Sol-gel synthesized rare earth La3+ ions doped Zn2SiO4 phosphors for lighting applications

In this study, Zn_2-xLa_xSiO₄ (x = 0.00, 0.02, 0.04, and 0.06) materials with varying weight percentages of lanthanum (La) in zinc silicate (Zn₂SiO₄) were synthesized using the sol-gel process. The effect of La dopant on the structure, morphology, and optical characteristics of Zn₂SiO₄ was investigated through various analytical and spectroscopical techniques. According to PXRD measurements, La³⁺ ions were incorporated into the host materials of Zn₂SiO₄, considerably affecting their crystallinity. Irregular granular and pebble stone-like morphology was observed in the FESEM analysis. The optical energy bandgap of La-doped Zn₂SiO₄ materials decreased from 5.09 eV to 3.80 eV while increasing the La dopant into Zn₂SiO₄ host systems. The photoluminescence (PL) spectra and photoluminescence quantum yield (PLQY) confirmed the increase of luminescent peak intensity at 730 nm. A tri-exponential fitting technique was used to determine the luminescence decay lifetime of the significant emissions of La-doped Zn₂SiO₄, and the average lifetime was found to be 30.4 ns. Dosimetry could benefit significantly from the thermoluminescence investigation conducted for the La-doped Zn₂SiO₄ phosphor at a linear heating rate of 8 °C/s.     

Thermal,Structural, and Enhanced Photoluminescence Properties of Eu3+‐doped Transparent Willemite Glass–Ceramic Nanocomposites

The precursor glass in the ZnO–Al₂O₃–B₂O₃–SiO₂ (ZABS) system doped with Eu₂O₃ was prepared by the melt‐quench technique. The transparent willemite, Zn₂SiO₄ (ZS) glass–ceramic nanocomposites were derived from this precursor glass by a controlled crystallization process. The formation of willemite crystal phase, size, and morphology with increase in heat‐treatment time was examined by X‐ray diffraction (XRD) and field‐emission scanning electron microscopy (FESEM) techniques. The average calculated crystallite size obtained from XRD is found to be in the range 18–70 nm whereas the grain size observed in FESEM is 50–250 nm. The refractive index value is decreased with increase in heat‐treatment time which is caused by the partial replacement of ZnO₄ units of ZS nanocrystals by AlO₄ units due to generation of vacancies. Fourier transform infrared (FTIR) reflection spectroscopy was used to evaluate its structural evolution. Vickers hardness study indicates marked improvement of hardness in the resultant glass‐ceramics compared with its precursor glass. The photoluminescence spectra of Eu³⁺ ions exhibit emission transitions of ⁵D₀→⁷F_j (j = 0, 1, 2, 3, and 4) and its excitation spectra show an intense absorption band at 395 nm. These spectra reveal that the luminescence performance of the glass–ceramic nanocomposites is enhanced up to 17‐fold with the process of heat treatment. This enhancement is caused by partitioning of Eu³⁺ ions into glassy phase instead of into the willemite crystals with progress of heat treatment. Such luminescent glass–ceramic nanocomposites are expected to find potential applications in solid‐state red lasers, phosphors, and optical display systems.     

Effect of Size-Dependent Thermal Instability on Synthesis of Zn<Subscript>2</Subscript> SiO<Subscript>4</Subscript>-SiO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Core–Shell Nanotube Arrays and Their Cathodoluminescence Properties

Vertically aligned Zn₂SiO₄-SiO _x (x < 2) core–shell nanotube arrays consisting of Zn₂SiO₄-nanoparticle chains encapsulated into SiO _x nanotubes and SiO _x -coated Zn₂SiO₄ coaxial nanotubes were synthesized via one-step thermal annealing process using ZnO nanowire (ZNW) arrays as templates. The appearance of different nanotube morphologies was due to size-dependent thermal instability and specific melting of ZNWs. With an increase in ZNW diameter, the formation mechanism changed from decomposition of “etching” to Rayleigh instability and then to Kirkendall effect, consequently resulting in polycrystalline Zn₂SiO₄-SiO _x coaxial nanotubes, single-crystalline Zn₂SiO₄-nanoparticle-chain-embedded SiO _x nanotubes, and single-crystalline Zn₂SiO₄-SiO _x coaxial nanotubes. The difference in spatially resolved optical properties related to a particular morphology was efficiently documented by means of cathodoluminescence (CL) spectroscopy using a middle-ultraviolet emission at 310 nm from the Zn₂SiO₄ phase.     

