KOH-activated hollow carbon spheres with surface functionalization for high-capacity and long-cycle-life lithium-selenium batteries.

Lithium-selenium (Li-Se) batteries are considered promising alternatives to lithium-ion batteries due to their higher volumetric capacity and energy density. However, they still face limitations in efficiently utilizing the active selenium. Here, we develop surface-functionalized mesoporous hollow carbon nanospheres as the selenium host. By using KOH activation, the surface of the carbon nanospheres is functionalized with hydroxyl groups, which greatly improve the utilization of selenium and facilitate the conversion of lithium selenides, leading to much higher capacities compared to ZnCl2 activation and untreated carbon nanospheres. Theory and experimental evidence suggest that surface hydroxyl groups can enhance the reduction conversion of polyselenides to selenides and facilitate the oxidation reaction of selenides to elemental selenium. In-situ and ex-situ characterization techniques provided additional confirmation of the hydroxyl groups electrochemical durability in catalyzing selenium conversion. The meticulously engineered Se cathode demonstrates a high specific capacity of 594 mA h g-1 at 0.5C, excellent rate capability of 464 mA h g-1 at 2C, and a stable cycling performance of 500 cycles at 2C with a capacity retention of 84.8 %, corresponding to an ultra-low-capacity decay rate of 0.0144 % per cycle, surpassing many reported lithium-selenium battery technologies.

Graphene oxide-polyamine preprogrammable nanoreactors with sensing capability for corrosion protection of materials.

Corrosion is one of the major issues for sustainable manufacturing globally. The annual global cost of corrosion is US$2.5 trillion (approximately 3.4% of the world's GDP). The traditional ways of corrosion protection (such as barriers or inhibiting) are either not very effective (in the case of barrier protection) or excessively expensive (inhibiting). Here, we demonstrate a concept of nanoreactors, which are able to controllably release or adsorb protons or hydroxides directly on corrosion sites, hence, selectively regulating the corrosion reactions. A single nanoreactor comprises a nanocompartment wrapped around by a pH-sensing membrane represented, respectively, by a halloysite nanotube and a graphene oxide/polyamine envelope. A nanoreactor response is determined by the change of a signaling pH on a given corrosion site. The nanoreactors are self-assembled and suitable for mass-line production. The concept creates sustainable technology for developing smart anticorrosion coatings, which are nontoxic, selective, and inexpensive.

Understanding the role of magnesium stearate in lowering punch sticking propensity of drugs during compression.

The sticking of active pharmaceutical ingredient (API) to the surfaces of compaction tooling, frequently referred to as punch sticking, causes costly downtime or product failures in commercial tablet manufacturing. Magnesium stearate (MgSt) is a common tablet lubricant known to ameliorate the sticking problem, even though there exist exceptions. The mechanism by which MgSt lowers punch sticking propensity (PSP) by covering API surface is sensible but not yet experimentally proven. This work was aimed at elucidating the link between PSP and surface area coverage (SAC) of tablets by MgSt, in relation to some key formulation properties and process parameters, namely MgSt concentration, API loading, API particle size, and mixing conditions. The study was conducted using two model APIs with known high PSPs, tafamidis (TAF) and ertugliflozin-pyroglutamic acid (ERT). Results showed that PSP decreases exponentially with increasing SAC by MgSt. The composition of material stuck to punch face was also explored to better understand the onset of punch sticking and the impact of possible MgSt-effected punch conditioning event.

Magnesium stearate surface coverage on tablets and drug crystals: Insights from SEM-EDS elemental mapping.

Scanning electron microscopy-based energy dispersive X-ray spectroscopy (SEM-EDS) is proposed as a versatile tool for quantifying surface area coverage (SAC) by magnesium stearate (MgSt) on pharmaceutical tablets and particles. Our approach involved fast elemental mapping and subsequent SAC quantitation by image analysis. The study was conducted using a multi-component system, but the particle-level mapping was limited to active pharmaceutical ingredient (API) crystals. For both tablets and API particles, the calculated SAC against MgSt loading afforded a positive linear correlation over the range of MgSt levels examined in this work. On the tablet surface, MgSt was found to be preferentially concentrated at or in the close vicinity of grain boundaries, supporting the idea of compression-driven migration and relocation of MgSt within the tablet. On the particle surface, only discrete aggregates of MgSt were observed, as opposed to the widely accepted phenomenon of the formation of a thin lubricant film around host particles. The selection of proper SEM-EDS operating conditions and the challenges confronted in particle surface mapping are discussed in detail.

