Detonation Nanodiamond Powder Research Articles

Extrastrong aggregates of detonation nanodiamonds: structure and formation

Commercially available powders of detonation nanodiamond (DND) contain extrastrong 20–120 nm sized aggregates, in an amount sometimes up to 50% by mass sustainable to the conventional methods of deaggregation. It demonstrates the significant inhomogeneity structure of products of detonation synthesis and noticeably reduces the yield of 4.0 − 5.0 nm individual isolated particles obtained from DNDs. The presence of these aggregates is obviously related to the some essential features of detonation synthesis. This work presents the results of studying such extrastrong aggregates from DND powder. In order to determine the structure we applied the heat treatment of samples in vacuum and in air, and the subsequent study using Raman spectroscopy, X-ray diffraction, UV–vis spectroscopy, analysis of specific surface and dynamic light scattering (DLS). As a result, a structural model of extrastrong aggregates is proposed. It is shown that extrastrong aggregates consist notably of relatively large (∼8.0 nm) single crystalline diamond particles bonded by facets and covered by smaller 4.5 − 3.0 nm and less crystalline grains. Our results add the details for description of formation processes of diamond particles and aggregates in detonation synthesis from excessive carbon in the composition of explosives.

Determination of non-combustible impurities in detonation nanodiamond powder

The study of the physicochemical (including adsorption) properties of nanodiamond requires the possibility of reproducible generation of the carbon surface of an individual particle without metal impurities of unknown composition. This kind of surface can be obtained through an additional deep cleaning of a commercially available sample. This article is dedicated to the study of the composition of non-combustible impurities of detonation nanodiamond powder. Using inductively coupled plasma mass spectrometry, iron and titanium were identified as the main metal components of the unburned residue, and the presence of Cr, Ni, Zr, As, and Sb was qualitatively established. The expected composition of the main molecular ions formed on the surface of the unburned residue in the course of laser desorption/ionisation mass spectrometry was presented. Based on the results of mass spectrometry analysis, a method of two-stage chemical treatment of detonation nanodiamond powder was proposed, which allowed reducing the mass fraction of non-combustible impurities during annealing in air from 2.0 to 0.1%.

ЭКСПЕРИМЕНТ ПО НИЗКОТЕМПЕРАТУРНОМУ ОБЛУЧЕНИЮ ПОРОШКА ФТОРИРОВАННЫХ ДЕТОНАЦИОННЫХ НАНОАЛМАЗОВ В РЕАКТОРЕ ВВР-К: УСЛОВИЯ И ПЕРВИЧНАЯ ХАРАКТЕРИЗАЦИЯ ОБРАЗЦОВ

Fluorine-doped detonation nanodiamond (DND) powders are considered as a new class of neutron reflectors and can significantly improve the performance of very cold and ultracold neutron sources, which in turn will lead to new types of experiments at a qualitative level. These improvements are achieved due to such properties of DNDas high diffusion and quasi-mirror reflection. The high reflectivity improves the neutron delivery efficiency and, consequently, the neutron fluxes at neutron facilities. On this basis, fluorinated DNDs are considered as a potential neutron reflector material for the designed very cold and ultracold neutron source at the WWR-K reactor. However, to date, experimental data on the behaviour of fluorinated DND in the neutron field are insufficient, and therefore, in order to study the radiation resistance of DND at the WWR-K reactor, work has been started on their irradiation and further study. For this purpose, an optimal irradiation capsule design was developed and comprehensive calculations were performed to justify the conditions and limits of reactor irradiation. This paper describes the irradiated samples and reactor experiment, the methodology and conditions for irradiating the samples, and the results of their initial characterisation after irradiation.

