Tailoring the capability of carbon nitride (C3N) nanosheets toward hydrogen storage upon light transition metal decoration.

To nurture the full potential of hydrogen (H2) as a clean energy carrier, its efficient storage under ambient conditions is of great importance. Owing to the potential of material-based H2 storage as a promising option, we have employed here first principles density functional theory calculations to study the H2 storage properties of recently synthesized C3N monolayers. Despite possessing fascinating structural and mechanical properties C3N monolayers weakly bind H2 molecules. However, our van der Waals corrected simulations revealed that the binding properties of H2 on C3N could be enhanced considerably by suitable Sc and Ti doping. The stabilities of Sc and Ti dopants on a C3N surface has been verified by means of reaction barrier calculations and ab initio molecular dynamics simulations. Upon doping with C3N, the existence of partial positive charges on both Sc and Ti causes multiple H2 molecules to bind to the dopants through electrostatic interactions with adsorption energies that are within an ideal range. A drastically high H2 storage capacity of 9.0 wt% could be achieved with two-sided Sc/Ti doping that ensures the promise of C3N as a high-capacity H2 storage material.

Oxidation behaviour of U3Si2: an experimental and first principles investigation.

Uranium-containing metallic systems such as U3Si2 are potential Accident Tolerant Fuels (ATFs) for Light Water Reactors (LWRs) and the next generation of nuclear reactors. Their oxidation behaviour, especially in oxygen and water-enriched environments, plays a critical role in determining their applicability in commercial reactors. In this work, we have investigated the oxidation behaviour of U3Si2 experimentally and by theoretical computation. The appearance of oxide signatures has been established from X-ray diffraction (XRD) and Raman spectroscopic techniques after oxidation of the solid U3Si2 sample in synthetic air (oxygen and nitrogen). We have also studied the changes in the electronic structure as well as the energetics of oxygen interactions on the U3Si2 surfaces using first principles calculations in the Density Functional Theory (DFT) formalism. The detailed charge transfer and bond length analyses revealed the preferential formation of mixed oxides of UO2 and SiO2 on the U3Si2{001} surface as well as UO2 alone on the U3Si2{110} and {111} surfaces. The formation of the peroxo (O22-) state confirmed the dissociation of molecular oxygen before U3Si2 oxidation. Core experimental analyses of the oxidized U3Si2 samples have revealed the formation of higher oxides from Raman spectroscopy and XRD techniques. This work is introduced to further a better understanding of the oxidation of U-Si metallic fuel compounds.

A Comparative Density Functional Theory Study of Hydrogen Storage in Cellulose and Chitosan Functionalized by Transition Metals (Ti, Mg, and Nb).

The focus of this work is hydrogen storage in pristine cellulose, chitosan, and cellulose. Chitosan doped with magnesium, titanium, and niobium is analyzed using spin unrestricted plane-wave density functional theory implemented in the Dmol3 module. The results of this study demonstrate that hydrogen interaction with pure cellulose and chitosan occurred in the gas phase, with an adsorption energy of Eb = 0.095 eV and 0.090 eV for cellulose and chitosan, respectively. Additionally, their chemical stability was determined as Eb= 4.63 eV and Eb = 4.720 eV for pure cellulose and chitosan, respectively, by evaluating their band gap. Furthermore, the presence of magnesium, titanium, and niobium on cellulose and chitosan implied the transfer of an electron from metal to cellulose and chitosan. Moreover, our calculations predict that cellulose doped with niobium is the most favorable medium where 6H2 molecules are stored compared with molecules stored in niobium-doped chitosan with Tmax = 818 K to release all H2 molecules. Furthermore, our findings showed that titanium-doped cellulose has a storage capacity of five H2 molecules, compared to a storage capacity of four H2 molecules in titanium-doped chitosan. However, magnesium-doped cellulose and chitosan have insufficient hydrogen storage capacity, with only two H2 molecules physisorbed in the gas phase. These results suggest that niobium-doped cellulose and chitosan may play a crucial role in the search for efficient and inexpensive hydrogen storage media.

Abnormal texture evolution of accumulative roll bonded Al-Cu by adding alumina particles.

