Cyan-Light-Emitting Chalcogenometallate Phosphor, KGaS2:Eu2+, for Phosphor-Converted White Light-Emitting Diodes.

A novel KGaS2 phosphor host that emits a cyan light was discovered to fill the cyan gap in the visible spectrum of phosphor-converted white light-emitting diodes (pc-wLEDs). KGaS2, belonging to the chalcogenometallates of the type ABQ2, was synthesized via a solid-state route with compositions optimized to achieve a phosphor host that would achieve the best photoluminescence (PL) properties. The activation with Eu2+ gave rise to PL in the cyan region of the spectrum with a PL maximum at ∼498 nm, as measured under the near-UV (420 nm) and blue (450 nm) excitations. The PL properties at the near-UV excitation are found to be much better, as compared to those obtained at the blue excitation. The Rietveld analysis, using high resolution synchrotron X-ray diffraction calibrated at a wavelength of 1.522 Å and selected area electron diffraction (SAED) pattern analysis of the composition optimized with the highest PL intensity, revealed a centrosymmetric monoclinic structure in the C2/c space group. The stoichiometry of the optimized composition, as estimated using Rietveld refinement, was revealed as KGa0.921S1.882:Eu2+. The decay curve measurement, using time-resolved spectroscopy, yielded a 10% decay time of 0.41 µs, which is much smaller compared with the decay time of the commercially available ß-SIALON phosphor that has a 10% decay time of 1.71 µs. The white pc-LED, fabricated with a cyan phosphor, had a higher value on the color rendering index and a lower value for color correlated temperatures, as compared with the version fabricated without a cyan phosphor, which makes this novel phosphor suitable for applications as a pc-wLED.

New red-emitting phosphor Rb x K3-x SiF7:Mn4+ (x = 0, 1, 2, 3): DFT predictions and synthesis.

Finding new phosphors through an efficient method is important in terms of saving time and cost related to the development of phosphor materials. The ability to identify new phosphors through preliminary simulations by calculations prior to the actual synthesis of the materials can maximize the efficiency of novel phosphor development. In this paper, we demonstrate the use of density functional theory (DFT) calculations to guide the development of a new red phosphor. We performed first-principles calculations based on DFT for pristine and Mn-doped Rb x K3-x SiF7 (x = 0, 1, 2, 3) and predicted their stability, electronic structure, and luminescence properties. On the basis of the results, we then synthesized the stable Rb2KSiF7:Mn4+ red conversion phosphor and investigated its luminescence, structure, and stability. As a result, we confirmed that Rb2KSiF7:Mn4+ emitted red light with a longer wavelength than that emitted by K3SiF7:Mn4+ and a wavelength similar to that of K2SiF6:Mn4+. These results show that DFT calculations can provide rational insights into the design of a phosphor material before it is synthesized, thereby reducing the time and cost required to develop new red conversion phosphors.

Hydrometallurgical recycling of surface-coated metals from automobile-discarded ABS plastic waste.

The ammoniacal leaching of surface-coated metals from automobile-discarded ABS plastics followed by their recovery through solvent extraction has been investigated. The leaching of ABS (typically containing 4.1% Cu, 1.3% Ni, and 0.03% Cr) could efficiently dissolve the ammine complexes of Cu and Ni, leaving Cr unleached as fine particles. The optimization studies for achieving the maximum efficiency revealed that the leaching of metal ions in different ammoniacal solutions follows the order CO32- > Cl- > SO42-. The leaching carried out in a carbonate medium by maintaining the total NH3 concentration 5.0 M at a NH4OH/(NH4)2CO3 ratio of 4:1, pulp density of 200 g/L, agitation speed of 400 rpm, temperature of 20 °C, and time of 120 min yielded the optimum efficiency of >99% Cu and Ni (i.e., 8.14 g/L and 2.57 g/L, respectively, in the leach liquor). Subsequently, the solvent extraction of metals from ammoniacal leach liquor as a function of extractant (LIX 84-I) concentration and organic-to-aqueous (O:A) phase ratio was examined. Based on the extraction data, a three-stage counter-current extraction at O:A = 1:1 was validated using 0.8 M LIX 84-I, yielding the quantitative extraction of both metals into the organic phase. Thereafter, the stripping of metals in acid solutions indicated that 0.5 M H2SO4 could quantitatively strip Ni from the loaded organic phase; however, ∼27% Cu was also co-stripped. The rest of Cu from the Ni-depleted organic phase was separately stripped with 1.0 M H2SO4 that can be directly sent to the electrowinning process. On the other hand, the co-stripped metals from the acidic solution can be easily separated, again using LIX 84-I as the extractant, by adopting the pH-swing method. Finally, a process has been proposed for the hydrometallurgical recovery of surface-coated metals from waste ABS plastics; that does not affect the physicochemical characteristics of the polymer substances for their reuse.