Effect of diamond seeds size on the adhesion of CVD diamond coatings on WC-Co instrument

In this study, we investigated the effect of the size of diamond seeds on the adhesion of multilayered polycrystalline diamond (PCD) films, grown by microwave plasma-assisted chemical vapor deposition (MPCVD). For that, identical WC-Co substrates were separately seeded by a set of diamond powders with various average particle sizes from water-based suspensions using similar seeding procedures. This investigation included powders with a difference in particle sizes of nearly 3 orders of magnitude: from 5 nm up to 2-4 μm. Seeded substrates were used to grow 8-10 μm thick multilayered PCD films using MPCVD with time-limited cycling injections of N2 gas. The Raman spectra and scanning electron microscopy (SEM) studies showed the similarity of microstructure and phase composition of all grown films, which confirmed that all films were grown in similar conditions. The performed scratch tests revealed sufficient differences in the adhesion of the films seeded with different diamond particles. The PCD film grown on 250-500 nm particles delaminated even before any mechanical investigations. The substrates seeded with 50 nm particles allowed the formation of the stable PCD film, but it started flaking under a load as small as 15 N. The 2-4 μm powder allowed the formation of PCD film with decent adhesion, which had local flaking under scratch test, which can be explained by the inhomogeneity of seeds distribution. Detonation nanodiamond (DND) powders allowed the formation of continuous diamond films with decent adhesion, however, powders with positive zeta potential were superior due to a much lower agglomeration of separate particles.

Enhanced directional extraction of very cold neutrons using a diamond nanoparticle powder reflector.

For more than a decade, detonation nanodiamond (DND) powders have been actively studied as a material for efficient reflectors of very cold neutrons (VCNs) and cold neutrons. In this work, we experimentally demonstrate, for the first time, the possibility of enhanced directional extraction of a VCN beam using a reflector made of fluorinated DND powder. With respect to the theoretical flux calculated from an isotropic source at the bottom of the reflector cavity, the gain in the VCN flux density along the beam axis is ∼10 for the neutron velocities of ∼57 and ∼75m/s. The use of such reflectors for enhanced directional extraction of VCN from neutron sources will make it possible to noticeably increase the neutron fluxes delivered to experiments and expand the scope of VCN applications.

Thermal Conductivity of Detonation Nanodiamond Hydrogels and Hydrosols by Direct Heat Flux Measurements.

The methodology and results of thermal conductivity measurements by the heat-flow technique for the detonation nanodiamond suspension gels, sols, and powders of several brands in the range of nanoparticle concentrations of 2–100% w/w are discussed. The conditions of assessing the thermal conductivity of the fluids and gels (a FOX 50 heat-flow meter) with the reproducibility (relative standard deviation) of 1% are proposed. The maximum increase of 13% was recorded for the nanodiamond gels (140 mg mL−1 or 4% v/v) of the RDDM brand, at 0.687 ± 0.005 W m−1 K−1. The thermal conductivity of the nanodiamond powders is estimated as 0.26 ± 0.03 and 0.35 ± 0.04 W m−1 K−1 for the RUDDM and RDDM brands, respectively. The thermal conductivity for the aqueous pastes containing 26% v/v RUDDM is 0.85 ± 0.04 W m−1 K−1. The dignities, shortcomings, and limitations of this approach are discussed and compared with the determining of the thermal conductivity with photothermal-lens spectrometry.

Effect of Particle Sizes on the Efficiency of Fluorinated Nanodiamond Neutron Reflectors.

Over a decade ago, it was confirmed that detonation nanodiamond (DND) powders reflect very cold neutrons (VCNs) diffusively at any incidence angle and that they reflect cold neutrons quasi-specularly at small incidence angles. In the present publication, we report the results of a study on the effect of particle sizes on the overall efficiency of neutron reflectors made of DNDs. To perform this study, we separated, by centrifugation, the fraction of finer DND nanoparticles (which are referred to as S-DNDs here) from a broad initial size distribution and experimentally and theoretically compared the performance of such a neutron reflector with that from deagglomerated fluorinated DNDs (DF-DNDs). Typical commercially available DNDs with the size of ~4.3 nm are close to the optimum for VCNs with a typical velocity of ~50 m/s, while smaller and larger DNDs are more efficient for faster and slower VCN velocities, respectively. Simulations show that, for a realistic reflector geometry, the replacement of DF-DNDs (a reflector with the best achieved performance) by S-DNDs (with smaller size DNDs) increases the neutron albedo in the velocity range above ~60 m/s. This increase in the albedo results in an increase in the density of faster VCNs in such a reflector cavity of up to ~25% as well as an increase in the upper boundary of the velocities of efficient VCN reflection.

