Scalable exfoliation process for highly soluble boron nitride nanoplatelets by hydroxide-assisted ball milling.

The scalable preparation of two-dimensional hexagonal boron nitride (h-BN) is essential for practical applications. Despite intense research in this area, high-yield production of two-dimensional h-BN with large-size and high solubility remains a key challenge. In the present work, we propose a scalable exfoliation process for hydroxyl-functionalized BN nanoplatelets (OH-BNNPs) by a simple ball milling of BN powders in the presence of sodium hydroxide via the synergetic effect of chemical peeling and mechanical shear forces. The hydroxide-assisted ball milling process results in relatively large flakes with an average size of 1.5 µm with little damage to the in-plane structure of the OH-BNNP and high yields of 18%. The resultant OH-BNNP samples can be redispersed in various solvents and form stable dispersions that can be used for multiple purposes. The incorporation of the BNNPs into the polyethylene matrix effectively enhanced the barrier properties of the polyethylene due to increased tortuosity of the diffusion path of the gas molecules. Hydroxide-assisted ball milling process can thus provide simple and efficient approaches to scalable preparation of large-size and highly soluble BNNPs. Moreover, this exfoliation process is not only easily scalable but also applicable to other layered materials.

Effects of Cold Sintering on the Performance of Zeolite 13X as a Consolidated Adsorbent for Cesium.

Cold sintering, a novel low-temperature consolidation technique, has shown promising results in various inorganic materials. However, the application of this technique to nanoporous materials for energy and environmental fields is not yet fully understood. This study investigates the effects of cold sintering on the relative densities, compressive strengths, chemical durabilities, crystal structures, specific surface areas, and adsorption capacities of zeolites. Cold sintering at 200 °C achieved 10 to 20% greater densification than conventional high temperature (700 °C) sintering; however, the original nanoporous structure of dry cold sintered zeolite was not maintained. Introducing liquid agents during the cold sintering process resulted in reduced degradation of the SSA and increased densification. Using NaOH as the liquid agent increased the solubility of elements in zeolite, which promoted chemical mobility and achieved the highest relative density (96.7 ± 2.8%). However, soluble layers between the particles led to fragmentation, making it unsuitable for aqueous applications. Using H2O as the liquid agent resulted in a relative density of 90.4 ± 4.1% while maintaining the nanoporous properties and structural integrity of zeolite under water. The cesium adsorption capacity (19.0 ± 0.1 mg·g-1) was similar to that of conventional zeolite ion exchangers, indicating that cold sintering with H2O was an efficient, economical, and safer alternative to conventional high-temperature consolidation method. Our findings suggest that this cold sintering can be applied to other nanoporous materials, such as metal-organic frameworks and covalent organic frameworks, in separation, catalysis, and adsorption applications.

Bi0-Reduced Graphene Oxide Composites for the Enhanced Capture and Cold Immobilization of Off-Gas Radioactive Iodine.

Radioactive waste management is critical for maintaining the sustainability of nuclear fuel cycles. In this study, we propose a novel bismuth-based reduced graphene oxide (Bi0-rGO) composite for the immobilization of off-gas radioactive iodine. This material synthesized via a solvothermal route exhibited a low surface area (2.96 m2/g) combined with a maximum iodine sorption capacity of 1228 ± 25 mg/g at 200 °C. The iodine sorbent was mixed with Bi2O3 powder and distilled water to fabricate waste matrices, which were cold-sintered at 300 °C under a uniaxial pressure of 500 MPa for 20 min to achieve a relative density of ∼98% and Vickers hardness of 1.3 ± 0.1 GPa. The utilized methodology reduced the iodine leaching rate by approximately 3 orders of magnitude through the formation of a chemically durable iodine-bearing waste form (BiOI). This study demonstrates the high potential of Bi0-rGO as an innovative solution for the immobilization of radioactive waste at relatively low temperatures.

Surface decontamination of protective duplex oxide layers on stainless steel waste using deep eutectic solvents.

The decontamination capabilities of deep eutectic solvents (DESs) formed from choline chloride (ChCl) and p-toluenesulfonic acid monohydrate (PtsA), ChCl:PtsA, under different conditions (hydrated, heated, and agitated) were tested with simulant oxidized stainless steel 304 specimens. Although the leaching rates were satisfactory under all conditions, hydrated and stirred ChCl:PtsA at 60 °C showed the fastest leaching rate of 0.1647 mg/min. Oxidized specimens with an average mass gain of 1.2 ± 1 mg were leached, and their masses were reduced by 558 ± 22 mg after 26 h. These results were understood by improved physical properties of ChCl:PtsA upon hydration. Metal oxide solubility of CoO and NiO increased with water, and those of Cr2O3 and Fe3O4 decreased with hydration. Importantly, the use of choline chloride-based DESs in decontamination applications may significantly reduce the cost of decontamination because these DESs can be mass-produced and their components are both easily obtainable and economical. Also, DESs are biodegradable and eco-friendly. The different speciation of Co and Ni, which bond with Cl-, compared with Fe and Cr, which bond with H2O, illustrated the potential for a metal recovery for secondary liquid waste reduction.

