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At least 829 records · Page 46

Ionic liquid assisted microwave synthesis route towards color-tunable luminescence of lanthanide- doped BiPO 4

Ln 3+ -doped (Ln=Sm, Eu, Tb, Dy) nanoparticles of BiPO 4 with a particle size below 10 nm were synthesized in a straightforward manner from the appropriate mixture of the respective metal acetates and the task-specific ionic liquids choline or butylammonium dihydrogen-phosphate by conversion in a laboratory microwave (120 °C, 10 min). The ionic liquid acts not only as a solvent and microwave susceptor, but also as the reaction partner and nanoparticle stabilizer. The materials were thoroughly characterized not only with respect to their optical properties but also by PXRD, FT-IR, TEM techniques. Furthermore, depending on the lanthanide, the nanomaterial shows intense luminescence of different colors such as: orange (Sm 3+ ), red (Eu 3+ ), green (Tb 3+ ) or even white (Dy 3+ ).

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Two convenient low-temperature routes to single crystals of plutonium dioxide

During the solvothermal synthesis of a low-dimensional borate, KB 5 O 7 (OH) 2 2H 2 O, in the presence of Pu(III), single crystals of plutonium dioxide unexpectedly formed. Single crystals of PuO 2 also formed during the hydrothermal synthesis of another borate, Na 2 B 5 O 8 (OH) 2 H2O, in the presence of Pu(III). The reactions were conducted at 170 °C and 150 °C, respectively, which are much lower temperature than previously reported preparations of crystalline PuO 2 . Yellow-green crystals with a tablet habit were characterized by single crystal X-ray diffraction and solid-state UV–vis–NIR absorption spectroscopy. The crystal structure was solved by direct methods with R 1 =1.26% for 19 unique observed reflections. PuO 2 is cubic, space group $Fm\bar{3}m$, and adopts the fluorite structure type. Finally, the lattice parameter was determined to be $a$=5.421(5)Å giving a volume of 159.3(2)Å3. The absorption spectrum is consistent with Pu(IV).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Understanding the structural and morphological effects of synthesis route on NpO 2

The availability of actinide standard materials for use in nuclear safeguard applications is critical, as is thorough characterization thereof. Although accurate trace element compositions and isotopic considerations are paramount for deployment of reference standards, structural characterization is also essential towards accurately describing the chemical form and potential matrix effects in candidate materials. Here, to this end, samples of NpO 2 were synthesized via a direct denitration (DD) method and probed with powder X-ray diffraction (PXRD), Raman spectroscopy, and scanning electron microscopy (SEM) for structural and morphological characterization and comparison with NpO 2 materials produced via modified direct denitration (MDD). PXRD confirmed the bulk identity of NpO 2 , and no additional phases were identified using this method. Analysis of Raman data collected using a 532 nm excitation wavelength indicates that samples are mostly phase pure; however, some variability in spectral features is observed. Analysis of additional spectroscopic data collected with a 785 nm excitation wavelength revealed variability in the relative intensity of spectral features. Raman spectroscopy indicates that the sample is primarily NpO 2 ; however, additional signals indicate possible structural disorder, oxidized species, or potential contributions from other Np phases. To further investigate the possibility of additional phase contributions within the sample of NpO 2 , Raman spectroscopic mapping was employed to examine the homogeneity of the sample produced via DD. From this analysis, we determined that despite variability in the intensity of Raman-active vibrational modes, consistent spectra are obtained throughout the area of the sample investigated. SEM images show aggregates with variable sizes and shapes, with rounded, primary particles possessing an average diameter of approximately 100 nm. Comparison of the results of these multimodal analyses to the literature indicates that the crystal chemical, spectroscopic, and microstructural properties of NpO 2 vary based on synthesis method, even if X-ray diffraction data indicate that the bulk phase is NpO 2 .