Toward understanding in vivo corrosion: Influence of interfacial hydrogen gas build-up on degradation of magnesium alloy implants.

Limited material transport, causing gas cavities formation, is commonly observed during the degradation of magnesium implants, yet its effects on corrosion are not understood. Herein, a bespoke cell was designed, allowing for the incorporation of an additional agarose layer above the corroding magnesium sample. This design replicates the limited material transport in vitro and enables us to understand its influence on corrosion of magnesium alloys. This work investigated the influence of varying thickness of agarose (0-0.9 mm) on the corrosion of Mg-Zn-Zr magnesium alloy maintained at 37°C in phosphate-buffered saline (PBS). The introduction of agarose slowed transport of material away from the corroding magnesium surface, including the evolved hydrogen forming a gas cavity. It has been found that an initial increase in the agarose thickness (or the reduction in material transport) of 0.3 mm leads to an increase in the corrosion rate of the magnesium alloy by 62%. However, with a further increase in agarose thickness from 0.3 to 0.9 mm, the corrosion rate decreases by 37%. This observation has been attributed to the accumulation of, and competition between, chloride and hydroxide ions near the alloy's surface. In the presence of materials barrier, hydrogen measurement is no longer a reliable method for the measurement of corrosion rates. This study underscores the importance of the consideration of limited material transport during the in vitro corrosion tests of biomedical implants.

Experimental Evaluation of the Impact of Rapid Environmental Changes on Stress Distribution in Tablet Coatings.

Drying-induced cracks in tablet coatings are undesirable as they not only affect tablet's appearance, but they may also interfere with its function. While it is well known that tensile stresses in the coating are responsible for coating failures, few have measured the stress in tablet coatings, especially when exposed to rapid environmental changes. In this study, two commercial tablet coatings based on Hydroxy Propyl Methyl Cellulose (HPMC) and Poly Vinyl Alcohol (PVA) are exposed to rapid variations in temperature and humidity to observe the variation in residual stress. Reducing temperature at a fixed humidity or reducing humidity at fixed temperature, both lead to high residual stresses. When both the humidity and temperature were reduced together, the residual stresses were very high causing delamination in the PVA-based film and cracking in the HPMC-based film. The changes in residual stress are almost instantaneous for the HPMC-based film while it is slower for the PVA-based film. The results highlight the importance of environmental conditions on the residual stress in the film and the resulting coating failure.

Impact of Rapid Environmental Changes on Stress Distribution in Tablet Coatings: Simulations.

Immediate-release film coatings, also known as "non-functional" film coating, are applied to core tablets to improve product appearance and swallowability, impart taste-masking properties, improve handling and stability of the dosage form, and reduce exposure to active drug substance for caregivers. The coatings have no measurable impact on bio-performance of the drug product but they protect tablets from negative effects of environment such as humidity, oxidation, and light. The mechanical stability and integrity of tablet coatings are therefore important to maintain drug product quality attributes such as appearance and stability. Therefore, environmental conditions under which these coatings may crack are important to understand so as to prevent their occurrence. In this work, we present a novel computational framework to assess the mechanical integrity of tablet coatings exposed to rapid variations in environmental conditions. We perform detailed stress and strain analysis of tablet coatings on tablet surfaces with debossed regions and identify conditions for cracking. Coatings with both elastic and viscoelastic properties are considered. Rapid changes in environmental temperature and humidity can cause differential expansion/contraction of coating and tablet core resulting in stresses that are higher than those experienced during the drying process in a coater. Debossed regions on the tablet surface with sharp surface curvatures act as stress concentrators that nucleate cracks. Small changes in the design of the debossed regions lead to modest reductions in the peak stress. Stress calculations show that coatings that are well bonded to tablet surface can crack only under very extreme conditions.

Digital twin of a continuous direct compression line for drug product and process design using a hybrid flowsheet modelling approach.

The pharmaceutical industry is continuously overcoming ways to reduce its development times to market and bring new medicines to patients with the highest quality standards faster. This can be achieved with continuous manufacturing and digital design by minimising the amount of active pharmaceutical ingredient (API) needed in drug product design, early project de-risking, and reducing the use of clinical manufacturing equipment, rework, and quality investigations. This paper presents the digital twin of a continuous direct compression line combining first-principles models, residence time distribution (RTD) models obtained from discrete element method (DEM) simulations, science of scale tools and data-driven models from process data in a hybrid flowsheet approach. The flowsheet predicts critical process parameters in the feeders, blender, and tablet press, and critical quality attributes, like tablet composition, weight, thickness, and hardness. It allows the study of the steady state operation in the design space, the impact of operating conditions, material and process parameters, and the dynamic response to disturbances. This is used to de-risk and optimise drug product and process development while reducing the number of experiments. The digital twin also has the potential to guide manufacturing runs and respond to new drug product market approval queries using flowsheet modelling.

