brick clay and 75 wt% of reactive materials, it is possible to obtain geopolymer materials. FTIR study reveals the presence of a Ca²⁺ release phenomena, with a simultaneous polycondensation reaction for products based on calcined brick clay, which is different according to the silicate solution. Moreover, a link between [M⁺+M²⁺] and the different networks formed in the samples based on calcined clay was found. Indeed, it appears that the concentration within the range 10.5–14 mol/l favors the geopolymer network formation.     

Synthesis and photoluminescence properties of the high-brightness Eu3+-doped Sr3Y(PO4)3 red phosphors

A series of red-emitting phosphors Eu³⁺-doped Sr₃Y(PO₄)₃ have been successfully synthesized by conventional solid-state reaction, and its photoluminescence properties have been investigated. The excitation spectra reveal strong excitation bands at 392 nm, which match well with the popular emissions from near-UV light-emitting diode chips. The emission spectra of Sr₃Y(PO₄)₃:Eu³⁺ phosphors exhibit peaks associated with the ⁵D₀ → ⁷F_J (J = 0, 1, 2, 3, 4) transitions of Eu³⁺ and have dominating emission peak at 612 nm under 392 nm excitation. The integral intensity of the emission spectra of Sr₃Y_0.94(PO₄)₃:0.06Eu³⁺ phosphors excited at 392 nm is about 3.4 times higher than that of Y₂O₃:Eu³⁺ commercial red phosphor. The Commission Internationale de l’Eclairage chromaticity coordinates, the quantum efficiencies and decay times of the phosphors excited under 392 nm are also investigated. The experimental results indicate that the Eu³⁺-doped Sr₃Y(PO₄)₃ phosphors are promising red-emitting phosphors pumped by near-UV light.     

Preparation and characterization of materials in the system xCuO-(50-x) CdO-50B2O3

New glassy materials in the system xCuO-(50-x) CdO–50B₂O₃ were prepared by a melting-quench technique. Their UV–vis, FTIR, electrical, dielectric, SEM, XRD patterns and density properties were investigated. SEM and XRD studies confirmed their amorphous nature and the presence of crystalline phases in the sample with 50 mol% CuO. Replacing CdO with increasing concentrations of CuO decreased the density and increased the molar volume. Optical reflectance spectra revealed the presence of Cu²⁺ ions in octahedral coordination, as well as the presence of Cu¹⁺ and Cuº in the samples with greater than 30% CuO. FTIR measurements confirmed the conversion of BO₄ units to BO₃ units with increasing CuO contents. The conduction in the CuO-containing samples increased as the CdO was completely replaced by CuO. The CuO-containing samples exhibited a slight increase in the ɛʹ values with increasing temperature and a decrease with increasing frequency. The ɛʹ values gradually increase upon replacing CdO with up to 40 mol% CuO. An abrupt increase in ɛʹ was recorded for the sample with 50 mol% CuO, particularly at high temperature. The latter sample showed an εʹ value of 927at 100 Hz and 298 K. Prepared samples with high ɛʹ values are promising candidates for capacitor materials in electronic devices.     

Synthesis and photoluminescence properties of Sr3(PO4)2:Re3+, Li+ (Re = Eu,Sm) red phosphors for white light-emitting diodes

Sr₃(PO₄)₂:Re³⁺, Li⁺ (Re = Eu, Sm) red phosphors were prepared via a high temperature solid state reaction, and their structure and luminescence properties were investigated. X-ray diffraction patterns indicate that the phase of as-prepared samples is in good agreement with standard Sr₃(PO₄)₂ structure. Under 395 nm excitation, the emission of Sr₃(PO₄)₂:Eu³⁺ consists of a strong peak centered at 622 nm and two weak peaks centered at 598 nm and 660 nm, which correspond to ⁵D₀→⁷F₂, ⁵D₀→⁷F₁ and ⁵D₀→⁷F₃ transitions, respectively. Also, the emission spectrum of Sr₃(PO₄)₂:Sm³⁺ shows three main peaks at 568 nm, 603 nm and 651 nm, which are attributed to ⁴G_5/2→⁶H_I/2 (I = 5, 7, 9) transitions of Sm³⁺. Furthermore, luminescence properties of Sr₃(PO₄)₂:Re³⁺, Li⁺ (Re = Eu, Sm) samples are enhanced significantly by Li⁺ ions doping as charge compensator. Results indicate that as-prepared Sr₃(PO₄)₂:Re³⁺, Li⁺ (Re = Eu, Sm) could be the potential red phosphors used in white light-emitting diodes.     