Non-volatile immobilization of iodine by the cold-sintering of iodosodalite.

A cold-sintering process at a very low temperature (300 °C) achieved stable immobilization of simulated radioiodine waste incorporated in sodalite (iodosodalite). The reported sintering temperature was much lower than conventional ceramic waste form processing temperatures (600-1100 °C) and had no effect on the stability of the loaded iodine waste. Excellent iodine retention (>93%) with relative sintered density 91% were achieved by the cold-sintering at 300 °C, respectively. The sintered body exhibited a micro-hardness value of 3.9 ±â€¯0.1 GPa and compressive strength of 198 ±â€¯11 MPa. The seven-day product consistency test found iodine leaching rates on order of the magnitude 10-4 g/m2⋅d. These results are the first example of the low temperature consolidation of iodine-bearing sodalite without using any additional material (e.g. glass, cement, etc.). High retention of the loaded simulated radioiodine without volatilization warrants the cold-sintering process for the environmental-friendly disposal of radioiodine.

Immobilization of radioactive corrosion products by cold sintering of pure hydroxyapatite.

An efficient method for the consolidation of cobalt (Co(II)) adsorbed calcium hydroxyapatite was investigated to develop a simplified route for decontamination of the coolant system of nuclear power plants and direct immobilization of as-spent adsorbent. Calcium hydroxyapatite nano-powder synthesized by a wet precipitation method was used as an adsorbent and 94% Co(II) surrogate removal from simulated water was measured. The as-spent adsorbent was sintered at 200 °C, a temperature significantly lower than conventional sintering temperatures (900-1300 °C) for hydroxyapatite, under a uniaxial pressure of 500 MPa for 10 min. The relative density after the cold sintering was >97% and sintered samples displayed good compressive strength (175 MPa). The normalized leaching rate of the Co(II) was measured as per ASTM-C1285 standard and found to be 2.5 × 10-5 g/m2/day. ANSI/ANS-16.1 test procedure was used to analyze the leachability of the sintered matrices and the measured leaching index value was 6.5. Thus, the use of pure calcium hydroxyapatite nano-powder as adsorbent and its cold sintering offers a mean by which radioactive waste form can be processed in an environment friendly manner.

Efficient immobilization of ionic corrosion products by a silica-hydroxyapatite composite via a cold sintering route.

We have successfully demonstrated a new method of radioactive waste immobilization by hosting a waste-bearing form in another waste matrix. A cold sintering route was used to consolidate a silica-incorporated hydroxyapatite (Si-HAp) composite at 200 °C by applying a uniaxial pressure of 500 MPa for a short holding time of 10 min. The higher relative sintered density of up to 98.0 ± 1.3% was achieved by 25 wt% Si loaded HAp. Results from high resolution X-ray diffraction, micro-hardness, and high resolution scanning electron microscopy confirmed the densification with good mechanical strength (micro-hardness = 2.9 ± 0.3 GPa). For practical applications, two kinds of wastes (25 wt% ionic corrosion product-sorbed EDTA functionalized mesoporous silica and 75 wt% ionic corrosion product-sorbed HAp) were mixed, consolidated and tested. The chemical stability of the solidified composite matrix was positively assessed for low leaching rates of 5.9 × 10-9 to 1.2 × 10-5 g per m2 per day using a standard product consistency test. The consolidated composite can bear compressive stress up to 358 MPa, which is orders of magnitude higher than the waste acceptance criteria of 3.5 MPa. The low process temperature can make this sintering process very powerful for the immobilization of radionuclides with volatility and low boiling point. Such a low temperature solidified matrix hosting various wastes may be a promising path for waste management because of its simplicity, reliability, scalability, cost effectiveness and environmental friendliness.

High-entropy alloy strengthened by in situ formation of entropy-stabilized nano-dispersoids.

A significant increase in compressive yield strength of the Al0.3CoCrFeMnNi high-entropy alloy (HEA) from 979 MPa to 1759 MPa was observed upon the introduction of 3 vol.% Y2O3. The HEAs were processed using spark plasma sintering of mechanically alloyed powders. Transmission electron microscopy and atom probe tomography confirmed the presence of compositionally complex nano-dispersoids in the Y2O3-added HEA. The significant increase in strength can be attributed to the nano-dispersoid strengthening coupled with grain refinement. Therefore, the in-situ formation of the compositionally complex nanoscale dispersoids during the alloy processing could be a novel approach to create entropy-stabilized oxide particles in strengthening of HEAs.