Evolution of the texture of an Al-Cu composite after addition of alumina particles was investigated in details using X-Ray Diffraction (XRD) method. Composite samples were produced by the Accumulative Roll Bonding (ARB) and alumina particles were uniformly added to the composite using anodizing technique. The process was accompanied by cutting, stacking and rolling the lamellar materials up to seven times. In early stage of ARB, a shear texture close to the Rotated Cube formed for the Al side. This texture development was also confirmed by microstructural investigation on shear bands during deformation employing optical and scanning electron microscopy. In the last two cycles, a nearly random orientation of grains was developed. For the Cu side, however, the recrystallized Cube texture component was prominent for early ARB cycles due to the recrystallization phenomenon. Moreover, a mixture of rolling and recrystallized texture was detected for the Cu side at higher ARB cycles. Furthermore, evaluation of the grain boundaries showed an increase in the number of high angle grain boundaries for the final ARB cycles in both Al and Cu sides, confirming the occurrence of grain refinement during ARB. Localized particle deformation zone (PDZ) around alumina particles was also proposed to have a contribution to textural evolution of the composite.

Effect of silylating agents on the superhydrophobic and self-cleaning properties of siloxane/polydimethylsiloxane nanocomposite coatings on cellulosic fabric filters for oil-water separation.

A new facile approach for preparing two nonfluorinated hybrid organic-inorganic siloxane/polydimethylsiloxane nanocomposite coatings for cotton fabrics is presented using two distinct silylating agents. The first coated fabric was prepared predominantly via trimethylsilyl modification using hexamethyldisilazane (HMDS) while higher amounts of trimethoxy(octadecyl)silane (TMOS) further enhanced the superhydrophobicity of the second coating matrix. Unlike HMDS with substituted silyl (Me3Si) groups, TMOS consists of hydrolysable trimethoxy silyl ((MeO)3Si) chemical groups that allowed for the formation of nanosilica with Si-O-Si linkages needed to foster stable coatings. After characterization and testing, these coated fabrics demonstrated varying responses to harsh solvents and thermal conditions. Both sets of coated fabrics exhibited unique capacities for self-cleaning and oil-water separation as superhydrophobic filters due to (a) their low surface energy silylated hybrid polysiloxane chemical groups, (b) their highly reduced surface wettability and (c) nanopatterned surface morphologies. In this study, coated superhydrophobic cotton fabrics revealed a higher static aqueous contact angle of more than 150° and sliding hysteresis angle of less than 5°. Coated fabrics with 30 mg TMOS/10 mg HMDS (CMF3) and 30 mg HMDS/10 mg TMOS (CTF3) exhibited optimal superhydrophobicity. Both fabrics also retained percentage separation efficiencies over 90% for both chloroform-water and toluene-water mixtures. However, CTF3 displayed with a recorded separation efficiency less than 90° after five filtration cycles.

In vitro corrosion studies of stainless-steel dental substrates during Porphyromonas gingivalis biofilm growth in artificial saliva solutions: providing insights into the role of resident oral bacterium.

Stainless-steel AISI 321 is an effective material for fabricating dental crowns and other implants utilized dental restorative protocols for elderly and pediatric populations. This unique clinical application is possible through the mechanical stability and corrosion-resistance properties of this metallic material. However, stainless-steel dental implants eventually fail, leading to the creation of surface cavities and cracks within their microstructures during persistent mechanical stresses and biocorrosion. In this study, the in vitro corrosion behaviour of a medical-grade stainless-steel dental substrate was investigated during Porphyromonas gingivalis biofilm growth process in artificial saliva culture suspension (ASCS). Among the causative bioagents of corrosion, P. gingivalis was chosen for this study since it is also responsible for oral periodontitis and a major contributing factor to corrosion in most dental implants. Increased P. gingivalis growth was observed within the incubation period under study as compact cellular clusters fouled the metal surfaces in ASCS media. This led to the corrosion of steel substrates after bacterial growth maturity within 90 days. Corrosion rate increased with higher CFU and bacterial incubation period for all test substrates due to biocorrosion incited by the volatile sulphide products of P. gingivalis metabolism. The presence of some of these volatile compounds has been observed from experimental evidences. Significant anodic degradation in the forms of localized pitting were also recorded by surface analytical techniques. Residual fluorinated ions within the ASCS media also increased the rate of anodic dissolution due to media acidity. This study has provided extensive insights into the fate of stainless-steel dental crown in oral environments infected by a resident oral bacterium. Influences of oral conditions similar to fluoride-enriched mouthwashes were reflected in a view to understanding the corrosion patterns of stainless-steel dental substrates.

