Oxide nanoparticles in an Al-alloyed oxide dispersion strengthened steel: crystallographic structure and interface with ferrite matrix

Abstract

Oxide nanoparticles are quintessential for ensuring the extraordinary properties of oxide dispersion strengthened (ODS) steels. In this study, the crystallographic structure of oxide nanoparticles, and their interface with the ferritic steel matrix in an Al-alloyed ODS steel, i.e. PM2000, were systematically investigated by high-resolution transmission electron microscopy. The majority of oxide nanoparticles were identified to be orthorhombic YAlO₃. During hot consolidation and extrusion, they develop a coherent interface and a near cuboid-on-cube orientation relationship with the ferrite matrix in the material. After annealing at 1200 °C for 1 h, however, the orientation relationship between the oxide nanoparticles and the matrix becomes arbitrary, and their interface mostly incoherent. Annealing at 1300 °C leads to considerable coarsening of oxide nanoparticles, and a new orientation relationship of pseudo-cube-on-cube between oxide nanoparticles and ferrite matrix develops. The reason for the developing interfaces and orientation relationships between oxide nanoparticles and ferrite matrix under different conditions is discussed.     

Effects of iron oxide nanoparticles on polyvinyl alcohol: interfacial layer and bulk nanocomposites thin film

Iron oxide (α-phase) nanoparticles with coercivity larger than 300 Oe have been fabricated at a mild temperature by an environmentally benign method. The economic sodium chloride has been found to effectively serve as a solid spacer to disperse the iron precursor and to prevent the nanoparticles from agglomeration. Higher ratios of sodium chloride to iron nitrate result in smaller nanoparticles (19 nm for 20:1 and 14 nm for 50:1). The presence of polyvinyl alcohol (PVA) limits the particle growth (15 nm for 20:1 and 13 nm for 50:1) and favors nanoparticle dispersion in polymer matrices. Obvious physicochemical property changes have been observed with PVA attached to the nanoparticle surface. With PVA attached to the nanoparticle surface, the nanoparticles are found not only to increase the PVA cross-linking with an increase in melting temperature but also to enhance the thermal stability of the PVA. The nanoparticles are observed to be uniformly dispersed in the polymer matrix. Scanning electron microscopy (SEM) microstructure also shows an intermediate phase with a strong interaction between the nanoparticles and the polymer matrices, arising from the hydrogen bonding between the PVA and hydroxyl groups on the nanoparticle surface. The addition of nanoparticles favors the cross-linkage of the bulk PVA matrices, resulting in a higher melting temperature, and an enhanced thermal stability of the polymer matrix.     

Synthesis,characterization, conductivity and sensor application study of polypyrrole/silver doped nickel oxide nanocomposites

Conducting polymer composites of polypyrrole (PPy) and silver doped nickel oxide (Ag-NiO) nanocomposites were synthesised by in situ polymerisation of pyrrole with different contents of Ag-NiO nanoparticles. The formation of nanocomposites were studied by Fourier transform infrared (FTIR) and UV–vis spectroscopy, field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and AC and DC conductivity measurements. The sensitivity of ammonia gas through the nanocomposite was analysed with respect to different contents of nanoparticles. Spectroscopic studies showed the shift in the absorption bands of polymer nanocomposite than that of pure PPy indicating the strong interaction between the nanoparticles and polymer chain. FESEM revealed the uniform dispersion of nanoparticles with spherically shaped metal oxide particles in PPy matrix. The XRD pattern indicated a decrease in amorphous domain of PPy with increase in loading of nanoparticles. The higher thermal stability and glass transition temperature of polymer nanocomposites than that of pure PPy were revealed from the TGA and DSC respectively. The dielectric properties, DC and AC conductivity of nanocomposites were much higher than PPy and these electrical properties increases with the loading of nanoparticles. The nanocomposites showed an enhancement in sensitivity towards ammonia gas detection than PPy.     

