Incorporate boron and nitrogen into graphene to make BCN hybrid nanosheets with enhanced microwave absorbing properties

This work demonstrates the conversion of graphene oxide into BCN hybrid nanosheets by reaction with boric acid and urea at 900 °C, during which boron and nitrogen atoms are incorporated into the graphene atomic sheets. X-ray diffraction pattern and X-ray photoelectron spectroscopy reveal the existence of h-BN. High-resolution electron microscopy and Raman spectrum indicate the presence of graphene-like layers with h-BN nanodomains. The content of h-BN in the BCN nanosheets can also be tuned by further heat-treatment in an ammonia environment, which in turn affects the band gap of these nanosheets. The electromagnetic parameters suggest that these samples can be used as good microwave absorbing materials at G band (5.6–8.2 GHz) and X band (8.2–12.4 GHz). This study provides a simple route to BCN hybrid nanosheets with tunable band gap and adjustable conductivity for microwave absorbing applications.     

Wetting behavior and interfacial interactions of molten Cu50Ti alloy with hexagonal BN and TiB2 ceramics

Wetting behavior of molten Cu50Ti alloy on hexagonal BN (h-BN) and TiB₂ ceramics has been studied under vacuum using a modified sessile drop method. Final contact angles of 8° and 3° are obtained at 1000 °C on h-BN and TiB₂, respectively. Interaction occurs at the interface between the molten alloy and BN, leading to the formation of a reaction layer containing TiB and Ti nitrides. Interfacial interaction of Cu50Ti with TiB₂ results in the formation of densely packed TiB layer about 60–100 μm thick and the detachment of TiB₂ grains. Spreading wetting of liquid Cu50Ti on h-BN is mainly controlled by the reactions between Ti and BN at the triple line. For Cu50Ti/TiB₂ system, spreading is mainly limited by the interfacial reaction in the first stage, and is possibly influenced by both the diffusion of boron atoms and viscous friction of the liquid in the second stage. Finally, brazing of graphite to CuCrZr alloy has been realized using Cu50TiH₂ with ceramic additives (including BN and TiB₂) as composite fillers. The joints exhibit favorable interfacial bonding between the filler layer and the substrates. The ceramic reinforcements in the filler layer could contribute to the improvement of the shear strength.     

New potential for preparation of performing h-BN coatings via polymer pyrolysis in RTA furnace

An innovative IR irradiation annealing process is used to increase the crystallization ratio of hexagonal boron nitride (h-BN) coatings on pure titanium pellets. Since the polymer pyrolysis route requires heating the green polymer at high temperature to convert it into a ceramic, the use of IR radiation furnace (compared to a resistive furnace) allows achievement of better crystallized h-BN while the substrate remains at relatively low temperature (<1000 °C). Annealing treatments have been performed under argon or nitrogen using either a halogen lamp or a Rapid Thermal Annealing (RTA) furnace. Advanced structural and chemical characterizations have shown a good chemical stability of the coatings. In addition, it has been revealed that samples annealed under Ar present a micro-composite structure at the interphase composed of a μ-layer of TiB₂/TiB/Ti(N)_x between the coating and the substrate, whereas samples annealed under nitrogen display a simpler structure at the interphase, with only TiN.     

Preparation and mechanical properties of laminated B4C–TiB2/BN ceramics

Laminated B₄C–TiB₂ ceramics with h-BN interface layers were successfully prepared by roll forming and tape casting, and samples with different numbers of stacked layers were obtained. Scanning electron microscopy and X-ray diffraction were used to analyze the microstructure and interlayer crystal phases of the composites, and the bending strength, fracture toughness, and work of fracture were measured. As the number of h-BN layers increased, the fracture toughness increased from 7.38 ± 0.5 MPa m^1/2 to 9.01 ± 0.61 MPa m^1/2, which is 2–3 times higher than that of monolithic B₄C ceramics. As the fracture toughness increased, the hardness remained at a high level (31.67 GPa). Bending tests showed that cracks deflected when they encountered the h-BN interfacial layers. The toughening mechanisms included the deflection and branching of cracks and generation of new microcracks, which increased the length of the propagation path and work of fracture.     