Direct denitration↗

Underlying limitations behind impedance rise and capacity fade of single crystalline Ni-rich cathodes synthesized via a molten-salt route

Layered oxide LiNi x Mn y Co z O 2 (NMC) cathodes are often synthesized as polycrystalline secondary particles. Due to intergranular fracture stemming from volume changes of randomly oriented primary particles during charge/discharge, the synthesis of larger single-crystalline cathodes is of high interest. In this work, molten salt assisted growth of micron-sized Ni-rich crystals is achieved with excellent crystallinity, low cation mixing, and negligible impurities. However, electrochemical performance is compromised by high surface reactivity resulting in decomposition of electrolyte and subsequent formation of a thick CEI layer. While intergranular fracture is eliminated, planar gliding and severe intragranular fracture along the (003) plane occurs in the high voltage region within the first few cycles and is associated primarily with H2 to H3 structural transitions. In addition, H2 to H3 transitions are highly irreversible with cyclic voltammograms revealing polarization growth within <5 cycles. Subsequently, the single-crystalline material exhibited markedly reduced available capacity and enhanced capacity fade from sharp impedance growth compared to its polycrystalline counterpart. Here, this work furthers a fundamental understanding into the limitations of single-crystalline Ni-rich cathodes, and the obstacles limiting the advantages offered by the single-crystalline morphology.

25 ENERGY STORAGE↗

NMR investigation of proton transport in polybenzimidazole/polyphosphoric acid membranes prepared via novel synthesis route

Here, in this work, we present a molecular-level view of the structural changes in polybenzimidazole (PBI) membranes doped with phosphoric acid (PA) generated by a novel membrane fabrication technique. The modified PA doped membranes displayed unprecedented ionic conductivity at elevated temperatures, comparable to the starting PBI gel membranes prepared by the commonly used PPA process, while also exhibiting enhanced mechanical properties. To elucidate the cause of these effects, we used multi-nuclear ( 1 H, 13 C, 31 P) 1D PFG, MAS and CPMAS, and 2D HETCOR magnetic resonance (NMR) techniques to characterize the structure and dynamics of the modified film and the original gel PBI membranes. 1 H diffusivity measurements show significantly enhanced proton diffusivity, both in magnitude and in lower activation energy, which were consistent with its high ionic conductivity despite the lower PA content compared to the original gel membrane. CPMAS experiments further substantiated that the location of these distinct phosphate environments as being close to the polymer network. Finally, the phosphate groups in the modified membrane were revealed to be strongly bounded to each other and to the PBI polymer backbone in contrast to the combination of weakly and strongly bounded groups of the original gel membrane.

74 ATOMIC AND MOLECULAR PHYSICS↗

Stepwise synthesis, characterization, and electrochemical properties of ordered mesoporous carbons containing well-dispersed Pt nanoparticles using a functionalized template route

A stepwise method is described for the accurately controlled growth of Pt nanoparticles supported on ordered mesoporous carbons (Pt-OMC) by the nanocasting of carbon and metal precursors in the pore channels of mesoporous silicas functionalized with Si-H groups. Results obtained from N{sub 2} adsorption/desorption isotherms and transmission electron microscopy showed well-dispersed Pt nanoparticles (2-3 nm) on Pt-OMC with high surface area (837 m{sup 2} g{sup -1}) and regular pore channels (2.9 nm), which facilitate reactant/product diffusion. X-ray diffraction and X-ray photoelectron spectroscopy indicated that Pt nanoparticles in the Pt-OMC sample were mostly present in the metallic form of a face-centered cubic (fcc) crystalline structure. The Pt-OMC catalyst was found to have superior electrocatalytic properties during oxygen reduction reaction as compared to typical commercial electrocatalysts. - Graphical abstract: A novel procedure has been developed to synthesize ordered carbon mesoporous carbons (OMC) containing well-dispersed and highly electrocatalytic Pt nanoparticles (Pt-OMC) for oxygen reduction reaction. Highlights: > A novel method to incorporate nanosized Pt particles on nanostructure carbons. > Functionalized silica templates were used to control size and distribution of Pt nanoparticles. > Electrochemical measurements of oxygen reduction demonstrated high catalytic activity compared to common commercial catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Decomposition of molybdate-hexamethylenetetramine complex: One single source route for different catalytic materials

