Green synthesis, structure feature and energy transfer of yellow-emitting (Y,Gd)2 O2 SO4 :Dy phosphors.

A green chemical precipitation route was used to yield a hydrated basic sulfate precursor upon calcination at 1000°C into a series of (Y,Gd)2 O2 SO4 :Dy particles. The phosphors exhibited characteristic Dy3+ emissions from 4 F9/2 →6 HJ (J = 15/2, 13/2, 11/2) transitions under ultraviolet light excitation; the quenching concentration of Dy3+ was determined to be 2.5 at.%. Substitution of Gd3+ for Y3+ led to an additional strong sharp band at ~277 nm (8 S7/2 →6 IJ transition of Gd3+ ) in the photoluminescence excitation spectra, upon which the (Gd0.975 Dy0.025 )2 O2 SO4 phosphor achieved a ~2.8-fold higher photoluminescence intensity via an effective energy transfer from Gd3+ to Dy3+ compared with the 354 nm excitation of Dy3+ . Both the photoluminescence and photoluminescence excitation intensities of (Y,Gd)2 O2 SO4 :Dy phosphors increased with rising Gd3+ concentration and calcination temperature in the range 750-1000°C. A higher Gd3+ concentration slightly prolonged the effective fluorescence lifetime.

EDTA-assisted phase conversion synthesis of (Gd0.95RE0.05)PO4 nanowires (RE = Eu, Tb) and investigation of photoluminescence.

Hexagonal (Gd0.95RE0.05)PO4·nH2O nanowires ~300 nm in length and ~10 nm in diameter have been converted from (Gd0.95RE0.05)2(OH)5NO3·nH2O nanosheets (RE = Eu, Tb) in the presence of monoammonium phosphate (NH4H2PO4) and ethylene diamine tetraacetic acid (EDTA). They were characterized by X-ray diffraction, thermogravimetry, electron microscopy, and Fourier transform infrared and photoluminescence spectroscopies. It is shown that EDTA played an essential role in the morphology development of the nanowires. The hydrothermal products obtained up to 180 °C are of a pure hexagonal phase, while monoclinic phosphate evolved as an impurity at 200 °C. The nanowires undergo hexagonal→monoclinic phase transformation upon calcination at ≥600 °C to yield a pure monoclinic phase at ~900 °C. The effects of calcination on morphology, excitation/emission, and fluorescence decay kinetics were investigated in detail with (Gd0.95Eu0.05)PO4 as example. The abnormally strong 5D0→7F4 electric dipole Eu3+ emission in the hexagonal phosphates was ascribed to site distortion. The process of energy migration was also discussed for the optically active Gd3+ and Eu3+/Tb3+ ions.

Prevention of thermal- and moisture-induced degradation of the photoluminescence properties of the Sr2Si5N8:Eu(2+) red phosphor by thermal post-treatment in N2-H2.

A red phosphor of Sr2Si5N8:Eu(2+) powder was synthesized by a solid state reaction. The synthesized phosphor was thermally post-treated in an inert and reductive N2-H2 mixed-gas atmosphere at 300-1200 °C. The main phase of the resultant phosphor was identified as Sr2Si5N8. A passivation layer of ∼0.2 µm thickness was formed around the phosphor surface via thermal treatment. Moreover, two different luminescence centers of Eu(SrI) and Eu(SrII) in the synthesized Sr2Si5N8:Eu(2+) phosphor were proposed to be responsible for 620 nm and 670 nm emissions, respectively. More interestingly, thermal- and moisture-induced degradation of PL intensity was effectively reduced by the formation of a passivation layer around the phosphor surface, that is, the relative PL intensity recovered 99.8% of the initial intensity even after encountering thermal degradation; both moisture-induced degraded external and internal QEs were merely 1% of the initial QEs. The formed surface layer was concluded to primarily prevent the Eu(2+) activator from being oxidized, based on the systemic analysis of the mechanisms of thermal- and moisture-induced degradation.

