Oxidation of detonation nanodiamonds in a reactive formulation

Nanodiamonds have been used as reducing agent in energetic compositions. The reactive formulations prepared by mixing detonation nanodiamond (DND) with potassium chlorate (PC) decompose according to two combustion modes, i.e. continuous or intermittent, depending on the nanodiamond proportion and pressing level used to shape the pellets. The analysis of a series of experimental results has led to build a predictive prevalence diagram of the combustion mode. In the continuous combustion domain, the reaction rate varies as a power law of the nanodiamond content: V = V₀[χ_DND]^− α. The pre-exponential factor gives an interesting estimate of the self-sustaining rate of the oxidation of pure nanodiamond loose powder (≈ 0.8 mm/s). Furthermore, the increase of the nanodiamond ratio in the composition makes the burning more regular, and slows down the combustion rate. The effect of pressing on the morphology of DND/PC compositions was intensively studied and led to the understanding of the combustion mechanisms. The porosity of interstitial DND powder acts as a thermal shield and favours the diffusion of the gaseous species released by the combustion in the fresh composition, leading to a convective propagation. This mechanism accounts for the continuous combustion. The thermal conductivity of DND powder measured experimentally is three orders of magnitude smaller than a typical value for bulk diamond (λ_D = 500 W·m^− 1·K^− 1). This result is in agreement with the values calculated from Maxwell's model, for spherical DND particles in a continuous fluid (air).     

Nanodiamond particles/reduced graphene oxide composites as efficient supercapacitor electrodes

The paper reports on the preparation of reduced graphene oxide (rGO) modified with nanodiamond particles composites by a simple solution phase and their use as efficient electrode in electrochemical supercapacitors. The technique relies on heating aqueous solutions of graphene oxide (GO) and nanodiamond particles (NDs) at different ratios at 100 °C for 48 h. The morphological properties, chemical composition and electrochemical behavior of the resulting rGO/NDs nanocomposites were investigated using UV/vis spectrometry, Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, transmission electron microscopy (TEM) and electrochemical means. The electrochemical performance, including the capacitive behavior of the rGO/NDs composites were investigated by cyclic voltammetry and galvanostatic charge/discharge curves at 1 and 2 A g⁻¹ in 1 M H₂SO₄. The rGO/ND matrix with 10/1 ratio displayed the best performance with a specific capacitance of 186 ± 10 F g⁻¹ and excellent cycling stability.     

Elemental analysis of nanodiamonds by inductively-coupled plasma atomic emission spectroscopy

A 68-element survey study was carried out on micro-impurities from 20 commercial nanodiamond samples from eight international manufacturers. The measurements were made using inductively coupled plasma atomic emission spectroscopy with detection limits for most elements below 1 ppm. Various methods of sample preparation were compared: direct introduction of suspensions, ashing with microwave-assisted acid digestion, and microwave-assisted acid extraction, and their advantages and disadvantages evaluated. The work demonstrates the feasibility of nanodiamond analysis by direct slurry nebulization, which provides a multi-element, rapid, simple, and relatively low-cost route for nanodiamond purity estimation. Most of the samples contain relatively high amounts of Fe, Na, Ca, Si, Cu, Al, S, and Ti (>100 ppm), while Pb, Zn, K, Mn, B, Cr, Mg, Mo, Sn, W, Ba, Sb, Co, and Sr are at low but significant amounts. In addition, in several samples, we found some uncommon elements like Ag, Ce, Y, Hf, Zr, and Hg. This study provides new possibilities for certifying nanodiamond purity, understanding their properties and behavior, and advancing their production technology.     

Dispersion and stability of 8 mol.% yttria stabilized zirconia suspensions for dip-coating filtration membranes

The dispersion and the stability of the suspensions from commercially available 8 mol.% yttria stabilized zirconia (8YSZ) powder have been systematically investigated as a function of the system factors such as pH value, temperature, solid loadings, molecular weight and amounts of polyacrylic acid (PAA) dispersant. The interaction mechanisms between YSZ particles and organic additives in suspensions were analyzed and discussed in detail. The crack-free tubular membranes derived from the fully dispersed and well stabilized YSZ suspensions with appropriate viscosity exhibited an average pore diameter of 0.31 μm and membranes thickness of 10 μm. The pure water permeability of the membrane was up to 1.7 m³ h⁻¹ bar⁻¹ m⁻².     