Microwave‐Assisted Hydrothermal Synthesis of Submicrometer Willemite Phase Zinc Silicate and Its Zinc Ion Release Behavior

As an important trace element in human bone, zinc (Zn) has a great influence on bone metabolism. The aim of this work was to prepare a Zn‐containing material that can release Zn ions. For this purpose, submicrometer willemite phase zinc silicate (Zn₂SiO₄, ZS) with poor crystallinity was synthesized at 110°C via the microwave‐assisted hydrothermal (MH) method. Under the MH condition, the growth of ZS was consistent with “multi‐core growth” mechanism. Moreover, the influences of the reaction temperature and the reactant concentration on the final products were investigated in detail. The inductively coupled plasma atomic emission spectroscopy (ICP) data indicated that the poor crystallinity ZS could successfully release Zn for at least 28 d as soaking in the simulated body fluid (SBF). Without the replenishment of SBF, ~333 μM Zn was released from ZS synthesized at 110°C (ZS‐110). If SBF was periodically replenished once a day, more Zn was released from ZS‐110, and the parascholzite phase calcium zinc phosphate hydrate (CaZn₂(PO₄)₂·2H₂O) formed during the soaking process of ZS‐110. Under the concentration of 6.25 mg/mL, the extract of ZS‐110 was proved to be nontoxic by assessing with mouse osteoblast cells (MC3T3). Therefore, the poor crystallinity ZS has potential to be incorporated into the orthopedic reconstructive materials as a source of Zn ions, which can improve the bioactivity of the materials.     

Photoluminescence of (ZnO)X-Z(SiO2)Y:(MnO)Z green phosphors prepared by direct thermal synthesis: The effect of ZnO/SiO2 ratio and Mn2+ concentration on luminescence

Green light emitting Zn₂SiO₄:Mn²⁺ phosphors have been synthetised by the solid-state reaction in ambient atmosphere at 1300 °C for 2 h, with ZnO, SiO₂ and MnO₂ as the reagents. The ZnO/SiO₂ molar ratio varied from 2 to 0.5. The doping level was in a lower concentration range (0.01≤x≤0.05). The effect of both the Mn²⁺ concentration and ZnO/SiO₂ molar ratio on luminescence intensity and decay was investigated in detail. The microstructure and phase composition of prepared phosphors were characterised by scanning electron microscopy (SEM) and X-ray powder diffraction (XRD). XRD results indicate that the pure α-Zn₂SiO₄ phase with rhombohedral structure was obtained after heat treatment. The prepared phosphors exhibit a strong green emission centred at 525 nm from the ⁴T₁→⁶A₁ forbidden transition. The highest emission intensity was observed for phosphors with ZnO/SiO₂ molar ratio equal to 1.0, and the Mn²⁺ concentration x=0.03 (ZSMn3). The emission intensity of the ZSMn3 phosphor is comparable with the commercial Zn₂SiO₄:Mn²⁺ phosphor. The decay curves can be characterised by double exponential function. After fitting a fast component τ₁∼2 ms and a slow component τ₂∼10 ms were obtained. The decay times decrease significantly with increasing Mn²⁺ concentration. The decay time and luminescence mechanism depend on the excitation light wavelength. Temperature dependent luminescence of the ZSMn3 phosphor in the temperature range of 25–200 °C was studied.     