Decomposition of ammonium heptamolybdate-hexamethylentetramine (HMTA) complex (HMTA){sub 2}(NH{sub 4}){sub 4}Mo{sub 7}O{sub 24}.2H{sub 2}O was studied as a function of treatment conditions in the range 300-1173 K. The evolution of solid products during decomposition was studied by thermal analysis and in situ EXAFS. Depending on the nature of the gas used for treatment, single phases of highly dispersed nitrides Mo{sub 2}N, carbide Mo{sub 2}C, or oxide MoO{sub 2} can be obtained. The nature of the products obtained was explained by qualitative thermodynamical considerations. Morphology of the solids considerably depends on such preparation parameters as temperature and mass velocity of the gas flow. For the nitride-based materials, catalytic activity was evaluated in the model thiophene HDS reaction. It was demonstrated that NH{sub 3}-treated samples showed better catalytic activity than N{sub 2}-treated ones due to cleaner surface and better morphology. Transmission microscopy, XRD and XPS studies showed that MoS{sub 2} is formed on the surface during HDS reaction or sulfidation with H{sub 2}S. Optimized nitride-derived catalysts showed mass activity several times higher than unsupported MoS{sub 2} or MoS{sub 2}/Al{sub 2}O{sub 3} reference catalyst. - Graphical Abstract: Depending on the conditions, decomposition of molybdate-HTMA complex yields highly dispersed molybdenum nitride, carbide or oxide. Research Highlights: > Decomposition of molybdate-HTMA complex yields highly dispersed Mo{sub 2}N, Mo{sub 2}C or MoO{sub 2}. > In situ EXAFS shows formation of common amorphous product MoC{sub x}N{sub y}O{sub z} at 673 K. > Crystalline Mo{sub 2}N with surface area near 200 m{sup 2}/g was obtained at 823 K. > High mass activity in thiophene HDS was observed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An improved pyrolysis route to synthesize carbon-coated CdS quantum dots with fluorescence enhancement effect

Well-dispersed carbon-coated CdS (CdS-C) quantum dots were successfully prepared via the improved pyrolysis of bis(1-dodecanethiol)-cadmium(II) under nitrogen atmosphere. This simple method effectively solved the sintered problem resulted from conventional pyrolysis process. The experimental results indicated that most of the as-prepared nanoparticles displayed well-defined core-shell structures. The CdS cores with diameter of {approx}5 nm exhibited hexagonal crystal phase, the carbon shells with thickness of {approx}2 nm acted as a good dispersion medium to prevent CdS particles from aggregation, and together with CdS effectively formed a monodisperse CdS-Carbon nanocomposite. This composite presented a remarkable fluorescence enhancement effect, which indicated that the prepared nanoparticles might be a promising photoresponsive material or biosensor. This improved pyrolysis method might also offer a facile way to prepare other carbon-coated semiconductor nanostructures. - Graphical abstract: We demonstrated a facile approach to synthesize well-dispersed carbon-coated CdS quantum dots. The as-prepared nanoparticles presented remarkable fluorescence enhancement effect. Highlights: > Carbon-coated CdS quantum dots were synthesized by an one-step pyrolysis method. > Well-dispersed CdS-carbon nanoparticles were obtained by an acid treatment process. > As-prepared nanoparticles presented remarkable fluorescence enhancement effect.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Colloidal CIGS and CZTS nanocrystals: A precursor route to printed photovoltaics