45S5 Bioglass(®)-MWCNT composite: processing and bioactivity.

Multi-walled carbon nanotube (MWCNT)-Bioglass (BG) matrix composite was fabricated using a facile and scalable aqueous colloidal processing method without using any surfactants followed by spark plasma sintering (SPS) consolidation. The individual MWCNTs were initially uniformly dispersed in water and then entirely immobilized on the BG particles during the colloidal processing, avoiding their common re-agglomeration during the water-removal and drying step, which guaranteed their uniform dispersion within the dense BG matrix after the consolidation process. SPS was used as a fast sintering technique to minimise any damage to the MWCNT structure during the high-temperature consolidation process. The electrical conductivity of BG increased by 8 orders of magnitude with the addition of 6.35 wt% of MWCNTs compared to pure BG. Short-duration tests were used in the present study as a preliminary evaluation to understand the effect of incorporating MWCNTs on osteoblast-like cells. The analysed cell proliferation, viability and phenotype expression of MG-63 cells showed inhibition on 45S5 Bioglass(®)-MWCNT composite surfaces.

Recent progress in advanced optical materials based on gadolinium aluminate garnet (Gd3Al5O12).

This review article summarizes the recent achievements in stabilization of the metastable lattice of gadolinium aluminate garnet (Gd3Al5O12, GAG) and the related developments of advanced optical materials, including down-conversion phosphors, up-conversion phosphors, transparent ceramics, and single crystals. Whenever possible, the materials are compared with their better known YAG and LuAG counterparts to demonstrate the merits of the GAG host. It is shown that novel emission features and significantly improved luminescence can be attained for a number of phosphor systems with the more covalent GAG lattice and the efficient energy transfer from Gd3+ to the activator. Ce3+ doped GAG-based single crystals and transparent ceramics are also shown to simultaneously possess the advantages of high theoretical density, fast scintillation decay, and high light yields, and hold great potential as scintillators for a wide range of applications. The unresolved issues are also pointed out.

Direct synthesis of MOF-derived nanoporous carbon with magnetic Co nanoparticles toward efficient water treatment.

Nanoporous carbon particles with magnetic Co nanoparticles (Co/NPC particles) are synthesized by one-step carbonization of zeolitic imidazolate framework-67 (ZIF-67) crystals. After the carbonization, the original ZIF-67 shapes are preserved well. Fine magnetic Co nanoparticles are well dispersed in the nanoporous carbon matrix, with the result that the Co/NPC particles show a strong magnetic response. The obtained nanoporous carbons show a high surface area and well-developed graphitized wall, thereby realizing fast molecular diffusion of methylene blue (MB) molecules with excellent adsorption performance. The Co/NPC possesses an impressive saturation capacity for MB dye compared with the commercial activated carbon. Also, the dispersed magnetic Co nanoparticles facilitate easy magnetic separation.

Electric double-layer capacitors based on highly graphitized nanoporous carbons derived from ZIF-67.

Nanoporous carbons (NPCs) have large specific surface areas, good electrical and thermal conductivity, and both chemical and mechanical stability, which facilitate their use in energy storage device applications. In the present study, highly graphitized NPCs are synthesized by one-step direct carbonization of cobalt-containing zeolitic imidazolate framework-67 (ZIF-67). After chemical etching, the deposited Co content can be completely removed to prepare pure NPCs with high specific surface area, large pore volume, and intrinsic electrical conductivity (high content of sp(2) -bonded carbons). A detailed electrochemical study is performed using cyclic voltammetry and galvanostatic charge-discharge measurements. Our NPC is very promising for efficient electrodes for high-performance supercapacitor applications. A maximum specific capacitance of 238 F g(-1) is observed at a scan rate of 20 mV s(-1) . This value is very high compared to previous works on carbon-based electric double layer capacitors.

Two-dimensional molybdenum carbides: potential thermoelectric materials of the MXene family.