Sintering of Polycrystalline Compacts from Cladded Detonation Nanodiamond Powders

Sintering of Polycrystalline Compacts from Cladded Detonation Nanodiamond Powders

Role of Nanodiamond Grains in the Exfoliation of WS2 Nanosheets and Their Enhanced Hydrogen-Sensing Properties.

Herein, for the first time, a combination of detonation nanodiamond (DND)-tungsten disulfide (WS2) was devised and studied for its selective H2-sensing properties at room temperature. DND-WS2 samples were prepared by a sonication-assisted (van der Waals interaction) liquid-phase exfoliation process in low-boiling solvents with DND as a surfactant. The samples were further hydrothermally treated in an autoclave under high pressure and temperature. The as-prepared samples were separated as two parts named DND-WS2 BH (before hydrothermal) and DND-WS2 AH (after hydrothermal). The exfoliated bilayer to few-layer DND-doped WS2 nanosheets were confirmed by ultraviolet-visible spectra, atomic force microscopy, and transmission electron microscopy studies. It was observed that the DND powder not only acted as a surfactant but also doped and expanded on WS2 nanosheets. The difference between samples BH and AH treatment was further investigated using Raman spectroscopy. The WS2 and DND-WS2 samples on SiO2/Si were fabricated using a sputtered Pd/Ag interdigitated electrode and utilized for H2 gas-sensing measurements. Surprisingly, the DND-WS2 exhibits an ultrahigh sensor response of 72.8% to H2 at 500 ppm when compared to only 9.9% for WS2 alone. Also, the DND-WS2 shows a fast response/recovery time, high selectivity, and stability toward H2 gas. It can be attributed to the correlation of the intergrain phase of DND nanoparticles and WS2 nanosheets, which contributes to the easy transportation of charge carriers when exposed to the air and H2 gas atmosphere. Moreover, it is believed that DND-induced WS2 exfoliation might inspire future synthesis of transition metal dichalcogenides induced by DND in green solvents.

Regulation of nanoporous structure of detonation nanodiamond powders by pressure: SANS study

Nanodiamonds combine unique mechanical, thermodynamic and optical properties of diamond with the peculiarities of colloidal dimensions and wide possibilities of chemical modification of their surface. Of particular practical interest is the presence of a branched porous structure inside detonation nanodiamond agglutinates in powders. Application of moderate (up to 1.5 GPa) static pressures allowed us to separate the contributions to small-angle scattering from micro- and nanosized pores. In continuation of the previous studies, the given research shows the possibilities of controlling the fractal structure of the porous system at the nanoscale by applying static pressure. Thus, the partial pore recombination in the pressure range covered leads to the formation of linear pores, in contrast to the branched system characteristic for the initial industrial samples. This modification can have a wide practical impact associated with the loading of anisotropic additives.

Clustering of Diamond Nanoparticles, Fluorination and Efficiency of Slow Neutron Reflectors.

Neutrons can be an instrument or an object in many fields of research. Major efforts all over the world are devoted to improving the intensity of neutron sources and the efficiency of neutron delivery for experimental installations. In this context, neutron reflectors play a key role because they allow significant improvement of both economy and efficiency. For slow neutrons, Detonation NanoDiamond (DND) powders provide exceptionally good reflecting performance due to the combination of enhanced coherent scattering and low neutron absorption. The enhancement is at maximum when the nanoparticle diameter is close to the neutron wavelength. Therefore, the mean nanoparticle diameter and the diameter distribution are important. In addition, DNDs show clustering, which increases their effective diameters. Here, we report on how breaking agglomerates affects clustering of DNDs and the overall reflector performance. We characterize DNDs using small-angle neutron scattering, X-ray diffraction, scanning and transmission electron microscopy, neutron activation analysis, dynamical light scattering, infra-red light spectroscopy, and others. Based on the results of these tests, we discuss the calculated size distribution of DNDs, the absolute cross-section of neutron scattering, the neutron albedo, and the neutron intensity gain for neutron traps with DND walls.