Improved Dielectric Breakdown Strength of Covalently-Bonded Interface Polymer–Particle Nanocomposites

Interfacial covalent bonding is an effective approach to increase the electrical resistance of a polymer–particle composite to charge flow and dielectric breakdown. A bifunctional tether reagent bonded to an inorganic oxide particle surface assists with particle dispersion within a thermosetting epoxy polymer matrix but then also reacts covalently with the polymer matrix. Bonding the particle surface to the polymer matrix resulted in a composite that maintained the pure polymer glass transition temperature, compared to modified or unmodified particle dispersions that lacked covalent bonding to the polymer matrix, which depressed the polymer glass transition to lower temperatures. The added interfacial control, directly bonding the particle to the polymer matrix, appears to prevent conductive percolation across particle surfaces that results in a reduced Maxwell–Wagner relaxation of the polymer–particle composite and a reduced sensitivity to a dielectric breakdown event. The inclusion of 5 vol% particles of higher permittivity produces a composite of enhanced dielectric constant and, with surface modification to permit surface cross-linking into the polymer, a polymer–particle composite with a Weibull E ₀ dielectric breakdown strength of 25% greater than that of the pure polymer resulted. The estimated energy density for the cross-linked interface composite was improved 260% compared to the polymer alone, 560% better than a polymer–particle composite synthesized using bare particles, and 80% better than a polymer–particle composite utilizing bare particles with a dispersant.     

Polymer-supported metals and metal oxide nanoparticles: synthesis,characterization, and applications

Metal and metal oxide nanoparticles exhibit unique properties in regard to sorption behaviors, magnetic activity, chemical reduction, ligand sequestration among others. To this end, attempts are being continuously made to take advantage of them in multitude of applications including separation, catalysis, environmental remediation, sensing, biomedical applications and others. However, metal and metal oxide nanoparticles lack chemical stability and mechanical strength. They exhibit extremely high pressure drop or head loss in fixed-bed column operation and are not suitable for any flow-through systems. Also, nanoparticles tend to aggregate; this phenomenon reduces their high surface area to volume ratio and subsequently reduces effectiveness. By appropriately dispersing metal and metal oxide nanoparticles into synthetic and naturally occurring polymers, many of the shortcomings can be overcome without compromising the parent properties of the nanoparticles. Furthermore, the appropriate choice of the polymer host with specific functional groups may even lead to the enhancement of the properties of nanoparticles. The synthesis of hybrid materials involves two broad pathways: dispersing the nanoparticles (i) within pre-formed or commercially available polymers; and (ii) during the polymerization process. This review presents a broad coverage of nanoparticles and polymeric/biopolymeric host materials and the resulting properties of the hybrid composites. In addition, the review discusses the role of the Donnan membrane effect exerted by the host functionalized polymer in harnessing the desirable properties of metal and metal oxide nanoparticles for intended applications.     

Mechanically Robust,Electrically Conductive Biocomposite Films Using Antimicrobial Chitosan‐Functionalized Graphenes

An effective way of covalently functionalizing graphene with a chitosan polymer via a nitrene chemistry is demonstrated. The biofunctionalized graphene is prepared by the chemical reduction of graphene oxide using a nitrene chemistry, and then covalently grafting chitosan to the graphene surface. The effectiveness of the biofunctionalized graphene as a reinforcing filler (4 wt%) in a chitosan polymer matrix is verified by the dramatic enhancement of the mechanical properties (breaking stress = 330%, Young's modulus = 243%) and the electrical conductivity (0.3 S m^?1) without much loss in the elongation‐at‐break. The reinforcing effect can be explained by both the homogeneous dispersion of graphene within the matrix and the strong bond arising from the intrinsically intimate contact between the graphene and the matrix. The high antimicrobial activity of the biofunctionalized graphene compared with graphene oxide and chemically reduced graphene may be because of the presence of chitosan polymer on the edges of the graphene. The strong, antimicrobial graphene‐filled composite film can be used for food packaging and for coating various biomedical devices, where bacterial surface colonization is undesirable.     