Effect of h-BN on the microstructure and fracture behavior of low carbon Al2O3-C refractories

h-BN is an ideal substitution candidate for graphite due to its similar crystal structure, better oxidation resistance. In this work, the effect of h-BN on microstructure and comprehensive properties of Al₂O₃-C refractories are investigated, and the specimen containing 0.5 wt% h-BN (G0.5N0.5) possesses the best comprehensive properties. The addition of h-BN could reduce the diameter of SiC whiskers, which leads to the highest strength of specimen G0.5N0.5 (42.63 ± 3.10 MPa). Moreover, the fracture behavior of the specimens is demonstrated using wedge splitting test. The results show that the specimen G0.5N0.5 possesses the highest crack initiation and propagation resistance, which could be attributed to the collaborative effect of h-BN and SiC whiskers. Noteworthily, the addition h-BN could improve the thermal shock resistance. The specimens containing h-BN possess the higher residual ratio, compared with the specimen containing no h-BN (G1N0), and the specimen G0.5N0.5 shows the highest residual strength (14.12 ± 0.67 MPa). Furthermore, the oxidation resistance could be enhanced with introducing the h-BN.     

Processing of CaLa2S4 infrared transparent ceramics: A comparative study of HP and FAST/SPS techniques

The densification of CaLa₂S₄ (CLS) powders prepared by combustion method was investigated by the use of Field-Assisted Sintering Technique (FAST) and Hot Pressing (HP). CLS powders were sintered using FAST at 1000°C at different pressures and heating rates and sintered by HP under 120 MPa from 800°C to 1100°C for 6 hours with a heating rate of 10°C/min. Comparison of both techniques was further realized by use of the same conditions of pressure, dwell time, and heating rate. Complementary techniques (XRD, SEM-EDS, density measurements, FTIR spectroscopy) were employed to correlate the sintering processes/parameters to the microstructural/compositional developments and optical transmission of the ceramics. Both sintering techniques produce ceramics with submicrometer grain size and relative density of about 99%. Nevertheless, HP is more suitable to densify CLS ceramics without fragmentation and also reach higher transmission than FAST. Transmission of 40%–45% was measured out of a possible maximum of 69% based on the Fresnel losses in the 8-14 μm window when HP is applied at 1000°C for 6 hours under 120 MPa. In both techniques, ceramics undergo reduction issues that originate from graphitic sintering atmosphere.     

Optimisation on the stability of CaO-doped partially stabilised zirconia by microwave heating

Partially stabilised zirconia has advantages for the applications in the metallurgical processes which have special requirements in corrosion resistance and high-temperature performance. In the present work, controllable microwave heating was used for the uniform thermal field and consequent microstructure improvement to further improve the stability of partially stabilised zirconia, which was 88.14% prepared by electric arc melting. Analyses including X-ray diffraction (XRD), Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy (Raman) were used to study the effect of temperature change on the phase composition and structure of the samples. After heating at temperatures of 900 °C, 1000 °C, 1100 °C, 1200 °C and 1300 °C for 1h, the stabilities of the heated product were 88.51%, 95.02%, 95.17%, 96.31% and 97.64%, respectively. From the phase transformations based on the experimental results, the discussion indicates that the martensitic transformation temperature of zirconia from m-ZrO₂ to t-ZrO₂ during the heating stage was reduced under the radiation of microwave energy.     

Comparison between microwave and conventional calcination techniques in regard to reactivity and morphology of co-precipitated BaTiO3 powder,and the electrical and energy storage properties of the sintered samples

Barium titanate (BaTiO₃) nanopowders were synthesized by an aqueous co-precipitation method followed by calcination. Either 2.45 GHz microwaves or conventional heating was used in order to investigate the impact of these techniques on the synthesis time, microstructure, and electrical properties of the materials. The heating temperatures ranged from 620 °C to 810 °C. X-ray diffraction (XRD) revealed pure BaTiO₃ formation by microwave heating in a noticeably shorter time (five minutes) compared to conventional heating (3 h). Field emission scanning electron microscopy (FESEM) results confirmed that the microwave process led to nanocube formation, whereas in the conventional procedure, the particles tended to form spherical shapes. To evaluate the electrical properties, the samples heated at 620 °C were conventionally sintered at 1280 °C, 1330 °C, and 1380 °C. Higher dielectric, piezoelectric, and ferroelectric properties and more energy-saving efficiency (ε_r=1012, tan δ=0.035 d₃₃=85 pC/N, p_r=6.2 µC/cm² and η=48% respectively) were achieved in the microwave-heated BaTiO₃ sintered at 1380 °C compared to the conventionally heated BaTiO₃ (ε_r=824, tan δ=0.030 d₃₃=75 pC/N, p_r=5 µC/cm² and η=27%) demonstrating that microwave calcination substantially affects the final electrical properties.     