This review article summarizes our research focused on Cu(In{sub 1-x}Ga{sub x})Se{sub 2} (CIGS) nanocrystals, including their synthesis and implementation as the active light absorbing material in photovoltaic devices (PVs). CIGS PV layers are typically made using a high temperature (>450 Degree-Sign C) process in which Cu, In and Ga are sequentially or co-evaporated and selenized. We have sought to use CIGS nanocrystals synthesized with the desired stoichiometry to deposit PV device layers without high temperature processing. This approach, using spray deposition of the CIGS light absorber layers, without high temperature selenization, has enabled up to 3.1% power conversion efficiency under AM 1.5 solar illumination. Although the device efficiency is too low for commercialization, these devices provide a proof-of-concept that solution-deposited CIGS nanocrystal films can function in PV devices, enabling unconventional device architectures and materials combinations, including the use of flexible, inexpensive and light-weight plastic substrates. - Graphical abstract: The semiconductor light-absorbing layers in photovoltaic devices can be deposited under ambient conditions using nanocrystal inks. Devices can be fabricated on glass or on mechanically flexible plastic substrates. Highlights: Black-Right-Pointing-Pointer CIGS and CZTS nanocrystals are synthesized and formulated into inks. Black-Right-Pointing-Pointer Nanocrystal films are spray deposited and used as light absorbing layers in photovoltaic devices. Black-Right-Pointing-Pointer Photovoltaic devices were constructed from nanowire mats. Black-Right-Pointing-Pointer Photovoltaic device efficiency is limited by electrical transport in the nanocrystal layers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Green route synthesis of high quality CdSe quantum dots for applications in light emitting devices

Investigation was made on light emitting diodes fabricated using CdSe quantum dots. CdSe quantum dots were synthesized chemically using olive oil as the capping agent, instead of toxic phosphine. Room temperature photoluminescence investigation showed sharp 1st excitonic emission peak at 568 nm. Bi-layer organic/inorganic (P3HT/CdSe) hybrid light emitting devices were fabricated by solution process. The electroluminescence study showed low turn on voltage ({approx}2.2 V) .The EL peak intensity was found to increase by increasing the operating current. - Graphical abstract: Light emitting diode was fabricated using CdSe quantum dots using olive oil as the capping agent, instead of toxic phosphine. Bi-layer organic/inorganic (P3HT/CdSe) hybrid light emitting device shows strong electroluminescence in the range 630-661 nm. Highlights: Black-Right-Pointing-Pointer CdSe Quantum dots were synthesized using olive oil as the capping agent. Black-Right-Pointing-Pointer Light emitting device was fabricated using CdSe QDs/P3HT polymer heterojunction. Black-Right-Pointing-Pointer The I-V characteristics study showed low turn on voltage at {approx}2.2 V. Black-Right-Pointing-Pointer The EL peak intensity increases with increasing the operating current.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solid-state chemistry route for supported tungsten and tungsten carbide nanoparticles

Nanoparticles of tungsten and tungsten carbide have been prepared using solid-state chemistry methods. After the vapor phase impregnation of a tungsten hexachloride precursor on a carbon support, a temperature-programmed reduction/carburization was performed. Several parameters were investigated and the evolution of obtained samples was followed by XRD and TEM. The optimization of the reaction parameters led to the preparation of W, W{sub 2}C and WC particles well dispersed on the support. WC phase however could not be obtained alone with less than 10 nm mean size. This could be explained by the carburization mechanism and the carbon diffusion on the support. - Graphical abstract: Bright field picture of carbon-supported WC nanoparticles dispersed on the surface of the sample 1223 K in 10% CH{sub 4}/90% H{sub 2}. Highlights: Black-Right-Pointing-Pointer We aimed at the preparation of supported nanoparticulate tungsten derivatives. Black-Right-Pointing-Pointer Several parameters were investigated. Black-Right-Pointing-Pointer The evolution of obtained samples was followed by XRD and TEM. Black-Right-Pointing-Pointer The optimal preparation led to W, W{sub 2}C and WC particles dispersed on the support.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Co-Al mixed metal oxides/carbon nanotubes nanocomposite prepared via a precursor route and enhanced catalytic property