Polymerizable Ligands as Stabilizers for Nanoparticles

Monomers bearing functional groups that can get chemisorbed on nanoparticles to form polymerizable monolayers have emerged as an interesting class of stabilizer ligands for various nanoparticles. High‐surface coverage, their ability to modify the properties of underlying nanoparticles, capability to form polymers of different molecular weights and possibility to make structural modifications make them attractive for their use as stabilizer ligands for nanoparticles. Both in situ and post‐synthesis grafting methods for attaching polymerizable ligands to nanoparticles are frequently used. The advantage of grafting polymerizable stabilizer on the surface of nanoparticles is that initially the polymerizable molecule acts as a proper stabilizer for the nanoparticles and later their surface polymerization or co‐polymerization with another suitable monomer can be carried out to generate the desired polymer scaffold around the nanoparticles, which ensures the increased stability of the resulting core‐polymerized shell nanoparticles. This review discusses interesting reports from recent literature on grafting of polymerizable ligands and their polymerization on gold, silver, silica, and iron oxide nanoparticles.     

Preparation of cytocompatible luminescent and magnetic nanohybrids based on ZnO, Zn0.95Ni0.05O and core@shell ZnO@Fe2O3 polymer grafted nanoparticles for biomedical imaging

ZnO, Zn_0.95Ni_0.05O and core@shell ZnO@??-Fe₂O₃ nanoparticles (NPs) have been prepared by forced hydrolysis in polyol medium and then coated via the ??grafting from?? approach with poly(sodium-4-styrenesulfonate) and poly(sodium-4-styrenesulfonate?Cco?Csodium methacrylate) in the case of ZnO. The surface-initiated atom transfer radical polymerization occurred from the surface-functionalized NPs with ??-bromoisobutyric acid as initiator. The polymer chains were grown from the surface to yield hybrid NPs with a 1?C3-nm thick organic shell. FT-IR, TGA and electron microscopy evidenced the presence of a polymer layer on the surface of NPs. Magnetic and optical properties of bare and coated NPs have been measured. Eventually, the weak cytotoxicity of coated NPs on human endothelial cell allows considering their potentialities as new tools for nanomedicine and biomedical imaging.     

Particle surface treatment for nanocomposites containing ceramic particles

Polymer matrix composites containing dispersed ceramic nanoparticles were formed by UV activated photopolymerization from the reactive liquid monomer hexanediol-diacrylate (HDODA). The polymer forming reaction proceeds by a free-radical mechanism. In forming polymer composites that contain nanoparticles, dispersing the particles as discrete entities is critical for developing optimum properties. In the as-received condition, ceramic particles are aggregated. They must be dispersed in the monomer but if the particles are not surface treated and stabilized, they rapidly settle out of the suspension. Surface modification of the ceramic allows the particles to be suspended in the organic monomer and stabilizes the dispersion so that the particles will not reagglomerate. In this study silanes were employed as surface modifiers to disperse two nano-particulate ceramics in the HDODA monomer. The ceramic particles used are silicon carbide (SiC) and barium titanate (BaTiO₃). The shapes and sizes of the ceramic particles were established using transmission electron microscopy (TEM). A method for dispersing nanoparticles was developed in which silane-treated particles were stabilized so that they did not settle out of the liquid monomer. An analytical method based on atomic force microscopy (AFM) was used to characterize the particle distribution in the cured composites. Focusing on work with SiC nanoparticles in HDODA as a model system, the process for silane application was advanced so that it successfully yielded composites having no aggregates with particle sizes closely matching those of the neat ceramic particles.     

In situ Radical Copolymerization in Presence of Surface‐Modified TiO2 Nanoparticles: Influence of a Double Modification on Properties of Unsaturated Polyester (UP) Nanocomposites

In the preparation of nanocomposites, there is competition between the dispersion of nanoparticles and the formation of agglomerates. In this study, radical copolymerization of ethyl acrylate and methyl methacrylate initiated by 2,2‐azobis (isobutyro) nitrile (AIBN) was performed, in the presence of titanium oxide (TiO₂) nanoparticles modified in a new approach; a good dispersion of the nanoparticles in the unsaturated polyester (UP) matrix was obtained. The TiO₂ nanoparticles were exposed to 3‐(methacryloxy) propyl trimethoxy silane as the coupling agent. The presence of coupling agent‐grafted TiO₂ nanoparticles in the copolymerization process resulted in the formation of a polymeric layer on the surface of the TiO₂ nanoparticles (doubly modified‐TiO₂). The grafting of coupling agent molecules and consequently copolymer macromolecular chains onto the surface of TiO₂ nanoparticles was investigated using Fourier transform infrared (FTIR) analysis. It found that the formation of an acrylate layer on the surface of nanoparticles was successful. Then, unsaturated polyester (UP)/TiO₂ nanocomposites were prepared. The morphology was studied using transmission electron microscopy (TEM). Mechanical properties and ultraviolet visible (UV/VIS) spectroscopy of various samples, including the doubly modified‐TiO₂ nanoparticles, with different nanoparticle inclusions and the unmodified‐TiO₂ nanoparticles, were also investigated. The results showed the doubly modified‐TiO₂ nanoparticles, compared to those of unmodified‐TiO₂, had better nanoparticle dispersion causing improvement in the mechanical properties and UV shielding.     