Novel Er-doped SiC/SiO2 nanocomposites: Synthesis via polymer pyrolysis and their optical characterization

Erbium activated SiC/SiO₂ nanocomposites doped with Er³⁺ concentrations ranging from 1 to 4 mol% were prepared by pyrolysis of sol–gel derived precursors. The gels were obtained from modified silicon alkoxides containing Si–CH₃ and Si–H groups. Thin discs obtained from the monolithic xerogels were pyrolyzed in an alumina tubular furnace in flowing Ar (100 ml/min) at 800, 1000, 1200 and 1300 °C. The samples were investigated by absorption and photoluminescence spectroscopies. Emission in the C-telecommunication band was observed at room temperature for all the samples upon continuous-wave excitation at 980 or 514.5 nm. The shape of the emission band corresponding to the ⁴I_13/2 → ⁴I_15/2 transition is found to be independent both on Erbium content and excitation wavelength, with a Full Width Half Maximum (FWHM) of 48 nm. By increasing the pyrolysis temperature the intensity of the luminescence increases and the electronic bandgap energy decreases.     

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⁺.     

Zn3N2 nanowires: growth,properties and oxidation

Zinc nitride (Zn₃N₂) nanowires (NWs) with diameters of 50 to 100 nm and a cubic crystal structure have been grown on 1 nm Au/Al₂O₃ via the reaction of Zn with NH₃ including H₂ between 500°C and 600°C. These exhibited an optical band gap of ≈ 3.2 eV, estimated from steady state absorption-transmission spectroscopy. We compared this with the case of ZnO NWs and discussed the surface oxidation of Zn₃N₂ NWs which is important and is expected to lead to the formation of a Zn₃N₂/ZnO core-shell NW, the energy band diagram of which was calculated via the self-consistent solution of the Poisson-Schrödinger equations within the effective mass approximation by taking into account a fundamental energy band gap of 1.2 eV. In contrast, only highly oriented Zn₃N₂ layers with a cubic crystal structure and an optical band gap of ≈ 2.9 eV were obtained on Au/Si(001) using the same growth conditions.     

Direct Formation and Luminescence Properties of Yttrium Niobate YNbO4 Nanocrystals via Hydrothermal Method

Yttrium niobate YNbO₄ nanocrystals with ellipsoidal morphology were directly formed from the precursor solution mixtures of YCl₃ and NbCl₅ under weakly basic conditions in the presence of aqueous ammonia by hydrothermal method. The hydrothermal treatment at 180°C for 5 h was necessary to obtain nanocrystals (18 nm) with sufficient crystallinity. The optical band gap of the as‐prepared samples was 3.6 eV. The as‐prepared YNbO₄ nanocrystals showed UV‐blue and broadband emission centered at 405 nm under excitation at 235 nm, which was due to the blue recombination luminescence, associated with charge‐transfer transitions involving the tetrahedral NbO₄ group. The emission intensity increased with increased hydrothermal treatment temperature. The photoluminescence intensity of the YNbO₄ was extremely improved via heating above 1000°C in air, which was accompanied by the increase in the optical band gap from 3.6 to 4.0 eV. By heat treatment at 1300°C, the intensity of the UV‐blue and broadband emission (with maximum at 400 nm) for the YNbO₄ became more than 22.5 times as strong as that before heat treatment.     

Enhanced structural,optical, and photocatalytic activity of novel Cd–Zn co-doped Mg0.25 Fe1.75O4 for degradation of RhB dye under visible light irradiation

Cd_xZn_1-xMg_0.25Fe_1.75O₄ (where x = 0.00, 0.25, 0.50, 0.75, 1.00) have been successfully produced by a facile hydrothermal technique for a thorough comparison of structural, optical, and photocatalytic properties (degradation of Rhodamine B -RhB dye under visible light irradiation). X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) confirmed the formation of cubic spinel structure for all of the samples. Fourier transform infrared (FTIR) spectroscopy verified the presence of metal-oxygen (M–O) bonding in the prepared samples with two frequency bands corresponding to phonon vibrational stretching in both the octahedral and tetrahedral lattice positions. UV–Visible Spectrophotometer and photoluminescence (PL) spectroscopy investigated the bandgap variation (2.7 eV-1.7 eV) and emission spectrum peaks appearing in the range of 405–471 nm region. The comparison in the photo-degradation of Rhodamine B (RhB) revealed the superior performance (98% degradation of RhB dye in 80 min having a K value of 0.04966 with excellent reusability) of Cd_0.50Zn_0.50Mg_0.25Fe_1.75O₄ sample having 50/50 dopant ratio of Cd and Zn in the parent Mg Ferrite, attributed to the lowest bandgap, longer lifetime of charge carriers, active octahedral lattice site, electron/hole pair recombination preventions, and the least value of ohmic impedance at higher frequency.     