Nano- and micro-crystalline diamond growth by MPCVD in extremely poor hydrogen uniform plasmas

It is well established that argon rich plasmas (> 90% Ar) in Ar/CH₄/H₂ gas mixtures lead to (ultra)nanodiamond nucleation and growth by microwave plasma chemical vapour deposition (MPCVD). Nonetheless, in the present work, both microcrystalline and nanocrystalline diamond deposits developed under typical conditions for ultrananocrystalline (UNCD) growth by MPCVD. Silicon substrates were pretreated by abrasion using two different diamond powder types, one micrometric (< 0.5 μm) and the other nanometric (∼ 4 nm), the latter obtained by detonation methods. Samples characterization was performed by SEM (morphology), AFM (roughness and morphology) and micro-Raman (structure).For all samples, Raman analysis revealed good crystalline diamond quality with an evident ∼ 1332 cm^− 1 peak. The Raman feature observed at ∼ 1210 cm^− 1 is reported to correlate with two other common bands at ∼ 1140 cm^− 1 and ∼ 1490 cm^− 1 characteristic of nano- and ultra-nanocrystalline diamond.A new growth process is proposed to explain the observed morphology evolution from nano- to microcrystalline diamond. Based on this, the microcrystalline morphology is in fact a crystallographically aligned construction of nanoparticles.     

Micrometer-sized mesoporous diamond spherical particles

Micrometer-sized porous diamond spherical particles (PDSPs) were fabricated from nanodiamond (ND) particles using spray drying and microwave plasma-assisted chemical vapor deposition (MPCVD). Nitrogen gas sorption measurement revealed that the PDSP fabricated from 5 nm detonation ND particles had a Brunauer–Emmett–Teller (BET) surface area of ca. 300 m² g^− 1 and a narrow pore diameter distribution around 10 nm. Nitrogen sorption analysis of PDSP fabricated from various ND particle sizes (diameters from 20 to 50 nm) showed that the BET surface area decreased (200–85 m² g^− 1) and the average pore diameter increased (4.6–9.3 nm) as the ND diameter increased from 20 to 50 nm. Calculation with a simple model revealed that the pores of the PDSP were derived from the interparticle space of the NDs. The PDSP was durable to immersion in aqueous solutions of HF and NaOH, which indicates the extremely high chemical stability of the diamond-based mesoporous material. The PDSP surface was modified with octadecyl groups using a photochemical method. A column packed with the modified PDSP was successfully employed in a reverse phase high performance liquid chromatography (HPLC) column, and the successful separation of organic compounds was demonstrated with a water/acetonitrile mixture mobile phase.     

Deagglomeration and functionalisation of detonation nanodiamond with long alkyl chains

We have achieved the covalent functionalisation of detonation nanodiamond by an esterification reaction of carboxylic acid chlorides on hydroxylated nanodiamond. The resulting “nanodiamond esters” with a surface loading of 0.3–0.4 mmol g^− 1 of alkyl groups have been characterized by FTIR spectroscopy, thermogravimetry and elemental analysis. They exhibit a significantly improved dispersibility in organic solvents such as tetrahydrofurane and dichloromethane.     

Separation and determination of cadmium in water by foam column prior to inductively coupled plasma optical emission spectrometry

The sorption profile of cadmium (II) ions from aqueous iodide media onto procaine hydrochloride (PQ⁺·Cl⁻) treated polyurethane foams (PUFs) solid sorbent was studied. PQ⁺·Cl⁻ treated PUFs solid sorbent was found suitable and fast for Cd²⁺ uptake as [CdI4]_aq²⁻. Thus, removal of Cd²⁺ at trace levels by the sorbent packed columns was achieved. The sorbed Cd²⁺ species onto packed column were recovered with HNO₃ (10.0 mL, 1.0 mol L⁻¹) prior determination by inductively coupled plasma-optical emission spectrometry (ICP-OES). Plot of Cd²⁺ ions concentration was linear in the range 0.05–15 μg L⁻¹. The limits of detection and quantification of Cd²⁺ were found 0.01 μg L⁻¹ and 0.033 μg L⁻¹, respectively. Such limits could be improved to lower values by retention of Cd²⁺ species from large sample volumes of the aqueous phase at the optimized conditions. The relative standard deviation of the packed column for the extraction and recovery of standard aqueous solutions (0.1 L) containing 1.0 and 5.0 μg L⁻¹ (n = 3) of Cd²⁺ ions at flow rate of 5.0 mL min⁻¹ were 1.98 and 2.9%, respectively. The method was validated by analysis of Cd in certified reference materials (CRMs) IAEA-Soil-7 and TMDW water and wastewater samples.     