Accelerated corrosion of pipeline steel in the presence of Desulfovibrio desulfuricans biofilm due to carbon source deprivation in CO2 saturated medium.

The chemistry of bacterial biofilms as well as the nutritional composition of culture environments may differ at any time within a growth process, especially for SRB consortia within oil wells with limited carbon sources. In the oilfield, the presence of SRB biofilms on surfaces of steel substrates leads to microbiologically influenced corrosion and compromised material integrity. In this work, the survival of SRB cells and their impact on the pipeline steel corrosion within simulated CO2-saturated oilfield-produced water with different concentrations of organic carbon source have been investigated. Cell counts reduced with the level of carbon source reduction (CSR) after incubation but more sessile cells survived at 80% CSR (moderate carbon starvation) compared to 100% CSR (extreme carbon starvation). The energy needed for cellular survival as well as biological support toward MIC could have been harnessed by a combination of extracellular Feo oxidation and intracellular sulfate reduction even after carbon source starvation. Severe anodic steel dissolution was observed at the end of the culture period within the simulated CO2-saturated oilfield-produced water, and this is attributed to SRB-led MIC and CO2 corrosion. Pipeline steel corroded more when cultured within 80% CSR compared to the medium with both lactate and citrate. Steel substrate corroded less with 100% CSR due to severely weakened SRB biofilms from nutrient deprivation.

DFT + U Study of the Adsorption and Dissociation of Water on Clean, Defective, and Oxygen-Covered U3Si2{001}, {110}, and {111} Surfaces.

The interfacial interaction of U3Si2 with water leads to corrosion of nuclear fuels, which affects various processes in the nuclear fuel cycle. However, the mechanism and molecular-level insights into the early oxidation process of U3Si2 surfaces in the presence of water and oxygen are not fully understood. In this work, we present Hubbard-corrected density functional theory (DFT + U) calculations of the adsorption behavior of water on the low Miller indices of the pristine and defective surfaces as well as water dissociation and accompanied H2 formation mechanisms. The adsorption strength decreases in the order U3Si2{001} > U3Si2{110} > U3Si2{111} for both molecular and dissociative H2O adsorption. Consistent with the superior reactivity, dissociative water adsorption is most stable. We also explored the adsorption of H2O on the oxygen-covered U3Si2 surface and showed that the preadsorbed oxygen could activate the OH bond and speed up the dissociation of H2O. Generally, we found that during adsorption on the oxygen-covered, defective surface, multiple water molecules are thermodynamically more stable on the surface than the water monomer on the pristine surface. Mixed molecular and dissociative water adsorption modes are also noted to be stable on the {111} surface, whereas fully dissociative water adsorption is most stable on the {110} and {001} surfaces.

Atomistic and experimental study on thermal conductivity of bulk and porous cerium dioxide.

Cerium dioxide (CeO2) is a surrogate material for traditional nuclear fuels and an essential material for a wide variety of industrial applications both in its bulk and nanometer length scale. Despite this fact, the underlying physics of thermal conductivity (kL), a crucial design parameter in industrial applications, has not received enough attention. In this article, a systematic investigation of the phonon transport properties was performed using ab initio calculations unified with the Boltzmann transport equation. An extensive examination of the phonon mode contribution, available three-phonon scattering phase space, mode Grüneisen parameter and mean free path (MFP) distributions were also conducted. To further augment theoretical predictions of the kL, measurements were made on specimens prepared by spark plasma sintering using the laser flash technique. Since the sample porosity plays a vital role in the value of measured kL, the effect of porosity on kL by molecular dynamics (MD) simulations were investigated. Finally, we also determined the nanostructuring effect on the thermal properties of CeO2. Since CeO2 films find application in various industries, the dependence of thickness on the in-plane and cross-plane kL for an infinite CeO2 thin film was also reported.