A newly synthesized family of two-dimensional transition metal carbides and nitrides, so-called MXenes, exhibit metallic or semiconducting properties upon appropriate surface functionalization. Owing to their intrinsic ceramic nature, MXenes may be suitable for energy conversion applications at high temperature. Using the Boltzmann theory and first-principles electronic structure calculations, we explore the thermoelectric properties of monolayer and multilayer M2C (M = Sc, Ti, V, Zr, Nb, Mo, Hf, and Ta) and M2N (M = Ti, Zr, and Hf) MXenes functionalized with F, OH, and O groups. From our calculations, it turns out that monolayer and multilayer nanosheets of Mo2C acquire superior power factors to other MXenes upon any type of functionalization. We therefore propose the functionalized Mo2C nanosheets as potential thermoelectric materials of the MXene family. The exceptional thermoelectric properties of the functionalized Mo2C nanosheets are attributed to the peculiar t2g band shapes, which are a combination of flat and dispersive portions. These types of band shapes allow Mo2C to gain a large Seebeck coefficient and simultaneously a good electrical conductivity at low carrier concentrations.

Reductant-free colloidal synthesis of near-IR emitting germanium nanocrystals: role of primary amine.

High temperature colloidal synthesis without using hazardous reducing agent is demonstrated here to develop a straight forward pathway for synthesizing near-IR (NIR) light emitting germanium nanocrystals (Ge NCs). The NCs were prepared by heating a mixture of germanium (II) iodide and organoamine. This article presents an important role of the primary amine which serves as a reducing agent as well as an inhibitor against oxidation by comparing with the tertiary amine. Interestingly, the difference in chemical reactivity between each amine causes the difference in major structural phase of the products. An efficient route to produce NIR light emitting Ge NCs is demonstrated.

Metal-ceramic/ceramic nanostructured layered composites for solid oxide fuel cells by spark plasma sintering.

In this work, bi-layered Fe-Ni-Co-YSZ/YSZ nanostructured composites for solid oxide fuel cells were obtained using the spark plasma sintering (SPS) technique. The microstructures of the anode and electrolyte were controlled by optimization of SPS consolidation parameters. The resulting bilayers have a full dense YSZ electrolyte and porous Fe-Ni-Co/YSZ anode as well as crack-free and well-bonded anode/electrolyte interface. On the other hand, SPS under non-optimized processing parameters cannot yield the desired results. The high resistance to thermal stresses of the fabricated half-cells was achieved with Fe-Ni-Co/YSZ anode. The developed anode showed higher thermal compatibility with YSZ electrolyte than usual Ni/YSZ cermet. Thus, with the successful combination of SPS parameters and anode material, we have obtained bi-layers for SOFCs with required microstructure and thermal compatibility.

Recent advances in understanding the reinforcing ability and mechanism of carbon nanotubes in ceramic matrix composites.

Since the discovery of carbon nanotubes (CNTs), commonly referred to as ultimate reinforcement, the main purpose for fabricating CNT-ceramic matrix composites has been mainly to improve the fracture toughness and strength of the ceramic matrix materials. However, there have been many studies reporting marginal improvements or even the degradation of mechanical properties. On the other hand, those studies claiming noticeable toughening measured using indentation, which is an indirect/unreliable characterization method, have not demonstrated the responsible mechanisms applicable to the nanoscale, flexible CNTs; instead, those studies proposed those classical methods applicable to microscale fiber/whisker reinforced ceramics without showing any convincing evidence of load transfer to the CNTs. Therefore, the ability of CNTs to directly improve the macroscopic mechanical properties of structural ceramics has been strongly questioned and debated in the last ten years. In order to properly discuss the reinforcing ability (and possible mechanisms) of CNTs in a ceramic host material, there are three fundamental questions to our knowledge at both the nanoscale and macroscale levels that need to be addressed: (1) does the intrinsic load-bearing ability of CNTs change when embedded in a ceramic host matrix?; (2) when there is an intimate atomic-level interface without any chemical reaction with the matrix, could one expect any load transfer to the CNTs along with effective load bearing by them during crack propagation?; and (3) considering their nanometer-scale dimensions, flexibility and radial softness, are the CNTs able to improve the mechanical properties of the host ceramic matrix at the macroscale when individually, intimately and uniformly dispersed? If so, how? Also, what is the effect of CNT concentration in such a defect-free composite system? Here, we briefly review the recent studies addressing the above fundamental questions. In particular, we discuss the new reinforcing mechanism at the nanoscale responsible for unprecedented, simultaneous mechanical improvements and highlight the scalable processing method enabling the fabrication of defect-free CNT-concentered ceramics and CNT-graded composites with unprecedented properties. Finally, possible future directions will be briefly presented.