Cd2+-sensiting bichromophore: Excimer emission from an EDTA-methylnaphthalene derivative

Chelating EDTA-based bichromophores, 1,4-bis(methylenecarboxy)-1,4-bis(N-1-naphthylmethylacetamide)-1,4- diazabutane (1) and its 2-napthyl isomer (2), were synthesized, and their fluorescence emission and complexation with Cd²⁺ and Zn²⁺ were studied. The fluorescence spectrum of 2 exhibited an emission band due to intramolecular excimer at about 400 nm in addition to a band from a monomeric (or isolated) chromophore at 335 nm. Complexation with Cd²⁺ sensitively intensified the excimer band and weakened the monomer band, as a result of formation of a [CdL₂]²⁻ type complex. In contrast, Zn²⁺ formed [ZnL]⁰, leading to depression of the excimer emission and enhancement of the monomer emission. The extent of the changes in emission intensities in the Cd²⁺ complex was larger than that of the Zn²⁺ complex contrary to the common metal-ion effect on fluorescence. Such a characteristic emission property was not observed for isomer 1. Ligand 2 has the high Cd-sensing capability that originates from monomer–excimer interconversion.     

Melt synthesis of Eu-doped oxide phosphors using arc-imaging furnace

To synthesize various complex oxide materials and their solid solutions, we applied a novel “melt-synthesis technique” rather than conventional solid-state reaction techniques. Rapid synthesis methods to develop those double oxides have been strongly anticipated. During melt synthesis, the mixture of oxides or their precursors is melted rapidly (1–60 s) in an arc-imaging furnace using strong light radiation. A spherical molten sample with multiple homogeneously mixed cations was solidified directly on a copper hearth with rapid cooling of ca. 10² °C/s.We studied the synthesis of A₂BO₄ type double oxides (AA′)₂BO₄ (A = Sr²⁺, Ca²⁺, A′ = La³⁺, Gd³⁺, Y³⁺, Eu³⁺, B = Al) using this method. Homogeneous samples with Eu³⁺ dopants were synthesized using liquid phase mixing in a few seconds, which is much faster than diffusions of ions in solid phase. Red fluorescence under the irradiation of ultraviolet light (254 and 365 nm) was observed. The excitation band shifted.     

Sorption of heavy metal ions from aqueous solution by a novel cast PVA/TiO2 nanohybrid adsorbent functionalized with amine groups

Sorption of Cd(II), Ni(II) and U(VI) ions onto a novel cast PVA/TiO₂/APTES nanohybrid adsorbent with variations in adsorbent dose, pH, contact time, initial metal concentration and temperature has been investigated. The adsorbent were characterized by SEM and FTIR analysis. BET surface area, pore diameter and pore volume of adsorbent were 35.98 m² g⁻¹, 3.08 nm and 0.059 cm³ g⁻¹, respectively. The kinetic and equilibrium data were accurately described by the double-exponential and Freundlich models for all metals. The maximum sorption capacities were 49.0, 13.1 and 36.1 mg g⁻¹ for Cd(II), Ni(II) and U(VI) ions with pH of 5.5, 5 and 4.5, respectively. Thermodynamic studies showed that the sorption process was favored at higher temperature. The adsorbent can be easily regenerated after 5 cycles of sorption–desorption.     