Metaheuristics-Assisted Combinatorial Screening of Eu2+-Doped Ca-Sr-Ba-Li-Mg-Al-Si-Ge-N Compositional Space in Search of a Narrow-Band Green Emitting Phosphor and Density Functional Theory Calculations.

A metaheuristics-based design would be of great help in relieving the enormous experimental burdens faced during the combinatorial screening of a huge, multidimensional search space, while providing the same effect as total enumeration. In order to tackle the high-throughput powder processing complications and to secure practical phosphors, metaheuristics, an elitism-reinforced nondominated sorting genetic algorithm (NSGA-II), was employed in this study. The NSGA-II iteration targeted two objective functions. The first was to search for a higher emission efficacy. The second was to search for narrow-band green color emissions. The NSGA-II iteration finally converged on BaLi2Al2Si2N6:Eu2+ phosphors in the Eu2+-doped Ca-Sr-Ba-Li-Mg-Al-Si-Ge-N compositional search space. The BaLi2Al2Si2N6:Eu2+ phosphor, which was synthesized with no human intervention via the assistance of NSGA-II, was a clear single phase and gave an acceptable luminescence. The BaLi2Al2Si2N6:Eu2+ phosphor as well as all other phosphors that appeared during the NSGA-II iterations were examined in detail by employing powder X-ray diffraction-based Rietveld refinement, X-ray absorption near edge structure, density functional theory calculation, and time-resolved photoluminescence. The thermodynamic stability and the band structure plausibility were confirmed, and more importantly a novel approach to the energy transfer analysis was also introduced for BaLi2Al2Si2N6:Eu2+ phosphors.

Discovery of a Red-Emitting Li3RbGe8O18:Mn4+ Phosphor in the Alkali-Germanate System: Structural Determination and Electronic Calculations.

A solid-state combinatorial chemistry approach, which used the A-Ge-O (A = Li, K, Rb) system doped with a small amount of Mn4+ as an activator, was adopted in a search for novel red-emitting phosphors. The A site may have been composed of either a single alkali metal ion or of a combination of them. This approach led to the discovery of a novel phosphor in the above system with the chemical formula Li3RbGe8O18:Mn4+. The crystal structure of this novel phosphor was solved via direct methods, and subsequent Rietveld refinement revealed a trigonal structure in the P3̅1m space group. The discovered phosphor is believed to be novel in the sense that neither the crystal structure nor the chemical formula matches any of the prototype structures available in the crystallographic information database (ICDD or ICSD). The measured photoluminescence intensity that peaked at a wavelength of 667 nm was found to be much higher than the best intensity obtained among all the existing A2Ge4O9 (A = Li, K, Rb) compounds in the alkali-germanate system. An ab initio calculation based on density function theory (DFT) was conducted to verify the crystal structure model and compare the calculated value of the optical band gap with the experimental results. The optical band gap obtained from diffuse reflectance measurement (5.26 eV) and DFT calculation (4.64 eV) results were in very good agreement. The emission wavelength of this phosphor that exists in the deep red region of the electromagnetic spectrum may be very useful for increasing the color gamut of LED-based display devices such as ultrahigh-definition television (UHDTV) as per the ITU-R BT.2020-2 recommendations and also for down-converter phosphors that are used in solar-cell applications.

Phosphor informatics based on confirmatory factor analysis.

The theoretical understanding of phosphor luminescence is far from complete. To accomplish a full understanding of phosphor luminescence, the data mining of existing experimental data should receive equal consideration along with theoretical approaches. We mined the crystallographic and luminescence data of 75 reported Eu(2+)-doped phosphors with a single Wyckoff site for Eu(2+) activator accommodation, and 32 descriptors were extracted. A confirmatory factor analysis (CFA) based on a structural equation model (SEM) was employed since it has been helpful in understanding complex problems in social sciences and in bioinformatics. This first attempt at applying CFA to the data mining of engineering materials provided a better understanding of the structural and luminescent-property relationships for LED phosphors than what we have learnt so far from the conventional theoretical approaches.