Al2O3 Colloidal Nanocrystals with Strong UV Emission

A facile sol–gel procedure has been developed for the synthesis of colloidal alumina nanocrystals. For the first time, optical characterization procedures were employed to study the quantum confinement effects in optical properties of the prepared Al₂O₃ sol. Accordingly, the hyperbolic band model was used to determine the optical band gap of colloidal alumina nanocrystals. X‐Ray diffraction pattern was used to study the crystallographic phase of the dried gel. Morphological characterization was performed using scanning electron microscopy (SEM). Inductively Coupled Plasma (ICP) emission spectroscopy was used to determination purity of the Al₂O₃ powder. High‐resolution TEM showed that the diameter of colloidal nanocrystals is about 10 nm. Photoluminescence spectroscopy demonstrated that quantum yields for colloidal nanocrystals are 68% with 300 nm excitation wavelength. The experimental observations confirm that highly stable alumina sol with strong UV emission was synthesized. The mentioned optical properties have not been reported before.     

Optical properties and radiation stability of SiO2/ZnO composite pigment prepared by co-sintering method

Thermal control coatings (TCCs) are an essential part of the thermal control systems in the spacecraft. Solar absorptance and emittance are the key performance parameters of TCCs. To develop an ultra-low solar absorption and stable inorganic TCCs for surface radiator, different TCCs were prepared by co-sintering ZnO and SiO₂ nanoparticles to form Zn₂SiO₄/SiO₂ pigment in this work, and the optical properties and radiation stability were systematically studied. It is found that the coating based on composite pigment has high reflectivity in the ultraviolet band and excellent optical performance possessing the low solar absorption of 0.06. In addition, the Zn₂SiO₄/SiO₂ coating demonstrates the highest proton and electron radiation stability because that SiO₂ between Zn₂SiO₄ particles acts as the relaxation center of the defects caused by radiation.     

Spinel nickel cobaltite nanoflakes anchored multiwalled carbon nanotubes driven photocatalyst for highly efficient degradation of organic pollutants using natural sunlight irradiation

Natural sun light driven photocatalytic materials have received remarkable attention due to their imminent applications in environmental remediation and energy conversions. In this study, natural sun light driven hierarchal spinel nickel cobaltite nanoflakes (NiCo₂O₄) anchored multiwalled carbon nanotubes (MWCNTs) nanocomposite was synthesized by using simple chemical route. The structural, morphological and functional group of as-prepared NiCo₂O₄ anchored MWCNTs was studied by using X-ray diffractometry, field emission scanning electron microscopy and Fourier transform infrared spectroscopy. The UV–vis diffusive reflectance spectroscopy results demonstrated decrease in optical bandgap from 1.32 to 1.16eV compared with pristine spinel NiCo₂O₄ nanoflakes. MWCNTs anchored NiCo₂O₄ showed extremely good photocatalytic behavior and we verified 98% degradation of MB in 35 min under natural sun light. NiCo₂O₄ anchored MWCNTs also confirmed its excellent stability and reusability by retaining 96% of photocatalytic efficiency after 7 cycles of operation. Improved photocatalytic behavior of NiCo₂O₄ anchored MWCNTs nanocomposite in comparison to NiCo₂O₄ nanoflakes is mainly attributed to excellent electron storage ability of MWCNTs which made catalyst a great acceptor. Moreover, porous structure of MWCNTs not only provides large surface area with more active sites but also increases conductivity and decreases agglomerations on the surface of material which render e^-/h⁺ pair recombination. Overall, this work shed new light for the synthesis of NiCo₂O₄ anchored MWCNTs with enhanced photocatalytic properties.     