Ultrasound-assisted synthesis of zinc molybdate nanocrystals and molybdate-doped epoxy/PDMS nanocomposite coatings for Mg alloy protection.

Zinc molybdate (ZM) is a safer anticorrosive additive for cooling systems when compared with chromates and lead salts, due to its insolubility in aqueous media. For most molybdate pigments, their molybdate anion (MoO4-2) acts as an anionic inhibitor and its passivation capacity is comparable with chromate anion (CrO4-2). To alleviate the environmental concerns involving chromates-based industrial protective coatings, we have proposed new alternative in this work. We have synthesized ZM nanocrystals via ultrasound-assisted process and encapsulated them within an epoxy/PDMS coating towards corrosion protection. The surface morphology and mechanical properties of these ZM doped epoxy/PDMS nanocomposite coatings is exhaustively discussed to show the effect of ZM content on protective properties. The presence of ZM nanocrystals significantly contributed to the corrosion barrier performance of the coating while the amount of ZM nanocrystals needed to prepare an epoxy coating with optimum barrier performance was established. Beyond 2 wt% ZM concentration, the siloxane-structured epoxy coating network became saturated with ZM pigments. This further broadened inherent pores channels, leading to the percolation of corrosion chloride ions through the coating. SEM evidence has revealed proof of surface delamination on ZM3 coating. A model mechanism of corrosion resistance has been proposed for ZM doped epoxy/PDMS nanocomposite coatings from exhaustive surface morphological investigations and evidence. This coating matrix may have emerging applications in cooling systems as anticorrosive surface paints as well as create an avenue for environmental corrosion remediation.

Cellular and molecular interactions between MC3T3-E1 pre-osteoblasts and nanostructured titanium produced by high-pressure torsion.

Ultra-fine surface features are commonly used to modulate cellular activity on a variety of materials. The continuing challenge for materials in contact with bone is the development of a material with both favorable surface and bulk properties to modulate not only the cell-substrate interactions, but also to ensure the long-term stability of the implant. In a combined approach involving material sciences and cell and molecular biology, the nature and mechanism of cell-substrate interaction, in particular, the molecular machinery controlling cell response to the surface of the nanostructured titanium based material produced by the high pressure torsion (HPT) process is assessed. The degree of pre-osteoblast attachment and rate of growth, which are regulated through the activity and interaction of proteins present in the extracellular matrix and associated with cytoskeleton and focal adhesion, are notably increased on the HPT-processed titanium substrates. The improved cell activity is attributed to the nanostructured feature of these substrates consisting of ultra-fine crystals (<50 nm) and a distinct surface oxide layer which provide higher degree of surface wettability. These findings demonstrate the advantages of HPT-processed titanium over the conventional and coated titanium implants, as both mechanical properties and cellular response are improved.

Study on Temper Embrittlement and Hydrogen Embrittlement of a Hydrogenation Reactor by Small Punch Test.

The study on temper embrittlement and hydrogen embrittlement of a test block from a 3Cr1Mo1/4V hydrogenation reactor after ten years of service was carried out by small punch test (SPT) at different temperatures. The SPT fracture energy Esp (derived from integrating the load-displacement curve) divided by the maximum load (Fm) of SPT was used to fit the Esp/Fm versus-temperature curve to determine the energy transition temperature (Tsp) which corresponded to the ductile-brittle transition temperature of the Charpy impact test. The results indicated that the ratio of Esp/Fm could better represent the energy of transition in SPT compared with Esp. The ductile-to-brittle transition temperature of the four different types of materials was measured using the hydrogen charging test by SPT. These four types of materials included the base metal and the weld metal in the as-received state, and the base metal and the weld metal in the de-embrittled state. The results showed that there was a degree of temper embrittlement in the base metal and the weld metal after ten years of service at 390 °C. The specimens became slightly more brittle but this was not obvious after hydrogen charging. Because the toughness of the material of the hydrogenation reactor was very good, the flat samples of SPT could not characterize the energy transition temperature within the liquid nitrogen temperature. Additionally, there was no synergetic effect of temper embrittlement and hydrogen embrittlement found in 3Cr1Mo1/4V steel.

The significance of crystallographic texture of titanium alloy substrates on pre-osteoblast responses.