Morphological, structural, and magnetic properties of Co nanoparticles in a silicon oxide matrix

We present a morphological, structural, and magnetic characterization of Co nanoparticles (mean diameter of 10.3 ± 1.8 nm) grown using a gas aggregation source and embedded in a silicon oxide matrix by sequential deposition of nanoparticles and silicon oxide. We show that the Co nanoparticles ??soft-land?? on the substrates and suffer a moderate oxidation in contact with the silicon oxide. Despite this moderate oxidation, it is found that, at room temperature, the magnetic volume of the resulting nanoparticles is below the superparamagnetic limit. The results presented in this article are compatible with the presence of an assembly of magnetically independent particles that also display a moderate exchange bias at low temperature.     

A neutron activation study of DNA-Gd nanocrystals

The properties of the cholesteric liquid-crystal dispersion containing deoxyribonucleic acid (DNA) molecules and gadolinium ions are investigated using the neutron activation analysis. The cholesteric structure of the DNA-Gd complex is formed by double-stranded DNA molecules and Gd³⁺ cations in nanoparticles. The DNA concentration in nanoparticles reaches 350 mg/ml. The gadolinium concentration in the DNA-Gd complex is determined using the neutron activation analysis. It is found that the DNA-Gd complex contains approximately 1.5 gadolinium atoms per phosphate group of the DNA molecule. The local gadolinium concentration in the nanoparticle reaches 250 mg/ml.     

Colloidal Core–Satellite Supraparticles via Preprogramed Burst of Nanostructured Micro‐Raspberry Particles

Colloidal molecules, or more general supraparticles, i.e., particles which are themselves assembled of smaller nanoparticles in a defined way, are known to be synthesizable via bottom‐up assembly techniques in colloidal dispersion. The amount of synthesizable particles is mostly limited to milligrams. Herein, a bottom‐up‐programed, triggerable top‐down process is reported to obtain core–satellite supraparticles, i.e., particles composed of a larger core particle surrounded by smaller satellite particles. The key is to prepare a nanostructured, microparticulate powder into which defined burst behavior is preprogramed. Once the system is mechanically triggered, it bursts into well‐defined nanosized core–satellite supraparticles. Scale‐up is easily feasible and several hundred grams per batch can be demonstrated. The product is a ready‐to‐use and flexibly processible powder. Upon simple mixing with a polymer, it disintegrates into the preprogramed core–satellite supraparticles, thus forming a highly sophisticated nanocomposite with the polymer matrix. A pure silica nanoparticle system and a silica–iron oxide nanoparticle hybrid system are presented to demonstrate the versatility of the approach. Enhanced mechanical and unexpected magneto‐optical properties with the particle system are found. The disintegration of the microparticles into individual core–satellite colloidal supraparticles is confirmed via in situ liquid cell transmission electron microscopy.     

Utilization of ultrasonic irradiation as a green and effective strategy to prepare poly(N-vinyl-2-pyrrolidone)/modified nano-copper (II) oxide nanocomposites

The present paper describes the result of investigations into preparation of novel nanocomposites (NCs) based on poly(N-vinyl-2-pyrrolidone) (PVP) as a biocompatible polymer and modified copper (II) oxide nanoparticles (NPs) as a nano-filler. To achieve optimum NCs properties, different ratios of modified copper (II) oxide NPs (3, 5, and 7 wt%) were used to fabricate PVP NCs and also the ultrasonic irradiation was utilized to perform these processes as a fast and effective method. Subsequently, the structure of the obtained nanohybrids was characterized by various techniques. The suitable incorporation between PVP matrix and modified CuO NPs can be seen from the FT-IR spectra. The obtained NCs indicated an efficient thermal improvement in comparison to the pristine polymer. Also, the uniform dispersion of modified CuO NPs in the PVP matrix was detected by FE-SEM and EDX. According to UV absorption spectra, it is clear that these NCs can be used in UV protecting applications.     