Selected sugar acids as highly effective deflocculants for concentrated nanoalumina suspensions

The possibility to fabricate nanoceramic materials by techniques based on colloidal processing requires the use of effectively working deflocculants (dispersing agents) which are able to stabilize and decrease the viscosity of aqueous nanopowders suspensions. Galacturonic and lactobionic acids have been used in the research as deffloculants for nanoalumina; they allowed to obtain ceramic suspensions of high solid loading (50 vol%) and relatively low viscosity (ca. 4 Pa s at a shear rate 10 s⁻¹). High solid loading could be achieved through combining three factors: the application of sugar acids as deflocculants, water leaching of the nanopowders from the surface impurities and precise defoaming of the slurries. Density of sintered bodies equalled 98% TD.     

Facile synthesis of functionalized porous carbon with three-dimensional interconnected pore structure for high volumetric performance supercapacitors

Functionalized porous carbon with three-dimensional (3D) interconnected pore structure has been successfully synthesized through direct heat-treatment of KOH-soaked soybeans. Benefiting from heteroatoms (N, O) doping, interconnected porous carbon framework with high surface area as well as high packing density (up to 1.1 g cm⁻³), the as-obtained porous carbon material exhibits high volumetric capacitance of 468 F cm⁻³, good rate capability and excellent cycling stability (91% of capacitance retention after 10,000 cycles) in 6 M KOH electolyte. More importantly, the as-assembled symmetric supercapacitor delivers high volumetric energy density of 28.6 Wh L⁻¹ in 1 M Na₂SO₄ aqueous solution.     

Graphene-wrapped polyaniline nanofibers as electrode materials for organic supercapacitors

Graphene-wrapped polyaniline nanofibers were prepared by assembly of negatively charged graphene oxide with positively charged aqueous dispersible polyaniline nanofibers in an aqueous dispersion, followed by the reduction of the graphene oxide. The hybrid material with a graphene oxide loading of 9.1 wt.% displayed a high specific capacitance of over 250 F g⁻¹ in a 1 M Et₄N⁺·BF₄⁻/propylene carbonate electrolyte, a 39.7% increase compared with pristine polyaniline nanofibers. A significant improvement in long-term cycle life was also realized. The hybrid exhibited an initial specific capacitance of 236 F g⁻¹, which remained as high as 173.3 F g⁻¹ over 1000 cycles, or a 26.3% decrease, much better than that for pure polyaniline nanofibers. An asymmetric supercapacitor based on this hybrid material and activated carbon was assembled. An energy density of 19.5 W h kg⁻¹ at a power density of 738.95 W kg⁻¹ was obtained for the cell under an operating voltage window of 2 V.     

High density carbon nanotube growth using a plasma pretreated catalyst

We have developed a direct current plasma pretreatment of the Fe catalyst to increase the area density of vertically-aligned carbon nanotube forests. The carbon wall density of the double- and multi-walled nanotubes reaches 4.8 × 10¹² cm⁻², with a 40% volume occupancy and a mass density of ∼0.4 g cm⁻³. The plasma pretreatment works by reducing the sintering of the catalyst nanoparticles during growth. This treatment increases the forest density by 8 times compared to the standard growth conditions.     