Structural and luminescence properties of undoped,Nd3+ and Er3+ doped TiO2 nanoparticles synthesized by flame spray pyrolysis method

Bulk and thin film forms of titanium dioxide (TiO₂) have been studied many times due to its very promising optical properties. In this study, low-cost flame spray pyrolysis (FSP) synthesis of Nd³⁺/Er³⁺doped TiO₂ nanoparticles has been reported for the first time. The produced particles were post-annealed after FSP process at 550 °C in order to obtain crystalline structure. The phase and elemental analysis of the produced materials were performed by X-Ray Diffraction (XRD) and X-Ray Photoelectron Spectroscopy (XPS), respectively. The surface morphology, accurate size and specific surface area of the primary particles were identified using scanning electron microscopy (SEM) and particle size analyser. Luminescent properties of the produced nanoparticles were investigated by steady state and time resolved fluorescence spectra. Doping of TiO₂ nanoparticles with the rare earths of Nd³⁺and Er³⁺resulted in visible and near-infrared light emission when excited at 364 nm. The utilized nanoparticles yielded bi-and tri-exponential decay curves. Additionally, they exhibited typical upconversion luminescence when radiated by 810 nm.     

Adsorption of heavy metals on amine-functionalized SBA-15 prepared by co-condensation: Applications to real water samples

SBA-15 functionalized with 3-aminopropyltrimethoxy-silane was studied as potential absorbent for Cd²⁺, Co²⁺, Cu²⁺, Zn²⁺, Pb²⁺, Ni²⁺, Al³⁺ and Cr³⁺. The adsorption capacity and selectivity of the materials were investigated in single and multi-metal solutions. Using single-metal solutions, the adsorbent was found to have an affinity (molar basis) for metal ions in decreasing order of Al³⁺ > Cu²⁺ > Ni²⁺ > Zn²⁺ > Co²⁺ > Cd²⁺ > Pb²⁺ > Cr³⁺. Using very dilute solutions, i.e., 10 ppm, more than 95% of cations were removed, except Co²⁺ and Cr³⁺, indicating the high sensitivity of the current adsorbent. The affinity for coexisting metal cations decreased in the order of Al³⁺ > Ni²⁺ > Cr³⁺ > Pb²⁺ > Zn²⁺ > Cd²⁺ > Co²⁺ > Cu²⁺. The adsorption capacities in multi-metal solutions were lower than in single-metal ones because of competition between metallic elements for the amine groups, with a preference for Al³⁺. The amine-modified SBA-15 adsorbent exhibited an excellent selectivity against sodium, potassium, and calcium, indicating that the ionic strength does not affect the adsorption properties. Application of this material to remove copper in tap water, river water, and electroplating wastewater was shown to be successful.     

Weak ferroelectricity and low-permittivity microwave dielectric properties of Ba2Zn(1+x)Si2O(7+x) ceramics

Ba₂Zn_(1+x)Si₂O_(7+x) ceramics were prepared using the conventional solid-state method at 1200 °C for 3 h in air. Apart from the previously reported Ba₂Zn_(1+x)Si₂O_(7+x) (x = 0) with a monoclinic structure (C 2/c), the end-member compositions at x = −1 and 1 exhibit single-phase β-BaSiO₃ with an orthorhombic structure (P2₁2₁2₁) and BaZnSiO₄ with a hexagonal structure (P6₃), and possess a coexistence of weak ferroelectricity and low-permittivity microwave dielectric properties. A reduction in Zn²⁺ content mainly decreases the intensity of the ε_r anomaly peak at lower temperature and increases the ε_r (or frequency) stability against temperature. The Zn²⁺-rich BaZnSiO₄ phase has a τ_f value of −181 ppm/°C, whereas the τ_f value of Zn²⁺-free BaSiO₃ phase decreases to −35.4 ppm/°C. The Zn²⁺ deficiency in Ba₂ZnSi₂O₇ composition could inhibit the presence of BaZnSiO₄ phase and improve the τ_f value, whereas excessive Zn²⁺ cations prompt the formation of the BaZnSiO₄ phase to deteriorate significantly the τ_f value.     