The present work reported the synthesis of Co-Al mixed metal oxides/carbon nanotubes (CoAl-MMO/CNT) nanocomposite from Co-Al layered double hydroxide/CNTs composite precursor (CoAl-LDH/CNT). The materials were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), low temperature nitrogen adsorption-desorption experiments, thermogravimetric and differential thermal analyses (TG-DTA), Raman spectra and X-ray photoelectron spectroscopy (XPS). The results revealed that in CoAl-MMO/CNT nanocomposite, the nanoparticles of cobalt oxide (CoO) and Co-containing spinel-type complex metal oxides could be well-dispersed on the surface of CNTs, thus forming the heterostructure of CoAl-MMO and CNTs. Furthermore, as-synthesized CoAl-MMO/CNT nanocomposite was utilized as additives for catalytic thermal decomposition of ammonium perchlorate (AP). Compared to those for pure AP and CoAl-MMO, the peak temperature of AP decomposition for CoAl-MMO/CNT was significantly decreased, which is attributed to the novel heterostructure and synergistic effect of multi-component metal oxides of nanocomposite. - Graphical abstract: Hybrid Co-Al mixed metal oxides/carbon nanotubes nanocomposite showed the enhanced catalytic activity in the thermal decomposition of ammonium perchlorate, as compared to carbon nanotubes and pure Co-Al mixed metal oxides. Highlights: Black-Right-Pointing-Pointer Co-Al mixed metal oxides/carbon nanotubes nanocomposite was synthesized. Black-Right-Pointing-Pointer Co-Al mixed metal oxides consisted of cobalt oxide and Co-containing spinels. Black-Right-Pointing-Pointer Nanocomposite exhibited excellent catalytic activity for the decomposition of AP. Black-Right-Pointing-Pointer The superior catalytic property is related to novel heterostructure and composition.

36 MATERIALS SCIENCE↗

A high-pressure route to thermoelectrics with low thermal conductivity: The solid solution series AgIn{sub x}Sb{sub 1−x}Te{sub 2} (x=0.1–0.6)

Metastable rocksalt-type phases of the solid solution series AgIn{sub x}Sb{sub 1−x}Te{sub 2} (x=0.1, 0.2, 0.4, 0.5 and 0.6) were prepared by high-pressure synthesis at 2.5 GPa and 400 °C. In these structures, the coordination number of In{sup 3+} is six, in contrast to chalcopyrite ambient-pressure AgInTe{sub 2} with fourfold In{sup 3+} coordination. Transmission electron microscopy shows that real-structure phenomena and a certain degree of short-range order are present, yet not very pronounced. All three cations are statistically disordered. The high degree of disorder is probably the reason why AgIn{sub x}Sb{sub 1−x}Te{sub 2} samples with 0.4<x<0.6 exhibit very low thermal conductivities with a total κ<0.5 W/K m and a lattice contribution of κ{sub ph} ∼0.3 W/K m at room temperature. These are lower than those of other rocksalt-type tellurides at room temperature; e.g. the well-known thermoelectric AgSbTe{sub 2} (κ ∼0.6 W/K m). The highest ZT value (0.15 at 300 K) is observed for AgIn{sub 0.5}Sb{sub 0.5}Te{sub 2}, mainly due to its high Seebeck coefficient of 160 µV/K. Temperature-dependent X-ray powder patterns indicate that the solid solutions are metastable at ambient pressure. At 150 °C, the quaternary compounds decompose into chalcopyrite-type AgInTe{sub 2} and rocksalt-type AgSbTe{sub 2}. - Graphical abstract: Reaction scheme, temperature characteristics of the ZT value and a selected-area electron diffraction pattern (background) of AgIn{sub 0.5}Sb{sub 0.5}Te{sub 2}, which crystallizes in a rocksalt-type structure with statistical cation disorder. Display Omitted - Highlights: • High-pressure synthesis yields the novel solid solution series AgIn{sub x}Sb{sub 1−x}Te{sub 2}. • In contrast to AgInTe{sub 2}, the compounds are inert at ambient pressure. • HRTEM shows no pronounced short-range order in the disordered NaCl-type structure. • The metastable phases exhibit very low total thermal conductivities <0.5 W/K m. • ZT values of 0.15 at room temperature were measured for AgIn{sub 0.5}Sb{sub 0.5}Te{sub 2}.