Luminescent metal nanoclusters: controlled synthesis and functional applications.

Luminescent metal nanoclusters that consist of only several, to tens of, metal atoms and which possess sizes comparable to the Fermi wavelength of electrons have recently attracted significant attention. This new class of luminescent materials not only provides the missing link between atomic and nanoparticle behaviors in metals but also they present abundant novel information for the development of new applicable material systems to meet urgent needs in many areas (such as ultrasensitive sensors for heavy metals, bioimaging, as well as information technology) mainly because of their attractive characteristics, including ultra-small size, good dispersibility, excellent biocompatibility and photostability. In this review, we summarize recent advances in the controlled synthesis and application of luminescent metal nanoclusters, with a particular emphasis on Pt, Mo, Bi and alloy clusters. We also speculate on their future and discuss potential developments for their use in sensors, bioimaging and energy harvesting and conversion.

Mechanically reliable thermoelectric (TE) nanocomposites by dispersing and embedding TE-nanostructures inside a tetragonal ZrO2 matrix: the concept and experimental demonstration in graphene oxide-3YSZ system.

Novel low-dimensional thermoelectric (TE) materials suffer from poor mechanical reliability, which limits their applications, especially in mechanically harsh environments. Here, we propose a new concept, in which the novel, abundant, thermally stable TE-nanostructures are dispersed and then intimately embedded inside a protective, mechanically reliable tetragonal ZrO2 (TZP) ceramic matrix with a low thermal conductivity. We also demonstrate an experimental proof-of-principle verification of our concept in reduced-graphene oxide (GO)-3 mol% Y2O3-ZrO2 (3YSZ or 3Y-TZP) nanocomposite system. TE characterizations suggest that our protective TZP matrix does not degrade the intrinsic TE property of the reduced GO network. These preliminary results are promising and encouraging to start research on similar TZP-matrix TE-nanocomposites, which contain more effective TE-nanostructures with larger intrinsic power factors. In this regard, we propose a scalable approach for fabrication of similar dense TE-nanocomposites composed of other one-dimensional and/or two-dimensional TE-nanostructures, which involves an aqueous colloidal approach and a subsequent spark plasma sintering. These new TZP-matrix TE-nanocomposites could be used for sustainable clean power generation, especially in mechanically harsh environments with thermal/mechanical shocks and vibrations, where energy availability, reliability and durability are more important than the energy efficiency. Considering the excellent biocompatibility of TZP matrix, they could even be used inside the body to power implanted medical devices.

The effect of the interlayer element on the exfoliation of layered Mo2AC (A = Al, Si, P, Ga, Ge, As or In) MAX phases into two-dimensional Mo2C nanosheets.

The experimental exfoliation of layered, ternary transition-metal carbide and nitride compounds, known as MAX phases, into two-dimensional (2D) nanosheets, is a great development in the synthesis of novel low-dimensional inorganic systems. Among the MAX phases, Mo-containing ones might be considered as the source for obtaining Mo2C nanosheets with potentially unique properties, if they could be exfoliated. Here, by using a set of first-principles calculations, we discuss the effect of the interlayer 'A' element on the exfoliation of Mo2AC (A = Al, Si, P, Ga, Ge, As or In) MAX phases into the 2D Mo2C nanosheets. Based on the calculated exfoliation energies and the elastic constants, we propose that Mo2InC with the lowest exfoliation energy and the highest elastic constant anisotropy between C11 and C33 might be a suitable compound for exfoliation into 2D Mo2C nanosheets.