Development of a predictive model for gravimetric powder feeding from an API-rich materials properties library.

A model was developed for predicting the feed factor profile of a powder, processed through a gravimetric feeder, as a function of material properties and process parameters. Predictive models proposed in existing literature have often used excipients and active pharmaceutical ingredients (APIs) with good powder flow characteristics in their development. In this work, a material properties library containing a large proportion of APIs, as well as excipients and co-processed blends, was used to build the model and enhance the prediction of feed factor profile for cohesive powders. Gravimetric feeder trials were performed at varying mass flow rates and screw geometries to determine the feed factor profiles. A semi-empirical exponential model, with parameters fmax, fmin, and ß, was then used to fit the experimental feed factor profiles. Bayesian optimisation and Support Vector Regression (SVR) modelling techniques were utilised to optimise and predict the exponential model parameters as a function of material properties. The parameters found to strongly influence the model were particle size, bulk density, FFC and FT4 rheometer parameters. Results showed low prediction errors between the estimated and experimental data. The final model produces good estimations of the feed factor profile and requires minimal powder consumption.

Can Finite Element Method Obtain SVET Current Densities Closer to True Localized Corrosion Rates?

In this paper, the finite element method was used to simulate the response of the scanning vibrating electrode technique (SVET) across an iron-zinc cut-edge sample in order to provide a deeper understanding of the localized corrosion rates measured using SVET. It was found that, if the diffusion layer was neglected, the simulated current density using the Laplace equation fitted the experimental SVET current density perfectly. However, the electrolyte was not perturbed by a vibrating SVET probe in the field, so a diffusion layer existed. Therefore, the SVET current densities obtained from the local conductivity of the electrolyte would likely be more representative of the true corrosion rates than the SVET current densities obtained from the bulk conductivity. To help overcome this difference between natural conditions and those imposed by the SVET experiment, a local electrolyte corrected conductivity SVET (LECC-SVET) current density was introduced, which was obtained by replacing the bulk electrolyte conductivity measured experimentally by the local electrolyte conductivity simulated using the Nernst-Einstein equation. Although the LECC-SVET current density did not fit the experimental SVET current density as perfectly as that obtained from the Laplace equation, it likely represents current densities closer to the true, unperturbed corrosion conditions than the SVET data from the bulk conductivity.

Self-Supported Transition Metal-Based Nanoarrays for Efficient Energy Storage.

Rechargeable batteries and supercapacitors are currently considered as promising electrochemical energy storage (EES) systems to address the energy and environment issues. Self-supported transition metal (Ni, Co, Mn, Mo, Cu, V)-based materials are promising electrodes for EES devices, which offer highly efficient charge transfer kinetics. This review summarizes the latest development of transition metal-based materials with self-supported structures for EES systems. Special focus has been taken on the synthetic methods, the selection of substrates, architectures and chemical compositions of different self-supported nanoarrays in energy storage systems. Finally, the challenges and opportunities of these materials for future development in this field are briefly discussed. We believe that the advancement in self-supported electrode materials would pave the way towards next-generation EES.

Continuous mixing technology: Validation of a DEM model.

Continuous powder mixing is an important technology used in the development and manufacturing of solid oral dosage forms. Since critical quality attributes of the final product greatly depend on the performance of the mixing step, an analysis of such a process using the Discrete Element Method (DEM) is of crucial importance. On one hand, the number of expensive experimental runs can be reduced dramatically. On the other hand, numerical simulations can provide information that is very difficult to obtain experimentally. In order to apply such a simulation technology in product development and to replace experimental runs, an intensive model validation step is required. This paper presents a DEM model of the vertical continuous mixing device termed CMT (continuous mixing technology) and an extensive validation workflow. First, a cohesive contact model was calibrated in two small-scale characterization experiments: a compression test with spring-back and a shear cell test. An improved, quicker calibration procedure utilizing the previously calibrated contact models is presented. The calibration procedure is able to differentiate between the blend properties caused by different API particle sizes in the same formulation. Second, DEM simulations of the CMT were carried out to determine the residence time distribution (RTD) of the material inside the mixer. After that, the predicted RTDs were compared with the results of tracer spike experiments conducted with two blend material properties at two mass throughputs of 15 kg/h and 30 kg/h. Additionally, three hold-up masses (500, 730 and 850 g) and three impeller speeds (400, 440 and 650 rpms) were considered. Finally, both RTD datasets from DEM and tracer experiments were used to predict the damping behavior of incoming feeder fluctuations and the funnel of maximum duration and magnitude of incoming deviations that do not require a control action. The results for both tools in terms of enabling a control strategy (the fluctuation damping and the funnel plot) are in excellent agreement, indicating that DEM simulations are well suited to replace process-scale tracer spike experiments to determine the RTD.