Near infrared emitting Cr3+ doped Zn3Ga2Ge2O10 long persistent phosphor for night vision surveillance and anti-counterfeit applications

The Cr³⁺ doped Zn₃Ga₂Ge₂O₁₀ long persistent phosphor materials were synthesized by solid state reaction method. The crystal structure of the synthesized phosphors are cubic with space group Fd3m. The band gap of the undoped host is about 4.48 eV. The materials show three photoluminescence excitation bands peaked at 260 nm, 412 nm and 580 nm. Due to the broad excitation band, the phosphors can be excited by UV light or visible light or sunlight. The phosphors shows a photoluminescence emission band peaked at 698 nm when excited by UV light. The afterglow emission shows a broad emission band with maximum at 700 nm. The detection of NIR light from the sample was observed by Night Vision Monocular for 24 h after switch off the excitation source. A mechanism is introduced to describe afterglow phenomenon and trap depth was calculated from thermoluminescence curve. As the material emit NIR persistent light, it was used as a secret light source for night vision devices. The developed material was used for tagging, tracking and locating purposes in defence application. The acrylic based paint was prepared to develop long persistent near infrared (NIR) paint, which can be coated on combat vehicle, ship, weapon, helmet, cloth, tent, rock for defence application. The NIR security ink was prepared and demonstrated to prevent counterfeit. Encryption and decryption method of confidential information was presented by using NIR security ink.     

Near-IR Emission and upconversion luminescent properties of Tb3+/Yb3+ Co-doped HfO2/SiO2 nanoparticles

The luminescent characteristics of spherical hafnia/silica (HfO₂/SiO₂) nanoparticles (NP?s) co-doped with Tb³⁺/Yb³⁺ were analysed. These NP?s were synthesized using the spray pyrolysis technique. The addition of SiO₂ and Tb³⁺/Yb³⁺ was found to induce a cubic phase in HfO₂. The luminescent spectra presented the characteristic emission peaks for inter-electronic energy levels transitions of the Tb³⁺ and Yb³⁺ ions, with an excitation band centred at 270 nm. Under solid-state laser excitation at 980 nm an upconversion emission related to the Tb³⁺ ion was observed. The maximum emission peak in the visible region was at 543 nm, associated with ⁵D₄ → ⁷F₅ transitions of the Tb³⁺ ions and an IR emission peak at 970 nm (²F_5/2 → ²F_7/2) pertaining to Yb³⁺, with irradiation at 270 nm (UV). The energy transfer mechanism from Tb³⁺→Yb³⁺ (excitation at 270 nm), is discussed based on the time decay of the luminescence intensity analysis and the energy transfer efficiency (η_ET) and was determined to be in the range of 29.2% to40.8%.     

Phase evolution and microwave dielectric properties of SrTiO3 added ZnAl2O4–Zn2SiO4–SiO2 ceramics

Phase evolution and microwave dielectric properties of SrTiO₃ added ZnAl₂O₄–3Zn₂SiO₄–2SiO₂ ceramics system were investigated. With the addition of SrTiO₃, the sintering temperature for dense ceramic is reduced from 1320 °C to 1180–1200 °C. According to the nominal composition ZnAl₂O₄–3Zn₂SiO₄–2SiO₂-ySrTiO₃, phase evolution is revealed by XRD patterns and Back Scattering Electron images: Zn₂SiO₄, ZnAl₂O₄ and SiO₂ phases coexist at y = 0; SrTiO₃ reacts with ZnAl₂O₄ and SiO₂ to form SrAl₂Si₂O₈, TiO₂ and Zn₂SiO₄ at y = 0.2 to 0.8, and SiO₂ phase disappears at y = 0.8; new phase of Zn₂TiO₄ is obtained at y = 1. The existence of TiO₂ has important effect on the dielectric properties. The optimized microwave dielectric properties are obtained at y = 0.6 and the ceramics show low dielectric constant (7.16), high-quality factor (57, 837 GHz), and low temperature coefficient of resonant frequency (−30 ppm °C⁻¹).     

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.     