A smart load-sensing system using standardized mechano-luminescence measurement.

The mechano-luminescence (ML) of phosphors has stirred a great deal of interest for its potential application in inexpensive, non-destructive load sensors. However, the most serious drawback of ML phosphors has been responses that differ according to the loading conditions. This has led to a lack of standardization in realizing smart ML sensor applications. We improved the applicability of ML phosphors to that of a smart, standardized load sensor by detecting ML based on the UV excitation above the threshold power density during the entire loading process. The ML behavior under these conditions was completely different from that of conventional ML behavior with UV excitation turned off. The ML output was clearly represented as a simple linear function of the applied load under conditions that could be either static or dynamic. In addition, neither a ML loss angle nor hysteresis behavior was observed under these ML measurement conditions.

Combinatorial screening of luminescent and structural properties in a Ce(3+)-doped Ln-Al-Si-O-N (Ln = Y, La, Gd, Lu) system: the discovery of a novel Gd3Al(3+x)Si(3-x)O(12+x)N(2-x):Ce(3+) phosphor.

The discovery of novel phosphors for use in light emitting diodes (LED) has gained in significance because LED-based solid-state lighting applications now attract a great deal of attention for energy savings and environmental concerns. Recent research trends have centered on the discovery of novel phosphors, not on slight variations of well-known phosphors. In a real sense, novelty goes beyond simple variations or improvements in existing phosphors. A brilliant strategy for the discovery of novel phosphors is to introduce an appropriate activator to existing inorganic compounds. These compounds have structures that are well-defined in crystallographic structure databases, but they have never been considered as a phosphor host. Another strategy is to discover new host compounds with structures that cannot be found in existing databases. We have simultaneously pursued both strategies by employing metaheuristics-assisted combinatorial material search techniques. In the present investigation, we screened a search space consisting of Ln-Al-Si-O-N (Ln = Y, La, Gd, Lu), and thereby we discovered a blue-light-emitting novel phosphor, Gd3Al(3+x)Si(3-x)O(12+x)N(2-x):Ce(3+), with a monoclinic system in the C2 space group--a potential candidate for UV-LED applications.

Selective recovery of gold from waste mobile phone PCBs by hydrometallurgical process.

The leaching of gold from the scrap mobile phone PCBs by electro-generated chlorine as an oxidant and its recovery by ion exchange process was investigated. The leaching experiments were carried out by employing separate leaching reactor connected with the anode compartment of a Cl(2) gas generator. The leaching of gold increased with increase in temperature and initial concentration of chlorine, and was favorable even at low concentration of acid, whereas copper leaching increased with increase in concentration of acid and decrease in temperature. In a two-stage leaching process, copper was mostly dissolved (97%) in 165 min at 25°C during the 1st stage leaching in 2.0 mol/L HCl by electro-generated chlorine at a current density of 714A/m(2) along with a minor recovery of gold (5%). In the 2nd stage gold was mostly leached out (93% recovery, ∼67 mg/L) from the residue of the 1st stage by the electro-generated chlorine in 0.1 mol/L HCl. Gold recovery from the leach liquor by ion exchange using Amberlite XAD-7HP resin was found to be 95% with the maximum amount of gold adsorbed as 46.03 mg/g resin. A concentrated gold solution, 6034 mg/L with 99.9% purity was obtained in the ion exchange process.

Recovery of H2SO4 from waste acid solution by a diffusion dialysis method.

A diffusion dialysis method using anion exchange membrane was used to recover H2SO4 from waste sulfuric acid solution produced at the diamond manufacturing process. Effects of flow rate, operation temperature, and metal ion concentration on the recovery of H2SO4 were investigated. The recovery of H2SO4 increased with the concentration of H2SO4 and operation temperature. It also increased with the flow rate ratio of water/H2SO4 solution up to 1, above which no further increase was observed. The flow rate did not affect the rejection of Fe and Ni ions. About 80% of H2SO4 could be recovered from waste sulfuric acid which contained 4.5M free-H2SO4 at the flow rate of 0.26x10(-3) m3/hm3. The concentration of recovered H2SO4 was 4.3M and the total impurity was 2000 ppm. Preliminary economic evaluation has revealed that the dialysis system is highly attractive one that has payback period of only few months.