Powder Metallurgy Processing of a WxTaTiVCr High-Entropy Alloy and Its Derivative Alloys for Fusion Material Applications.

The WxTaTiVCr high-entropy alloy with 32at.% of tungsten (W) and its derivative alloys with 42 to 90at.% of W with in-situ TiC were prepared via the mixing of elemental W, Ta, Ti, V and Cr powders followed by spark plasma sintering for the development of reduced-activation alloys for fusion plasma-facing materials. Characterization of the sintered samples revealed a BCC lattice and a multi-phase structure. The selected-area diffraction patterns confirmed the formation of TiC in the high-entropy alloy and its derivative alloys. It revealed the development of C15 (cubic) Laves phases as well in alloys with 71 to 90at.% W. A mechanical examination of the samples revealed a more than twofold improvement in the hardness and strength due to solid-solution strengthening and dispersion strengthening. This study explored the potential of powder metallurgy processing for the fabrication of a high-entropy alloy and other derived compositions with enhanced hardness and strength.

Synthesis of Chemically Ordered Pt3Fe/C Intermetallic Electrocatalysts for Oxygen Reduction Reaction with Enhanced Activity and Durability via a Removable Carbon Coating.

Recently, Pt3M (M = Fe, Ni, Co, Cu, etc.) intermetallic compounds have been highlighted as promising candidates for oxygen reduction reaction (ORR) catalysts. In general, to form those intermetallic compounds, alloy phase nanoparticles are synthesized and then heat-treated at a high temperature. However, nanoparticles easily agglomerate during the heat treatment, resulting in a decrease in electrochemical surface area (ECSA). In this study, we synthesized Pt-Fe alloy nanoparticles and employed carbon coating to protect the nanoparticles from agglomeration during heat treatment. As a result, Pt3Fe L12 structure was obtained without agglomeration of the nanoparticles; the ECSA of Pt-Fe alloy and intermetallic Pt3Fe/C was 37.6 and 33.3 m2 gPt-1, respectively. Pt3Fe/C exhibited excellent mass activity (0.454 A mgPt-1) and stability with superior resistances to nanoparticle agglomeration and iron leaching. Density functional theory (DFT) calculation revealed that, owing to the higher dissolution potential of Fe atoms on the Pt3Fe surface than those on the Pt-Fe alloy, Pt3Fe/C had better stability than Pt-Fe/C. A single cell fabricated with Pt3Fe/C showed higher initial performance and superior durability, compared to that with commercial Pt/C. We suggest that Pt3M chemically ordered electrocatalysts are excellent candidates that may become the most active and durable ORR catalysts available.

Enhanced Electrical Networks of Stretchable Conductors with Small Fraction of Carbon Nanotube/Graphene Hybrid Fillers.

Carbon nanotubes (CNTs) and graphene are known to be good conductive fillers due to their favorable electrical properties and high aspect ratios and have been investigated for application as stretchable composite conductors. A stretchable conducting nanocomposite should have a small fraction of conductive filler material to maintain stretchability. Here we demonstrate enhanced electrical networks of nanocomposites via the use of a CNT-graphene hybrid system using a small mass fraction of conductive filler. The CNT-graphene hybrid system exhibits synergistic effects that prevent agglomeration of CNTs and graphene restacking and reduce contact resistance by formation of 1D(CNT)-2D(graphene) interconnection. These effects resulted in nanocomposite materials formed of multiwalled carbon nanotubes (MWCNTs), thermally reduced graphene (TRG), and polydimethylsiloxane (PDMS), which had a higher electrical conductivity compared with MWCNT/PDMS or TRG/PDMS nanocomposites until specific fraction that is sufficient to form electrical network among conductive fillers. These nanocomposite materials maintained their electrical conductivity when 60% strained.

Enhancement of toughness and wear resistance in boron nitride nanoplatelet (BNNP) reinforced Si3N4 nanocomposites.

Ceramics have superior hardness, strength and corrosion resistance, but are also associated with poor toughness. Here, we propose the boron nitride nanoplatelet (BNNP) as a novel toughening reinforcement component to ceramics with outstanding mechanical properties and high-temperature stability. We used a planetary ball-milling process to exfoliate BNNPs in a scalable manner and functionalizes them with polystyrene sulfonate. Non-covalently functionalized BNNPs were homogeneously dispersed with Si3N4 powders using a surfactant and then consolidated by hot pressing. The fracture toughness of the BNNP/Si3N4 nanocomposite increased by as much as 24.7% with 2 vol.% of BNNPs. Furthermore, BNNPs enhanced strength (9.4%) and the tribological properties (26.7%) of the ceramic matrix. Microstructural analyzes have shown that the toughening mechanisms are combinations of the pull-out, crack bridging, branching and blunting mechanisms.