Densification and mechanical properties of boron carbide prepared via spark plasma sintering with cubic boron nitride as an additive

Hexagonal boron nitride (h-BN) can reinforce boron carbide (B₄C) ceramics, but homogeneous dispersion of h-BN is difficult to achieve using conventional methods. Herein, B₄C/h-BN composites were manufactured via the transformation of cubic (c-) BN during spark plasma sintering at 1800 °C. The effects of the c-BN content on the microstructure, densification, and mechanical properties of B₄C/h-BN composites were evaluated. In situ synthesized h-BN platelets were homogeneously dispersed in the B₄C matrix and the growth of B₄C grains was effectively suppressed. Moreover, the c-BN to h-BN phase transformation improved the sinterability of B₄C. The sample with 5 vol.% c-BN exhibited excellent integrated mechanical properties (hardness of 30.5 GPa, bending strength of 470 MPa, and fracture toughness of 3.84 MPa⋅ m^1/2). Higher c-BN contents did not significantly affect the bending strength and fracture toughness but clearly decreased the hardness. The main toughening mechanisms were crack deflection, crack bridging, and pulling out of h-BN.     

A new approach to the synthesis of nanosized powder CaO and its application as precursor for the synthesis of calcium borates

A procedure for the synthesis of calcium oxide has been developed, which consists in heat treatment of an aqueous solution of calcium acetate and d-glucose at 350 and then at 700 °C. The process parameters have been determined. It has been shown that when d-glucose is used and the reaction mixture is heat treated at 700 °C, highly dispersed calcium oxide with an average particle size of 77 nm is formed. CaO formed has been used as a precursor for the synthesis of priceite (Ca₂(B₅O₇)(OH)₅ · H₂O) during hydrothermal treatment of CaO in an aqueous solution of boric acid. It has been found that the optimal conditions for the synthesis of monophase priceite under hydrothermal conditions include the temperature range of 170–200 °C and the heating time of 12 h. When heating priceite at 800 °C in air for 1 h, highly dispersed powder calcium bis(borate) Ca(BO₂)₂ has been isolated as the final product. It is shown that the use of synthesized powder CaO leads to the formation of fine-crystalline powders of calcium borates. Samples obtained at each stage of the proposed synthesis of highly dispersed calcium oxide and calcium borates, using the example of priceite and calcium bis(borate), have been studied by powder X-ray diffraction, SEM, TEM, BET, IR spectroscopy, and DTA.     

Study of oxide layer formation on Inconel 718 during isothermal oxidation between 800 °C to 1200 °C in hot air

The present study is to investigate the isothermal oxidation behavior of Inconel 718 (a Cr/Ni/Mo/Si-based alloy) because of their excellent thermo-mechanical properties, which are important in aerospace applications. X-ray diffraction (XRD) study confirmed the formation of spinel element of NiCr₂O₄ along with Cr₂Ni₃ at 1000 °C. X-ray photoelectron spectroscopy (XPS) is used to define the elemental composition of oxides and Raman spectroscopy to ascertain the state of oxides. Different morphologies such as tetragonal biaxial pyramids, flakes, and polygonal plates were observed on heated samples. Cross-sectional and EDS studies clearly revealed the drastic increase of oxide layer from 800 °C to 1200 °C. Finally, electrochemical impedance spectroscopy (EIS) analysis was carried out at 800 °C, 1000 °C and 1200 °C with a tenant period and ramping rate of 24 h and 10 min respectively. The EIS results divulged that charge transfer resistance values drastically increased with increasing temperature due to oxide layer.     