The aim of this study is to investigate the effects of grain orientation in polycrystalline materials on cell-substrate interactions. Samples are prepared from rods and sheets of Ti-6Al-4V substrates with predominately two distinct crystallographic orientations. X-ray diffraction analysis indicates that 36% of the surfaces of rod samples consist of (1010) plane, while the predominant orientation in the surface of the sheet samples is (1120) plane (29%). Morphological studies and cell biological experiments including cell attachment, proliferation and differentiation are conducted using MC3T3 pre-osteoblast cells cultured on these two different samples. The number of attached cells on the rod Ti-(1010) samples (70% after 1 h and 50% after 2 h) is higher than on the sheet Ti-(1120) samples. Cell proliferation after 3 days is also significantly higher on the Ti-(1010) samples. Alkaline phosphatase activity, however, shows no significant difference between the two samples. Scanning electron microscopy (SEM) analysis of MC3T3 cells grown on samples with different crystallographic texture demonstrate significant differences in morphology with respect to attachment and growth pattern. This study shows that crystal orientation of the substrate can influence cell responses and, therefore, substrate engineering can be used to improve and control cell-substrate interactions.

Hydrogen Storage Performance in Pd/Graphene Nanocomposites.

We have developed a Pd-graphene nanocomposite for hydrogen storage. The spherically shaped Pd nanoparticles of 5-45 nm in size are homogeneously distributed over the graphene matrix. This new hydrogen storage system has favorable features like desirable hydrogen storage capacity, ambient conditions of hydrogen uptake, and low temperature of hydrogen release. At a hydrogen charging pressure of 50 bar, the material could yield a gravimetric density of 6.7 wt % in the 1% Pd/graphene nanocomposite. As we increased the applied pressure to 60 bar, the hydrogen uptake capacity reached 8.67 wt % in the 1% Pd/graphene nanocomposite and 7.16 wt % in the 5% Pd/graphene nanocomposite. This system allows storage of hydrogen in amounts that exceed the capacity of the gravimetric target announced by the U.S. Department of Energy (DOE).

Synthesis of Ni/Graphene Nanocomposite for Hydrogen Storage.

We have designed a Ni-graphene composite for hydrogen storage with Ni nanoparticles of 10 nm in size, uniformly dispersed over a graphene substrate. This system exhibits attractive features like high gravimetric density, ambient conditions, and low activation temperature for hydrogen release. When charged at room temperature and an atmospheric hydrogen pressure of 1 bar, it could yield a hydrogen capacity of 0.14 wt %. When hydrogen pressure increased to 60 bar, the sorbent had a hydrogen gravimetric density of 1.18 wt %. The hydrogen release could occur at an operating temperature below 150 °C and completes at 250 °C.

Layer-by-Layer Assembly of a Self-Healing Anticorrosion Coating on Magnesium Alloys.

Fabrication of self-healing anticorrosion coatings has attracted attention as it has the ability to extend the service life and prevent the substrate from corrosive attack. However, a coating system with a rapid self-healing ability and an improved corrosion resistance is rarely reported. In this work, we developed a self-healing anticorrosion coating on a magnesium alloy (AZ31). The coating comprises a cerium-based conversion layer, a graphene oxide layer, and a branched poly(ethylene imine) (PEI)/poly(acrylic acid) (PAA) multilayer. We incorporated the graphene oxide as corrosion inhibitors and used the PEI/PAA multilayers to provide the self-healing ability to the coating systems. X-ray diffraction (XRD) and Raman spectroscopy were used to characterize the composition of the multilayers, and scanning electron microscopy (SEM) was used to analyze the surface morphology. The electrochemical impedance spectroscopy (EIS) results illustrate the improved corrosion resistance of the coating. The proposed coating also has a rapid self-healing ability in the presence of water.

Impact of trench aspect ratio on microstructure variation in as-deposited and annealed damascene Cu interconnect lines.