Continuous Mixing Technology: Characterization of a Vertical Mixer Using Residence Time Distribution.

Continuous powder mixing technology (CMT) application during continuous direct compression has emerged as a leading technology used in the development and manufacture of solid oral dosage forms. The critical quality attributes of the final product are heavily dependent on the performance of the mixing step as the quality of mixing directly influences the drug product quality attributes. This study investigates the impact of blend material properties (bulk density, API particle size distribution) and process parameters (process throughput, hold up mass and impeller speed) on the mixing performance. Mixing of the blend was characterized using the Residence Time Distribution (RTD) of the process by trending the outlet stream of the mixer using a near-infrared (NIR) probe after the injection of a small mass of tracer at the inlet stream. The outcomes of this study show that the RTDs of the mixer with throughput ranging between 15 and 30 kg/h; impeller speed ranging between 400 and 600 rpm and hold up mass (HUM) ranging between 500 and 850 g can be described by a series of two ideal Continuous Stirred Tank Reactors (CSTRs) with different volumes, and correspondingly, different mean residence times. It is also observed that the mixing is mainly occurring in the lower chamber of the CMT and the normalized RTDs of the mixer are similar across the range of process conditions and material attributes studied. The results also showed that the formulation blend with different API particle sizes and bulk properties, like bulk density and flowability, provide insignificant impact on the mixing performance. The CMT allows independent selection of target set points for HUM, impeller rotational speed and line throughput and it shows great robustness and flexibility for continuous blending in solid oral dose manufacturing.

A systematic investigation on synergistic electroplating and capacitive removal of Pb2+ from artificial industrial waste water.

A capacitive deionization cell designed with symmetric activated carbon electrodes was demonstrated to be able to successfully reduce wastewater Pb2+ concentrations to below the 5 ppm statuary limited for discharge into public sewers. The investigation found that the removal efficiency shows a maximum of 98% with an initial Pb2+ concentration of 100 ppm under an optimized voltage of 1.3 V. Although the reversibility of the process was poor during the first charge/discharge cycle, in part due to cathodic electrodeposition of lead hydroxycarbonates, this was improved by acidification of the electrolyte and subsequent cycles showed good reversibility. Finally, it was demonstrated that Na+ ions, with 50% removal efficiency and 100% reversibility, do not interfere with either the removal rate of Pb2+ ions or the reversibility of this process, providing a new angle on desalination applications for the system.

Tuning oxygen reduction activity on chromia surface via alloying: a DFT study.

Economical electro-catalysts for the oxygen reduction reaction (ORR) are highly desirable for a range of advance energy storage technologies. Chromium compounds have been suggested as one possible source of non-precious metal based catalysts for oxygen reduction reaction (ORR), especially chromia (Cr2 O3 ) which is the most stable form of Cr oxide at room temperature. Using density functional theory+U calculations, we investigate the 4-electron ORR on the hydroxylated Cr2 O3 surfaces alloyed with 17 different transition metals. On the one hand, we find that the ORR overpotential is lower when the Cr2 O3 surface alloyed with elements towards the end of both the first and second rows of transition metals. Among these elements, Cd alloyed Cr2 O3 surface is found to promote the ORR the most, but due to its high toxicity and price it loses out to Zn as the recommended alloyant. On the other hand, we find that the ORR overpotential is generally higher and less varied on the Cr2 O3 surface alloyed with the early-to-mid row transition metal elements (e. g. Zr, Ti). As Cr2 O3 is also a major component in the passive film on stainless steels, where a low ORR rate is desirable to reduce the impact of localized corrosion. This implies that alloying with early-to-mid row transition elements could be beneficial to stainless steels. The difference in oxygen reduction activity is attributed to the tendency of forming stable ORR intermediates during the oxygen reduction process.

Three Dimensionally Free-Formable Graphene Foam with Designed Structures for Energy and Environmental Applications.