Photocatalytic activities of N-doped nano-titanias and titanium nitride

TiO₂ doped with various loadings of nitrogen was prepared by nitridation of a nano-TiO₂ powder in an ammonia/argon atmosphere at a range of temperatures from 400 to 1100 °C. The nano-TiO₂ starting powder was produced in a continuous hydrothermal flow synthesis (CHFS) process involving reaction between a flow of supercritical water and an aqueous solution of a titanium salt. The structures of the resulting nanocatalysts were investigated using powder X-ray diffraction (XRD) and Raman spectroscopy. Products ranging from N-doped anatase TiO₂ to phase-pure titanium nitride (TiN) were obtained depending on post-synthesis heat-treatment temperature. The results suggest that TiN started forming when the TiO₂ was heat-treated at 800 °C, and that pure phase TiN was obtained at 1000 °C after 5 h nitridation. The amounts and nature of the Ti, O and N at the surface were determined by X-ray photoelectron spectroscopy (XPS). A shift of the band-gap to lower energy and increasing absorption in the visible light region, were observed by increasing the heat-treatment temperature from 400 to 700 °C.     

Generation of hydrogen gas from polyethylene mechanically milled with Ni-doped layered double hydroxide

A process for generating hydrogen gas from polyethylene (PE) by milling and heating with Ni-doped layered double hydroxide (LDH), which was prepared also by a mechanochemical route of two-step milling operation, was reported in this work. A mixture of PE and the prepared Ni-doped LDH was first milled in a planetary ball mill for 1 h followed by heating the milled product to 700 °C under He/Ar gas environment for hydrogen emission. Characterizations by a set of analytical methods of X-ray diffraction (XRD), thermogravimetry-mass spectroscopy (TG-MS) and gas chromatography (GC) were performed on the milled and heated samples to monitor the process. Gaseous products obtained during heating mainly consisted of H₂, CH₄, CO, CO₂ with H₂ concentration over 80% between 450 and 550 °C. Such a process could be developed to treat hydrocarbon based solid wastes for hydrogen generation.     

Sono-synthesis of nanohydroxyapatite: Effects of process parameters

Hydroxyapatite (HA) [Ca₁₀(PO₄)₆(OH)₂] is a bioactive ceramic with excellent osteoconductive properties. This characteristic helps HA to be integrated into the bone without provoking an immune reaction, thus making it a useful biocompatible material for load bearing bone implant. In this study, nanohydroxyapatite (NHA) was synthesised using a precipitation method assisted with ultrasonication. The process parameters such as ultrasonic time (t) (10–30 min), ultrasonic amplitude (A) (50–70%), solution temperature (T) (50–90 °C), and solution pH (7–9) were varied on the basis of single factor and their effects on NHA synthesis was investigated. Besides that, the effect of calcination on the NHA powder morphology was also studied by varying the calcination time (2, 4 and 6 h) and temperature (400, 800 and 1200 °C). The characterisations of the synthesised NHA powder were conducted using thermogravimetric analysis (TGA), field emission scanning electron microscope (FESEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET), transmission electron microscope (TEM), zeta-sizer and Fourier transform infrared spectroscopy (FTIR). It was found that nano-sized HA particles can be produced at optimum set of process parameters of t=25 min, T=90 °C, A=65%, and pH=8. Results revealed that the thermal stability, morphology and crystallinity of the NHA powder was further improved by calcinating the powder at optimum temperature and time of 800 °C and 2 h, respectively.     

Effects of annealing temperature on the phase formation,optical, photoluminescence and magnetic properties of sol-gel YFeO3 films