Luminescence enhancement of single-component Ca19Zn2(PO4)14:Dy3+ white-emitting phosphor powders through partial substitution of PO43− with SiO44− and BO33-

A series of Ca₁₉Zn₂(PO₄)_14-yAG_y:Dy³⁺ (AG = BO₃^3?, SiO₄^4?) white-emitting phosphors with partial PO₄^3? substitution were synthesized through high-temperature solid-state reaction. The BO₃^3? and SiO₄^4? anionic groups were introduced into Ca₁₉Zn₂(PO₄)₁₄:Dy³⁺ for enhancing the luminescence of Dy³⁺. The X-ray diffraction results exhibited that all samples were assigned to the standard trigonal Ca₁₉Zn₂(PO₄)₁₄ structure with R3c (161) space group. The white emission spectrum of Dy³⁺-doped phosphors was composed of several characteristic peaks located at 484 nm, 575 nm and 665 nm, corresponding to ⁴F_9/2 → ⁶H_15/2, ⁶H_13/2 and ⁶H_11/2 electron transitions, respectively. After partial SiO₄^4? and BO₃^3? substituting PO₄^3?, the luminescence intensity of Ca_18.62Zn₂(PO₄)_13.75(SiO₄)_0.25:0.38Dy³⁺ and Ca_18.62Zn₂(PO₄)_13.65(BO₃)_0.35:0.38Dy³⁺ samples were higher by 1.68 and 1.49 times than that of Ca_18.62Zn₂(PO₄)₁₄:0.38Dy³⁺ sample, respectively, due to the charge compensation and crystal field environment effect. The actual w-LEDs fabricated with as-prepared Ca_18.62Zn₂(PO₄)_13.75(SiO₄)_0.25:0.38Dy³⁺ and Ca_18.62Zn₂(PO₄)_13.65(BO₃)_0.35:0.38Dy³⁺ phosphors showed excellent optical performances. All results indicated that the single component Ca_18.62Zn₂(PO₄)_14-yAG_y:0.38Dy³⁺ white-emitting phosphors could have a potential application in w-LEDs.     

Synthesis and Luminescence Properties of Blue‐Emitting Phosphor Eu2+‐Doped Zinc Fluoro‐Phosphate Zn2[PO4]F

Eu²⁺‐doped zinc fluoro‐phosphate Zn₂[PO₄]F was synthesized by the conventional high‐temperature solid‐state reaction. The phase formation was confirmed by X‐ray powder diffraction measurements and the structure refinement. The photoluminescence excitation and emission spectra, and the decay curves were measured. The natures of the Eu²⁺ emission in inorganic hosts, e.g., the emission and excitation properties, the chromaticity coordinates, the Stokes shifts, the absolute quantum efficiency, and the luminescence thermal stability were reported. Under the excitation of near‐UV light, Eu²⁺‐doped Zn₂[PO₄]F presents a narrow blue‐emitting band centered at 423 nm. The thermal stability of the blue luminescence was evaluated by the luminescence intensities as a function of temperature. The phosphor shows an excellent thermal stability on temperature quenching effects.     

Oxidation behavior of hot pressed ZrB2–SiC and HfB2–SiC composites

Non-isothermal, isothermal and cyclic oxidation behavior of hot pressed ZrB₂–20 (vol.%) SiC (ZS) and HfB₂–20 SiC (HS) composites have been compared. Studies involving heating in thermogravimetric analyzer have shown sharp mass increases at 740 and 1180 °C for ZS, and mass gain till 1100 °C followed by loss for HS. Isothermal oxidation tests for 1, 24 and 100 h durations at 1200 or 1300 °C have shown formation of partially and completely stable oxide scales after ～24 h exposure for ZS and HS, respectively. X-ray diffraction, scanning electron microscopy and energy or wavelength dispersive spectroscopy has confirmed presence of ZrO₂ or HfO₂ in oxide scales of ZS or HS, respectively, besides B₂O₃–SiO₂. Degradation appears more severe in isothermally oxidized ZS due to phase transformations in ZrO₂; and is worse in HS on cyclic oxidation at 1300 °C with air cooling, because of higher thermal residual stresses in its oxide scale.