Sodium storage properties of thin phosphorus-doped graphene layers developed on the surface of nanodiamonds under hot pressing conditions

Phosphorus-doped graphene layers have been formed on the surface of nanodiamond (ND) particles by hot pressing of a mixture of purified detonation ND powder and triphenylphosphine (TPP) at 1000 °C and 100 bar. X-ray photoelectron spectroscopy detected about 1.7 at.% of phosphorus in the product, most of which was in the oxidized form. The same treatment conditions of the ND powder without the addition of TPP resulted in the only partial covering of some ND particles by sp2-hybridized carbon layers. The tests in Na-ion half-cells found that the pure carbon sample can reversibly sustain 42 mAh g−1 at a current density of 0.1 A g−1. For the phosphorus-doped sample, this value increases up to 54 mAh g−1 due to mainly accumulation of sodium at various defects created in the graphitic layers as a result of phosphorus incorporation. Taking into account inertness of inner diamond cores, specific capacity values are 417 mAh g−1 for phosphorus-doped graphene layers and 587 mAh g−1 for non-doped ones.

Cинтез сверхтвердых материалов на основе сфалеритного нитрида бора с применением наночастиц углерода в качестве катализатора фазового превращения

Using modern ideas about the form of the phase diagram of boron nitride, the paper considers thermodynamic parameters and mechanisms of the synthesis of dense phases of boron nitride under equilibrium and nonequilibrium conditions. It has been verified that nanodiamonds, like fullerenes and carbon nanotubes, have catalytic properties and contribute to the solid-state conversion of graphite-like boron nitride to sphalerite modification at high pressures and temperatures. We propose a mechanism for the interaction of nanodiamond under high pressures with the surface of graphite-like boron nitride, which leads to a change in the type of electronic bond in its lattice from sp2 to sp3 with the formation of boron nitride with a wurtzite structure and its subsequent transformation into sphalerite boron nitride by the shear mechanism. The use of carbon-coated nanodiamonds resulted in an increase in the catalytically active centers of phase transformation in boron nitride in comparison with unmodified nanodiamonds, which was manifested in an increase in the content of sphalerite boron nitride in materials obtained under comparable technological synthesis conditions. Modified nanodiamonds also contribute to the intensification of the synthesis of superhard polycrystals as compared to uncoated nanodiamond additives, both due to the diffusion of carbon atoms along the grain boundaries of sphalerite boron nitride and due to the rearrangement of graphite microgroups into a diamond structure and sintering of the obtained diamond blocks with grains of sphalerite boron nitride. The process parameters of obtaining superhard polycrystals based on sphalerite boron nitride with the addition of detonation nanodiamond powders after chemical cleaning and surface modification with non-diamond forms of carbon were found.

Observation of Conducting Structures in Detonation Nanodiamond Powder by Electron Paramagnetic Resonance

We have used electron paramagnetic resonance (EPR) to study high-purity detonation nanodiamond (DND) powders at room temperature. In recording the EPR signal with g factor 2.00247 and line width 0.890 mT, with automatic frequency control locking the frequency of the microwave generator (klystron) to the frequency of the experimental cavity, we observed a change in the shape of the EPR signal from the DND powder due to formation of an anisotropic electrically conducting structure in the powder. The electrical conductivity of the DND sample is apparent in the Dysonian EPR lineshape (strongly asymmetric signal with g factor 2.00146 and line width 0.281 mT) together with an abrupt shift of the baseline at the time of resonant absorption, and in the decrease in the cavity Q due to nonresonant microwave absorption. The observed effect can be explained by transition of the DND powder from a dielectric state to a state with metallic conductivity, due to spin ordering in a preferred direction.

Consolidation of nanocrystals of detonation diamonds at high-pressure high-temperature sintering

The process of consolidation of nanocrystals of detonation nanodiamond (DND) into polycrystalline aggregates during their annealing at high pressures and temperatures (HPHT) was studied. The experiments on HPHT annealing of DND powder were carried out using a high pressure apparatus BARS at 5GPa and 1100, 1200°С. It was established that after HPHT annealing the microhardness of sintered DND samples had a value of 14GPa. It was proposed that HPHT annealing of DNDs leads to deep purification of nanoparticle surface, resulting in formation of strong nanodiamond polycrystalline aggregates. The observed growth can be a result of interaction of neighboring DND nanocrystals along the contact areas that are purified of impurities during the HPHT annealing.