YFeO₃ (YFO) thin films were deposited onto quartz substrates via sol-gel spin-coating technique and annealed at different temperature ranged between 650 and 900 °C. The impact of annealing temperature on the phase formation, microstructural, optical, photoluminescence (PL) and magnetic properties of the films were systematically investigated. X-ray diffraction analysis revealed an amorphous structure in film annealed at 650 °C and formation of hexagonal-YFO (h-YFO) phase in films annealed at 750–800 °C. The films annealed at 850–900 °C exhibited an orthorhombic-YFO (o-YFO) structure. Atomic force microscopy images of h-YFO films showed homogeneous surface with uniform particles size and shape. The particle size increased and had irregular shape in o-YFO films. The average particle size was 44 and 117 nm, while the root square roughness was 1.38 and 2.55 nm for h- and o-YFO films annealed at 750 and 850 °C, respectively. The optical band gap (E_g) was 2.53 and 2.86 eV for h- and o-YFO films annealed at 750 and 850 °C, respectively. The PL spectra of h-YFO films were red-shifted compared with that of o-YFO films. The PL emission related to near band edge was observed at 459.0 and 441.9 nm for h- and o-YFO films annealed at 750 and 850 °C, respectively. The magnetization was enhanced with the increasing of annealing temperature and has the value of 4.8 and 12.5 emu/cm³ at 5000 Oe for h- and o-YFO films annealed at 750 and 850 °C, respectively.     

Thermal decomposition products of the heteronuclear complex,LaNi(dhbaen)(NO3)(H2O)n

The heteronuclear LaNi(dhbaen)(NO₃)(H₂O)_n complex was synthesized and its thermal decomposition products were analyzed by differential thermal analysis (TG/DTA), X-ray diffraction (XRD), Fourier-transform infrared (FT-IR) spectroscopy, Auger electron spectroscopy (AES) with scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Hexagonal perovskite-type LaNiO₃ having fine particle size was obtained by sintering at 600 °C. AES showed that the elemental distributions of La, Ni, and O on the surface were very homogeneous for the sample decomposed at 900 °C. The LaNiO₃ decomposed to La₃Ni₂O₇ and NiO when the heating temperature increases up to 1000 °C. Heteronuclear LnNi(dhbaen)(NO₃)(H₂O)_n complexes (with Ln=Pr, Nd, Sm, and Gd) were also synthesized. The perovskite-type LnNiO₃ phase could not be formed by their thermal decomposition.     

Allochroic effect of praseodymium doped neodymium molybdate pigment synthesized by solid-state reaction

This paper was to synthesize praseodymium-doped neodymium molybdate allochroic pigments with different molar ratios of molybdenum (Mo), neodymium (Nd) and praseodymium (Pr) through solid-state reactions. The pigments synthesized were investigated by X-ray diffraction (XRD), selected area electron diffraction (SAED), thermogravimetry and differential thermal analysis (TG-DSC), diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS) and colorimeter. The results show that a pure neodymium molybdate (i.e., Nd₂MoO₆) can be formed after sintering at 1000 °C for 3 h, and praseodymium-doped neodymium molybdate can be synthesized after sintering at 1000 °C for 3 h due to praseodymium ions entering in the lattice of Nd₂MoO₆. The crystal structure in the pigment synthesized can transform from cubic to tetragonal depending on the molar ratio of neodymium/molybdenum and sintering procedure. The color properties of pigments were measured in color space CIEL*a*b* under different standard illuminants (i.e., solar-light (D65), incandescent light (A), cool white fluorescent lamp (F2), and three-band fluorescent lamp (F11)). The results show that the colors of the pigments vary under different illuminants. According to the color difference (ΔE) analysis, neodymium molybdate pigment exhibits a maximum color difference of 10.69, and the maximum color difference of praseodymium-doped neodymium molybdate pigment with doping content of 0.2 increases to 17.63 due to the Pr³⁺ ions substitution for Nd³⁺ ions in the lattice. In addition, the color difference of the pigments with allochroic effect was discussed based on the colorimetry. The color difference of the pigments is due to a high reflectance region at 540–550 nm and a low reflectance region at 380–500 nm.     