Microstructure and high-temperature strength of textured and non-textured ZrB2 ceramics.

Zirconium diboride (ZrB2) ceramic possesses a unique combination of nice mechanical performance, high melting point (> 3000 °C) and great high-temperature oxidation resistance (up to 1600 °C), which makes it a promising material system for ever-increasing ultra-high temperature (UHT) applications. However, ZrB2 suffers from poor mechanical performance at UHTs, which could strongly limit its applications at UHT. Here, we successfully demonstrate that texturing is an effective strategy to greatly enhance the flexural strength of monolithic ZrB2, reaching a high value of 810 ± 60 MPa at 1600 °C when loaded in c-axis direction. We thoroughly discuss the strengthening mechanism by in-depth microstructural observations and analysis. Our discovery has technological and scientific implications for other UHT ceramic systems, especially those using ZrB2 as a matrix.

Tens of micron-sized unilamellar nanosheets of Y/Eu layered rare-earth hydroxide: efficient exfoliation via fast anion exchange and their self-assembly into oriented oxide film with enhanced photoluminescence.

Layered rare-earth hydroxide (LRH) crystals of (Y0.95Eu0.05)2(OH)5NO3·nH2O with a lateral size of ∼ 300 µm and a thickness of ∼ 9 µm have been synthesized via a hydrothermal reaction of mixed nitrate solutions in the presence of mineralizer NH4NO3 at 200 °C for 24 h. LRH exhibits the ability to undergo intercalation and anion exchange with DS- (C12H25OSO3-) via hydrothermal treatment. Compared with traditional anion exchange at room temperature, hydrothermal processing not only shortens the anion exchange time from 720 to 24 h but also increases the basal spacing. The arrangements of DS- in the interlayer of LRH are significantly affected by the DS- concentration and reaction temperature, and the basal spacing of the LRH-DS sample in the crystal edge is assumed to be larger than that in the crystal center. A higher DS- concentration and reaction temperature both induce more intercalation of DS- anions into the interlayer gallery, thus yielding a larger basal spacing. Unilamellar nanosheets with a lateral size of ≽60 µm and a thickness of ∼ 1.6 nm can be obtained by delaminating LRH-DS in formamide. The resultant unilamellar nanosheets are single crystalline. Transparent (Y0.95Eu0.05)2O3 phosphor films with a uniform [111] orientation and a layer thickness of ∼ 90 nm were constructed with the nanosheets as building blocks via spin-coating, followed by proper annealing. The oriented oxide film exhibits a strong red emission at 614 nm (the 5D0-7F2 transition of Eu3+), whose intensity is ∼ 2 times that of the powder form owing to the significant exposure of the (222) facets.

Facile and green synthesis of (La0.95Eu0.05)2O2S red phosphors with sulfate-ion pillared layered hydroxides as a new type of precursor: controlled hydrothermal processing, phase evolution and photoluminescence.

This study presents a facile and green route for the synthesis of (La0.95Eu0.05)2O2S red phosphors of controllable morphologies, with the sulfate-type layered hydroxides of Ln2(OH)4SO4·2H2O (Ln = La and Eu) as a new type of precursor. The technique takes advantage of the fact that the precursor has had the exact Ln:S molar ratio of the targeted phosphor, thus saving the hazardous sulfurization reagents indispensable to traditional synthesis. Controlled hydrothermal processing at 120 °C yielded phase-pure Ln2(OH)4SO4·2H2O crystallites in the form of either nanoplates or microprisms, which can both be converted into Ln2O2S phosphor via a Ln2O2SO4 intermediate upon annealing in flowing H2 at a minimum temperature of ∼ 700 °C. The nanoplates collapse into relatively rounded Ln2O2S particles while the microprisms retain well their initial morphologies at 1 200 °C, thus yielding two types of red phosphors. Photoluminescence excitation (PLE) studies found two distinct charge transfer (CT) excitation bands of O2- → Eu3+ at ∼ 270 nm and S2- → Eu3+ at ∼ 340 nm for the Ln2O2S phosphors, with the latter being stronger and both significantly stronger than the intrinsic intra-f transitions of Eu3+. The two types of phosphors share high similarities in the positions of PLE/PL (photoluminescence) bands and both show the strongest red emission at 627 nm (5D0 → 7F2 transition of Eu3+) under S2- → Eu3+ CT excitation at 340 nm. The PLE/PL intensities show clear dependence on particle morphology and calcination temperature, which were investigated in detail. Fluorescence decay analysis reveals that the 627 nm red emission has a lifetime of ∼ 0.5 ms for both types of the phosphors.