Three-dimensional assemblies of graphene have been considered as promising starting materials for many engineering, energy, and environmental applications due to its desirable mechanical properties, high specific area, and superior thermal and electrical transfer ability. However, little has been done to introduce designed shapes into scalable graphene assemblies. In this work, we show here a combination of conventional graphene growing technique-chemical vapor deposition with additive manufacturing. Such synthesis collaboration enables a hierarchically constructed porous 3D graphene foam with large surface area (994.2 m2/g), excellent conductivity (2.39 S/cm), reliable mechanical properties (E = 239.7 kPa), and tunable surface chemistry that can be used as a strain sensor, catalyst support, and solar steam generator.

Detailed modeling and process design of an advanced continuous powder mixer.

A vertical in-line continuous powder mixing device (CMT - Continuous Mixing Technology) has been modelled with the discrete element method (DEM) utilizing a calibrated cohesive contact model. The vertical design of the mixing device allows independent control of mean residence time (MRT) and shear rate. The hold-up mass and outlet flow are controlled by an exit valve, located at the bottom of the in-line mixer. A virtual design of experiments (DoE) of DEM simulations has been performed and parameters such as particle velocities, powder bed shape, residence time distribution (RTD), travel distance, and mixing quality are evaluated for the complete operating space. The RTD of the DEM model has been validated with tracer experiments. The resulting RTD has been fitted with an analytical form (generalized cascade of n continuous stirred tank reactors) and utilized to study the downstream response of the continuous mixing device to upstream fluctuations in the inlet material stream. The results indicate a high mixing quality and good filtering properties across the operating space. However, the combination of low hold-up mass and high impeller speeds leads to a reduced filtering capability and wider exit valve openings, indicating a less desirable operating point.

Quantifying and reducing powder shear sensitivity when manufacturing capsules with lubricants.

The purpose of this work was to develop a methodology that quantifies the extent of shear induced during an encapsulation process and show how formulation composition and manufacturing process designs can be changed to reduce the negative impact on drug product quality attributes. The powder feed system used in a dosing disc type pharmaceutical capsule filling machine induced additional shear of the powder prior to slug formation. The shear occurred both in the hopper portion, via the rotation of the feed auger and impeller, and in the powder bowl via the tamping pin agitation and/or shear against the stationary surfaces such as the powder level scraper. The extent of shear was quantified to assess the impact of further dispersing the hydrophobic lubricant, magnesium stearate, in both active and placebo formulations. Stratified samples over the course of the encapsulation run showed suppression in the drug dissolution profiles and decrease in the interparticulate tensile strength of the encapsulated product. The amount of shear (duration and rate) induced during the encapsulation unit operation can be much greater than that from typical bin blending operations and therefore requires consideration during product design and scale-up to ensure product robustness.

Development of a Nanostructured α-MnO2/Carbon Paper Composite for Removal of Ni2+/Mn2+ Ions by Electrosorption.

Toxic metal ions, such as Ni2+ and Mn2+, in industrial waste streams are nonbiodegradable and can cause damage to the human body. Electrochemical cleaning techniques are attractive as they offer more control and produce less sludge than do chemical/biological approaches without the high pressures needed for membranes. Here, nanoneedle-structured α-MnO2/carbon fiber paper (CFP) composites were synthesized by a hydrothermal approach and used as electrodes for combined electroadsorption and capacitive deionization removal of nickel and manganese ions from pseudoindustrial waste streams. The specific performance of α-MnO2/CFP (16.4 mg Ni2+ per g of active material) not only shows a great improvement in comparison with its original CFP substrate (0.034 Ni2+ mg per g), but also is over 6 times that of activated carbon (2.5 mg Ni2+ per g). The high performance of α-MnO2/CFP composites is attributed to their high surface area, desirable mesoporosity, pore-size distribution that permits the further access of ions, and their property as a pseudocapacitor, which contributes to a more efficient electron/charge transfer in the faradic process. Unfortunately, it was also found that some Mn2+ ions are released due to the partial reduction of MnO2 when operated as a negative electrode. For the removal of Mn2+ ions, an asymmetric arrangement, consisting of a MnO2/CFP positive electrode and an activated carbon negative electrode, was employed. This arrangement reduced the Mn2+ concentration from 100 ppm to less than 2 ppm, a vast improvement over the systematical two-activated carbon electrode system that could only reach 42 ppm under the same conditions. It was also observed that as long as the MnO2/CFP composite was maintained as a positive electrode, it was completely stable. The technique was able to reduce both Ni2+ and Mn2+ ions to well below the 10 ppm requirement for discharge into public sewers in Singapore.