Effect of heat treatment on the synthesis of hydroxyapatite from Indian clam seashell by hydrothermal method

Hydroxyapatite (HA) powder has been successfully synthesized from low-cost Indian clam seashells by using hydrothermal method. The mixture of tri-calcium phosphate [Ca₃(PO₄)₂], heat-treated ball-milled clam seashell, and demineralized water are heat-treated at several temperatures (700 °C, 800 °C, 900 °C, 1000 °C, and 1100 °C) for various time periods (1 h, 2 h, and 3 h) to perform the hydrothermal reactions. The phases and microstructure of the solid-state reaction products are analyzed through X-ray diffraction (XRD) method and field emission scanning electron microscopy (FESEM) respectively. The crystallite size of all the synthesized powders is calculated by using Scherrer's model. Mainly HA phase is obtained in all the different reaction products. However, these HAs are found to be non-stoichiometric in nature. As per the literature, non-stoichiometric HA is a more biologically active material compared to the stoichiometric one. Almost pure HA is formed with any selected reaction temperature applied for 2 h time duration. The crystallinity and Ca/P ratio of the synthesized pure HA are estimated by using standard model and energy-dispersive X-ray spectroscopy (EDS) analysis, respectively. The highest amount of near stoichiometric crystalline HA has been obtained at 900 °C of reaction temperature applied for 2 h time duration. With raising reaction temperature, the grain size of pure HA is found to be increased. Needle/rod shaped nano grains are noticed to form at lower reaction temperature whereas; beyond 1000 ^oC of temperature globular/spherical shaped grains are also observed to form. At 3 h reaction time agglomeration of grains is found to occur in all the synthesized powders.     

Single-source-precursor synthesis of soft magnetic Fe3Si- and Fe5Si3-containing SiOC ceramic nanocomposites

We present here the single-source-precursor synthesis of Fe₃Si and Fe₅Si₃-containing SiOC ceramic nanocomposites and investigation of their magnetic properties. The materials were prepared upon chemical modification of a hydroxy- and ethoxy-substituted polymethylsilsesquioxane with iron (III) acetylacetonate (Fe(acac)₃) in different amounts (5, 15, 30 and 50 wt%), followed by cross-linking at 180 °C and pyrolysis in argon at temperatures ranging from 1000 °C to 1500 °C. The polymer-to-ceramic transformation of the iron-modified polysilsesquioxane and the evolution at high temperatures of the synthesized SiFeOC-based nanocomposite were studied by means of thermogravimetric analysis (TGA) coupled with evolved gas analysis (EGA) as well as X-ray diffraction (XRD). Upon pyrolysis at 1100 °C, the non-modified polysilsesquioxane converts into an amorphous SiOC ceramic; whereas the iron-modified precursors lead to Fe₃Si/SiOC nanocomposites. Annealing of Fe₃Si/SiOC at temperatures exceeding 1300 °C induced the crystallization of Fe₅Si₃ and β-SiC. The crystallization of the different iron-containing phases at different temperatures is considered to be a consequence of the in situ generation of a Fe–C–Si alloy within the materials during pyrolysis. Depending on the Fe and Si content in the alloy, either Fe₃Si and graphitic carbon (at 1000–1200 °C) or Fe₅Si₃ and β-SiC (at T > 1300 °C) crystallize. All SiFeOC-based ceramic samples were found to exhibit soft magnetic properties. Magnetization versus applied field measurements of the samples show a saturation magnetization up to 26.0 emu/g, depending on the Fe content within the SiFeOC-based samples as well as on the crystalline iron silicide phases formed during pyrolysis.     

Mild hydrothermal formation and comparative coprecipitation route for EuTiNbO6 fine phosphor

Aeschynite-type EuTiNbO₆ fine phosphor with sufficient luminescence intensity was directly formed as homogeneous cuboid particles with high crystallinity in the range of 1–2 μm from precursor solution mixtures of EuCl₃, TiOSO₄, and NbCl₅ under weakly basic conditions via hydrothermal treatment at 240 °C for 5 h. The as-prepared aeschynite phase stably existed after heating at 1000–1400 °C for 1 h in air. Under excitation at wavelengths of 395 nm, among all samples before and after heating in air, the as-prepared EuTiNbO₆ fine crystals before heating emitted luminescence with the highest intensity in the red spectral region with strong red and weak orange light corresponding to ⁵D_0→⁷F₂ and ⁵D_0→⁷F₁ transitions of Eu³⁺, respectively. The amorphous coprecipitation powder crystallized into euxenite-type phase at 700–1000 °C and transformed into aeschynite-type phase at 1000–1200 °C. High-temperature heating at 1400 °C was essential for the coprecipitation powder to obtain almost a single phase of aeschynite-type EuTiNbO₆ and sufficient emission intensity.