Early stage of diamond growth at low temperature

We investigate the first stages of nanocrystalline diamond (NCD) thin film growth at low substrate temperature. NCD films were grown on silicon substrates by microwave plasma enhanced chemical vapor deposition (CVD) for 0–300 min at a temperature of 410 °C. Si substrates were ultrasonically seeded in suspension of detonation nanocrystalline diamond powder. The seeding density approached values up to 1 ⁎ 10¹² cm^− 2, which allows growth of ultra-thin fully closed layers. Stagnation of the AFM roughness indicates that the low temperature NCD growth is a) delayed due to the surface contamination of the used nanodiamond powder and b) possibly dominated by the growth in the lateral direction. XPS measurements showed that the measured surface exhibits changes from a multi-phase composite (seeding layer) to single-phase one (NCD layer).     

New data on arsenic sorption properties of Zn–Al sulphate layered double hydroxides: Influence of competition with other anions

The adequacy of synthetic Zn–Al-sulphate LDHs to remove arsenic from aqueous systems was tested through sorption experiments, using a series of aqueous solutions with dissolved HAsO₄^2 − together with other anions (Cl⁻, SO₄^2 −, MoO₄^2 −, HCO₃⁻, CO₃^2 −) to assess their competition influence on the As removing process. The competitors were added into the solution both simultaneously and afterwards with respect to HAsO₄^2 − in order to verify the effectiveness and the possible reversibility of the As sorption process. The results showed that only carbonates species, in particular in the fully deprotonated form CO₃^2 −, affect significantly the otherwise high efficacy of the sorption process. In fact, up to ~ 90% of HAsO₄^2 − can be removed from the solution, decreasing to ~ 60% in the presence of CO₃^2 −, whilst up to ~ 30% of HAsO₄^2 − can be desorbed when CO₃^2 − is added afterwards into the solution. Considering the very restricted range of pH where HAsO₄^2 − and CO₃^2 − are simultaneously the predominant species in the solution (~ 10 < pH < ~ 11.5), Zn–Al-sulphate LDHs could be successfully used for the treatment of As contaminated waters with pH ranging from circum-neutral to moderately alkaline.     

Bulk preparation of (−)-epigallocatechin gallate-rich extract from green tea

(−)-Epigallocatechin gallate (EGCg)-rich extract (EGCg > 700 mg g⁻¹) was prepared from green tea leaves through a three-stage process consisting of liquid–liquid extraction and silica column purification. Crude tea extract was dissolved in ethyl acetate. After filtration, the solution was extracted by 10 g L⁻¹ citric acid solution twice, and then passed through silica column. The catechins compounds in the ethyl acetate eluate were back extracted to the aqueous phase, then extracted with a mixed solution of n-hexane/ethyl acetate (2/5, v/v) 3 times, concentrated, and freeze dried. 12.8 g EGCg-rich extract containing 709 mg g⁻¹ EGCg and 965 mg g⁻¹ total catechins was obtained from 300 g green tea leaves, with an EGCg recovery of 26.1% and a yield of 4.3%. This method was suitable for bulk preparation of EGCg-rich catechins from green tea leaves.     

Rheology and sedimentation velocity of alkaline suspensions of hematite particles at elevated temperature

This study aims to characterize the sedimentation velocity and the rheology of suspensions of hematite particles suspended in strongly alkaline media at 100 and 110 °C, as done for an alternative electrochemical process in development for iron production by direct electrode reduction of hematite. Considering the medium used in the process, i.e. 12% (v/v) suspension of hematite particles in 50% sodium hydroxide aqueous, the sedimentation velocity of hematite particle at 110 °C is 0.010 mm/s, which is very slow because the average size of the solid particles is around 10 μm and the significant collisions and interactions occuring between the particles in the concentrated suspension. Two geometries were used to characterize the rheological behavior of the apparent viscosity of the suspension of 12% (v/v) (i.e. 33 wt%) at 100 °C: a conventional Couette geometry and a helical ribbon mixer. The suspension was found shear thinning in the range of shear rate studied. The rheological behavior of the suspension can be described by a power-law model. The apparent viscosity of the hematite suspension estimated at a shear rate between 0.5 and 10 s⁻¹ is between 100 and 20 mPa s for the two geometries. The apparent viscosity calculated from the terminal velocity of 10 μm particles is of the same order of magnitude of the results obtained with the two rheometer configurations. The effect of the particle concentration on the sedimentation velocity and viscosity of the hematite suspensions was also studied.     