Size-dependent color tuning of efficiently luminescent germanium nanoparticles.

It is revealed that rigorous control of the size and surface of germanium nanoparticles allows fine color tuning of efficient fluorescence emission in the visible region. The spectral line widths of each emission were very narrow (<500 meV). Furthermore, the absolute fluorescence quantum yields of each emission were estimated to be 4-15%, which are high enough to be used as fluorescent labeling tags. In this study, a violet-light-emitting nanoparticle is demonstrated to be a new family of luminescent Ge. Such superior properties of fluorescence were observed from the fractions separated from one mother Ge nanoparticle sample by the fluorescent color using our developed combinatorial column technique. It is commonly believed that a broad spectral line width frequently observed from Ge nanoparticle appears because of an indirect band gap nature inherited even in nanostructures, but the present study argues that such a broad luminescence spectrum is expressed as an ensemble of different spectral lines and can be separated into the fractions emitting light in each wavelength region by the appropriate postsynthesis process.

Unprecedented simultaneous enhancement in strain tolerance, toughness and strength of Al2O3 ceramic by multiwall-type failure of a high loading of carbon nanotubes.

Carbon nanotubes (CNTs) have a remarkable load-bearing ability. Recently, however, multi-walled CNTs (MWCNTs) have been shown to possess dramatically higher load-bearing ability when intimately embedded in an oxide ceramic (Al2O3), because the load could be transferred not to only their outermost walls but also their generally unloaded inner walls via the strong interwall shear resistance originating from residual compressive stresses. This phenomenon is characterized by an uncommon, highly energy-dissipating, multiwall-type failure of individual MWCNTs during hybrid fracture, with no evidence of pullout. Here, we demonstrate that this nanoscale in-MWCNT load-transfer process, at an optimized, high loading of MWCNTs (10 vol%) and in a pore-free and uniform platform, leads to unprecedented, dramatic simultaneous enhancement in strain tolerance (81%), fracture toughness (52.2%), and flexural strength (22%) of the Al2O3 ceramic matrix. The extent of toughening by this mechanism is also the highest ever reported. This unprecedented performance by using a high loading of functional MWCNTs, namely, toughening, strengthening, softening and lightening, simultaneously and at this level, has implications for many functional and structural applications.

Spark plasma sintered Ni-YSZ/YSZ bi-layers for solid oxide fuel cell.

Ni-YSZ/YSZ bi-layers for SOFCs were fabricated by spark plasma sintering (SPS). Optimization of SPS parameters of YSZ and NiO/YSZ powders was performed in order to fabricate anode and electrolyte with desired microstructures. The effect of sintering conditions on microstructure and electrical properties of YSZ was studied. The influence of processing parameters and amount of pore-forming agent on the microstructures of Ni/YSZ cermets was also investigated. It was shown that the amount of pore-former and in situ reduction of nickel oxide had a substantial effect on microstructure of the cermets. The in situ reduced anode demonstrates sufficiently homogeneous distribution of Ni and YSZ making a conduction path for electrons and ions. Ni-YSZ/YSZ bi-layers with crack-free and well-bonded anode/electrolyte interface were obtained. Furthermore, warping was not observed for the produced bi-layers.