Microstructure variation with trench aspect ratio has been investigated in both as-deposited and annealed damascene Cu interconnect lines using Orientation Imaging Microscopy (OIM). The microstructure was characterized by measuring mean grain size, grain size and grain boundary distribution and grain aspect ratio. Since the lines were highly twinned, the mean grain size was measured both before and after neglecting the presence of Sigma3 boundaries. The mean grain size was higher for the annealed lines compared to as-deposited lines and increased proportionally with decreasing trench aspect ratio in the annealed Cu lines with higher aspect ratio. The distribution of coincident site lattice (CSL) boundaries revealed a higher fraction of Sigma3 boundaries in all the lines; their increase upon annealing in the majority of the specimens was accompanied by a decrease of Sigma9 CSL boundaries. The fraction of CSL boundaries was higher in the lines with higher aspect ratios and increased upon annealing in most of the lines. The role of pitch distance (line spacing) in influencing the mean grain size and CSL boundary distribution was identified. Additionally the microstructure was characterized by measuring the grain boundary misorientation distribution. The grain shape was characterized by measuring the grain aspect ratio. Strain distribution in the lines was examined using the Image Quality (IQ) parameter.

X-ray chemical imaging and the electronic structure of a single nanoplatelet Ni/graphene composite.

Chemical imaging and quantitative analysis of a single graphene nanoplatelet grown with Ni nanoparticles (Ni/graphene) has been performed by scanning transmission X-ray microscopy (STXM). Local electronic and chemical structure of Ni/graphene has been investigated by spatially resolved C, O K-edges and Ni L-edge X-ray absorption near edge structure (XANES) spectroscopy, revealing the covalent anchoring of Ni(0) on graphene. This study facilitates the understanding of the structure modification of host materials for hydrogen storage and offers a better understanding of interaction between Ni particles and graphene.

On the importance of crystallographic texture in the biocompatibility of titanium based substrate.

The role of grain size and crystallographic orientation on the biocompatibility of commercially pure titanium was investigated. Samples, with significant differences in crystallographic texture and average grain size (from 0.4 to 40 µm) were produced by equal channel angular pressing (ECAP) and post deformation annealing. X-ray diffraction and electron back scattered diffraction (EBSD) were used to evaluate differences in texture and microstructural characteristics. The titanium oxide film present on the surface of the samples was analyzed to determine the oxidation state of titanium and the chemical bonds between oxygen and titanium using X-ray photoelectron spectroscopy (XPS). Biocompatibility experiments were conducted using MC3T3 preosteoblast cells. Cell attachment was found to be texture-sensitive, where the number of attached cells was higher on the samples with higher number of (0002) planes exposed to the surface, regardless of the grain size. A relationship was also found between the titanium oxide species formed on the surface and the crystallographic texture underneath. The surface texture consisting of more densely packed basal planes promote the formation of Ti-OH on the surface, which in turn, enhances the cell-substrate interactions. These surface characteristics are deemed responsible for the observed difference in cell attachment behaviour of surfaces with different textures. Finally, it is inferred that texture, rather than the grain size, plays the major role in controlling the surface biocompatibility of biomedical devices fabricated from pure metallic titanium.

Enhancement of biocompatibility of 316LVM stainless steel by cyclic potentiodynamic passivation.

Passivation of stainless steel implants is a common procedure used to increase their biocompatibility. The results presented in this work demonstrate that the electrochemical cyclic potentiodynamic polarization (CPP) of a biomedical grade 316LVM stainless steel surface is a very efficient passivation method that can be used to significantly improve the material's general corrosion resistance and thus its biocompatibility. The influence of a range of experimental parameters on the passivation/corrosion protection efficiency is discussed. The passive film formed on a 316LVM surface by using the CPP method offers a significantly higher general corrosion resistance than the naturally grown passive film. The corresponding relative corrosion protection efficiency measured in saline during a 2-month period was 97% +/- 1%, which demonstrates a very high stability of the CPP-formed passive film. Its high corrosion protection efficiency was confirmed also at temperatures and chloride concentrations well above normal physiological levels. It was also shown that the CPP is a significantly more effective passivation method than some other surface-treatment methods commonly used to passivate biomedical grade stainless steels. In addition, the CPP-passivated 316LVM surface showed an enhanced biocompatibility in terms of preosteoblast (MC3T3) cells attachment. An increased thickness of the CPP-formed passive film and its enrichment with Cr(VI) and oxygen was determined to be the origin of the material's increased general corrosion resistance, whereas the increased surface roughness and surface (Volta) potential were suggested to be the origin of the enhanced preosteoblast cells attachment.