Infrared spectroscopic study to determine thermal resistance of the functionalized surface of a detonation nanodiamond

Infrared spectroscopy was used to analyze detonation nanodiamond powder with surfaces functionalized by fluorine- or oxygen-bearing groups before and after heat treatment in air. Fluorination at T=500°C has a significant effect on the actual condition of the diamond surface. The infrared absorption bands associated with the fluorocarbon groups occur at 1092, 1156, 1248, and 1340 cm−1. We show that heat treatment does not have any qualitative effect on the broad infrared absorption band between 1000 and 1400 cm−1 characterizing the fluorinated surface when the sample is heat treated at temperatures up to 520°C. This can be attributed to the entire surface of the detonation nanodiamond particles being covered by saturated, strong, covalent C–F bonds arising from the use of an element more electronegative than oxygen.

Reinforcement effect of acid modified nanodiamond in epoxy matrix for enhanced mechanical and electromagnetic properties

We applied acid treatment for the surface modification of detonation nanodiamond (DND) powder by minimizing their surface energy to overcome agglomeration and improve dispersion of DNDs. Different concentrations of acid modified DND in 828 epoxy matrix were fabricated to check their mechanical and electromagnetic properties. Mechanical properties were checked in terms of ultimate tensile strength (UTS), toughness, energy to break, percent strain break and Young's modulus while electromagnetic shielding properties were studied in frequency range of 11–17GHz. To analyze electrical and magnetic properties of the nanocomposites, relative permittivity and permeability tests were performed. Excellent interactions among acid modified DND and epoxy resin was observed due to carboxyl and hydroxyl functional groups that results in the formation of efficient load transfer interface, which in turn enhance the mechanical and electromagnetic properties of epoxy nanocomposites. During investigation it was observed that mechanical properties and relative permittivity showed enhancements when, 0.2wt% acid modified DND were used as a nano-filler, while on further increment of modified DND these properties start decreasing. Unlike this, the relative permeability, reflection and transmission loss values were increased with the increase of acid modified DND content.

Improvement of manufacture technology of nanostructured diamond materials with the use of physicochemical nonequilibrium analysis

The thermodynamic conditions for the synthesis of diamond nanomaterials from detonation nanodiamond powders are studied and the technological parameters of the synthesis are determined on the basis of the physicochemical analysis of the constitutional diagram of carbon.

Electrochemistry of Methyl Viologen and Anthraquinonedisulfonate at Diamond and Diamond Powder Electrodes: The Influence of Surface Chemistry

The electrochemical behaviour of methyl viologen and anthraquinonedisulfonate was studied at electrodes produced from differing forms of diamond, including microcrystalline boron doped diamond, boron doped diamond powder and detonation nanodiamond powder. Two types of electrode pretreatment were employed to produce two dissimilar surface terminations: hydrophobic H-terminated and hydrophilic O-terminated. In the case of methyl viologen, it was found that the reduced neutral molecule adsorbed on all three electrodes if they were hydrogen terminated, but not if they were oxygen terminated. For anthraquinonedisulfonate, no adsorption was found on the solid diamond electrode, although again significant adsorption was noted on the powder electrodes, provided they were hydrogen terminated. The reasons underlying these observations are discussed in terms of hydrophobic and electrostatic interactions and the electrode morphology. The work provides information into the likely occurrence of adsorption and concomitant electrode fouling, which may be experienced in electroanalytical applications using solid and powdered forms of diamond.

Modification and Comparative Study of Commercial Nanodiamonds

Detonation nanodiamond powders produced by different manufacturers were surface modified to reduce the amount of surface impurities and impart to the particles a high colloidal stability in aqueous suspensions. Modified DNDs (MDNDs) were separated into fractions and evaluated by the zeta potential, particles size distribution and elemental composition. MDNDs retain colloidal stability after the hydrosols are dried and the resulting powders are resuspended. Sedimentation stability and fraction composition are proposed as parameters for standardization of commercial nanodiamonds.