High-concentration aqueous dispersions of graphene produced by exfoliation of graphite using cellulose nanocrystals

Stable high-concentration aqueous dispersions (>1 mg ml⁻¹) of single and few-layer graphene flakes were produced by direct exfoliation of graphite using cellulose nanocrystals (CNC). Biodegradable and widely available from renewable sources, CNC have proven to be very efficient graphene stabilizers even at low concentrations (0.2 mg ml⁻¹), thus enabling remarkably high graphene/CNC ratios (up to 3.8).     

High-yield graphene exfoliation using sodium dodecyl sulfate accompanied by alcohols as surface-tension-reducing agents in aqueous solution

The exfoliation of graphite was investigated in aqueous solutions containing sodium dodecyl sulfate (SDS) as a surfactant. The exfoliation was greatly enhanced near the surface aggregation concentration (SAC) of SDS, 2.6 mM, and then decreased for higher SDS contents. However, the flakes exfoliated near the SAC were graphite, whereas graphene was obtained above the critical micelle concentration (CMC). The effect of the use of alcohols as surface-tension-reducing agents (STRAs) on the exfoliation was then investigated. With ethyl alcohol, a dispersion of 2.1 mg ml⁻¹ graphene was achieved from 2.6 mM SDS after only 1 h of sonication, whereas a dispersion of 0.2 mg ml⁻¹ was obtained above the CMC in the absence of STRAs. The results demonstrate that the SDS content near the SAC is highly beneficial for exfoliation as long as the surface tension is maintained near 41.0 mN ml⁻¹. This finding supports the notion that the structure of the adsorbed SDS, depending on its concentration, strongly affects the exfoliation of graphite into graphene.     

Aqueous slurry of S-doped carbon nanotubes as conductive additive for lithium ion batteries

S-doped carbon nanotubes (SCNTs) obtained by a post treatment approach are used as conductive additive for LiFePO₄ (LFP) cathodes in Lithium ion batteries (LIBs). The SCNTs exhibit higher specific surface area, higher conductivity and better hydrophily as compared to the pristine CNTs because of S doping. Thus the SCNTs can be stably dispersed in water, forming an aqueous conductive slurry. The LFP cathode using the aqueous SCNTs slurry as conductive additive exhibits excellent electrochemical performances in terms of capacity (143 mA h g⁻¹ at 2 C), rate capability and cycling stability (99.6% of initial capacity after 200 cycles) due to the uniform dispersibility of SCNTs in the bulk of electrodes forming a continuous conductive network. The full cell configuration with graphite as anode, affords a high reversible capability (150 mA h g⁻¹ at 0.2 C), good cycling stability (capacity retention of 87.6% at 2 C), ultrahigh energy density of 163.7 W h kg⁻¹ and power density of 296.8 W kg⁻¹. Our results provide an easy approach to prepare high performance LIB cathodes using water as solvent, thus leading to lower cost and more secure for the electrode production.     

Improved electrochemical performances of reduced graphene oxide based supercapacitor using redox additive electrolyte

Reduced graphene oxide (rGO) is prepared by simple and eco-friendly hydrothermal reduction method. X-ray photoelectron spectroscopy and Ultraviolet–visible analysis corroborated the reduction of graphene oxide into rGO in basic medium. The flexibility of the prepared rGO is inferred from transmission electron micrographs. Further, the identification of suitable electrolyte is carried out using different anions (SO₄²⁻, Cl⁻, OH⁻) and cations (K⁺, Na⁺) for the superior performance of the rGO based supercapacitors. The electrochemical performance revealed that K⁺ and OH⁻ ions are more active species in aqueous solutions. Subsequently, an effort was taken to improve the specific capacitance in the optimized 1 M KOH electrolyte by KI as redox additive at different concentrations (0.025, 0.05, 0.075 and 0.1 M). The calculated specific capacitance and energy density of rGO electrode in the optimized 1 M KOH + 0.05 M KI electrolyte is 500 F g⁻¹ and 44 Wh kg⁻¹, respectively. On the other hand, it exhibited the specific capacitance of 298 F g⁻¹ at 0.83 A g⁻¹ in non-aqueous polymer gel (PVA + KOH + KI) electrolyte. Finally, the charged aqueous device is utilized to glow the light emitting diode.