Effect of Sr/Ca substitution on phase structure and photoluminescence properties of micro-SrxCa1−xAlSiN3: Eu2+ phosphor for high CRI white LEDs

Sr_xCa_1−xAlSiN₃: Eu²⁺ phosphors were prepared by using the high temperature solid state reaction in a 1.1 Mpa N₂ atmosphere. The phase structures, photoluminescence (PL) properties, and chromaticity properties of the phosphors affected by Sr/Ca Substitution have been investigated in detail. With increasing Sr content (x value), the crystal grain became bigger and the average grain size increased from 5 µm to 10 µm. PL emission bands of Sr_xCa_1−xAlSiN₃: Eu²⁺ showed a blue-shift from 660 (x=0) to 617 nm (x=0.8), the shoulder of the excitation spectra around 550 nm showed a slightly blue-shift and decay lifetime shortened from 776.96 (x=0.2) to 642.35 ns (x=0.8). Both the emission and excitation intensity of peak position increased with Sr content increased. The ideal white light with high CRI (Ra>88) can be obtained by mixing the Sr_xCa_1−xAlSiN₃: Eu²⁺ phosphors and commercial green phosphors with appropriate proportion of the components.     

Composition design,phase transitions and electrical properties of Sr2+-substituted xPZN–0.1PNN–(0.9−x)PZT piezoelectric ceramics

The influences of PZN content and Sr²⁺ substitution on the structure and electrical properties of Pb(Zn_1/3Nb_2/3)O₃–Pb(Ni_1/3Nb_2/3)O₃–Pb(Zr_0.52Ti_0.48)O₃ (abbreviated as PZN–PNN–PZT) piezoelectric ceramics were studied. All as-prepared PZN–PNN–PZT ceramics presented single phase of perovskite structure, while higher PZN contents favored rhombohedral symmetry and larger grain size. Meanwhile, with the increase in Sr²⁺ content, the phase structure changed from a mix of tetragonal and rhombohedral symmetries to a pure rhombohedral symmetry. Although the ferroelectric Curie temperature (T_C) was decreased with increasing the PZN and Sr²⁺ contents, the piezoelectric constant (d₃₃) exhibited the opposite trend. As a result, optimum comprehensive electrical properties were obtained in the 0.1PZN–0.1PNN–0.8PZT composition with 10 mol% Sr²⁺ substitution: d₃₃~800 pC/N, k_p ~0.65, ɛ_r~4081, T_C~176 °C, P_r~30.92 µC/cm². Thus, the 10 mol% Sr²⁺-substituted 0.1PZN–0.1PNN–0.8PZT ceramic is a promising candidate for high performance applications.     

Effective Cd2+ chelating fiber based on polyacrylonitrile

A reusable chelating fiber containing polyamino–polycarboxylic acid ligands was prepared via the stepwise modification of polyacrylonitrile fiber with diethylenetriamine and chloroacetic acid. The amination and carboxylmethylation conditions were optimized, and the modified fiber was characterized by elemental analysis, XRD, SEM and FTIR. For Cd²⁺ in water, this chelating fiber has prominent adsorption abilities such as low adsorption limitation (0.001 mg/L), high adsorption capacity (1.34 mmol/g) and fast response speed (half-saturation adsorption time less than 0.5 min based on 1 mg/mL Cd²⁺). The effectiveness of this chelating fiber has been proved by using it to treat actual sewage water, where the concentration of Cd²⁺ was reduced from 0.540 to below 0.001 mg/L. This level easily meets drinking water standards (0.003 mg/L) issued by the World Health Organization. Moreover, this chelating fiber is also very effective at treating other metal ions such as Cu²⁺, Ca²⁺, Zn²⁺, Mg²⁺, Pb²⁺, Ni²⁺, Ag⁺ and Hg²⁺.