36 MATERIALS SCIENCE↗

Investigation of some new hydro(solvo)thermal synthesis routes to nanostructured mixed-metal oxides

We present a study of two new solvothermal synthesis approaches to mixed-metal oxide materials and structural characterisation of the products formed. The solvothermal oxidation of metallic gallium by a diethanolamine solution of iron(II) chloride at 240 °C produces a crystalline sample of a spinel-structured material, made up of nano-scale particles typically 20 nm in dimension. XANES spectroscopy at the K-edge shows that the material contains predominantly Fe{sup 2+} in an octahedral environment, but that a small amount of Fe{sup 3+} is also present. Careful analysis using transmission electron microscopy and powder neutron diffraction shows that the sample is actually a mixture of two spinel materials: predominantly (>97%) an Fe{sup 2+} phase Ga{sub 1.8}Fe{sub 1.2}O{sub 3.9}, but with a minor impurity phase that is iron-rich. In contrast, the hydrothermal reaction of titanium bis(ammonium lactato)dihydroxide in water with increasing amounts of Sn(IV) acetate allows nanocrystalline samples of the SnO{sub 2}–TiO{sub 2} solid solution to be prepared directly, as proved by powder XRD and Raman spectroscopy. - Graphical abstract: New solvothermal synthesis approaches to spinel and rutile mixed-metal oxides are reported. - Highlights: • Solvothermal oxidation of gallium metal in organic iron(II) solution gives a novel iron gallate spinel. • Hydrothermal reaction of titanium(IV) complex and tin(IV) acetate produces the complete SnO{sub 2}–TiO{sub 2} solid solution. • Nanostructured mixed-metal oxide phases are produced directly from solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hierarchical Na-doped cubic ZrO{sub 2} synthesis by a simple hydrothermal route and its application in biodiesel production

Hierarchical growth of cubic ZrO{sub 2} phase was successfully synthesized via a simple hydrothermal process in the presence of different surfactants (cationic, non-ionic and anionic) and sodium hydroxide. The structural and microstructural characterizations of different ZrO{sub 2} powders were performed using various techniques, such as X-ray diffraction, transmission electron microscopy, N{sub 2} adsorption–desorption, scanning electron microscopy and infrared. Results indicated that sodium addition stabilized the cubic ZrO{sub 2} phase by a Na-doping process, independently of the surfactant used. In contrast, microstructural characteristics varied as a function of the surfactant and sodium presence. In addition, water vapor (H{sub 2}O) and carbon dioxide (CO{sub 2}) sorption properties were evaluated on ZrO{sub 2} samples. Results evidenced that sample surface reactivity changed as a function of the sodium content. Finally, this surface reactivity was evaluated on the biodiesel transesterification reaction using the different synthesized samples, obtaining yields of 93%. - Graphical abstract: Hierarchical growth of cubic Na-ZrO{sub 2} phase was synthesized by hydrothermal processes in the presence of surfactants and sodium. Sodium addition stabilized the cubic phase by a Na-doping process, while the microstructural characteristics varied with surfactants. Finally, this surface reactivity was evaluated on the biodiesel transesterification reaction. - Highlights: • Cubic-ZrO{sub 2} phase was synthesized via a simple hydrothermal process. • ZrO{sub 2} structure and microstructures changed as a function of the surfactant. • Cubic-ZrO{sub 2} phase was evaluated on the biodiesel transesterification reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rapid solid-state metathesis route to transition-metal doped titanias

Rapid solid-state metathesis (SSM) reactions are often short-lived highly exothermic reactions that yield a molten alkali halide salt that aids in product growth and crystallization. SSM reactions may also produce kinetically stabilized structures due to the short (seconds) reaction times. This report describes the investigation of rapid SSM reactions in the synthesis of transition-metal doped titanias (M–TiO{sub 2}). The dopant targeted compositions were ten mol percent and based on elemental analysis, many of the M–TiO{sub 2} samples were close to this targeted level. Based on surface analysis, some samples showed large enrichment in surface dopant content, particularly chromium and manganese doped samples. Due to the highly exothermic nature of these reactions, rutile structured TiO{sub 2} was observed in all cases. The M–TiO{sub 2} samples are visible colored and show magnetic and optical properties consistent with the dopant in an oxide environment. UV and visible photocatalytic experiments with these visibly colored rutile M–TiO{sub 2} powders showed that many of them are strongly absorbent for methylene blue dye and degrade the dye under both UV and visible light illumination. This work may open up SSM reactions as an alternate non-thermodynamic reaction strategy for dopant incorporation into a wide range of oxide and non-oxides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