Catalyst design using an inverse strategy: From mechanistic studies on inverted model catalysts to applications of oxide-coated metal nanoparticles

Metal-oxide interfaces are of great importance in catalytic applications since each material can provide a distinct functionality that is necessary for efficient catalysis in complex reaction pathways. Moreover, the synergy between two materials can yield properties that exceed the superposition of single sites. While interfaces between metals and metal oxides can play a key role in the reactivity of traditional supported catalysts, significant attention has recently been focused on using “inverted” oxide/metal catalysts to prepare catalytic interfaces with unique properties. In the inverted systems, metal surfaces or nanoparticles are covered by oxide layers ranging from submonolayer patches to continuous films with thickness at the nanometer scale. Inverse catalysts provide an alternative approach for catalyst design that emphasizes control over interfacial sites, including inverted model catalysts that provide an important tool for elucidation of mechanisms of interfacial catalytic reactions and oxide-coated metal nanoparticles that can yield improved stability, activity and selectivity for practical catalysts.This review begins by providing a summary of recent progress in the use of inverted model catalysts in surface science studies, where oxides are usually deposited onto the surface of metal single crystals under ultra-high vacuum conditions. Surface-level studies of inverse systems have yielded key insights into interfacial catalysis and facilitated active site identification for important reactions such as CO oxidation, the water-gas shift reaction, and CO₂ reduction using well-defined model systems, informing strategies for designing improved technical catalysts. We then expand the scope of inverted catalysts, using the “inverse” strategy for preparation of higher-surface area practical catalysts, chiefly through the deposition of metal oxide films or particles onto metal nanoparticles. The synthesis techniques include encapsulation of metal nanoparticles within porous oxide shells to generate core-shell type catalysts using wet chemical techniques, the application of oxide overcoat layers through atomic layer deposition or similar techniques, and spontaneous formation of metal oxide coatings from more conventional catalyst geometries under reaction or pretreatment conditions. Oxide-coated metal nanoparticles have been applied for improvement of catalyst stability, control over transport or binding to active sites, direct modification of the active site structure, and formation of bifunctional sites. Following a survey of recent studies in each of these areas, future directions of inverted catalytic systems are discussed.     

Preparation and optical properties of ZnO@PPEGMA nanoparticles

The poly(poly(ethylene glycol) methyl ether monomethacrylate) (PPEGMA) grafted zinc oxide (ZnO) nanoparticles were successfully prepared via the surface-initiated atom transfer radical polymerizations (ATRP) from the surfaces functionalized ZnO nanoparticles. The 2-bromoisobutyrate (BIB) was immobilized onto the surface of the ZnO nanoparticles through the reaction between 2-bromoisobutyryl bromide (BIBB) and the hydroxyl groups on nanoparticles, serving as the initiator to induce the ATRP of poly(ethylene glycol) monomethacrylate (PEGMA). Well-defined polymer chains were grown from the surfaces to yield hybrid nanoparticles comprised of ZnO cores and PPEGMA polymer shells having multifunctional end groups. The structure and morphology of the nanoparticles were characterized using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), X-ray diffraction (XRD) and transmission electron microscopy (TEM). The optical properties of the nanoparticles were investigated by UV-vis absorption spectroscopy and photoluminescence spectroscopy (PL). The results showed that the dispersion and near-band edge (NBE) emission of ZnO nanoparticles could be improved by the grafted PPEGMA polymer segments.     

Ultrasonic dispersion of inorganic nanoparticles in epoxy resin

The incorporation of nanoscale fillers into a polymer can lead to a considerable improvement of mechanical properties, i.e. stiffness and toughness of a material can be enhanced simultaneously by the insertion of nanofillers. Thereby, the crucial difference between conventional microscale fillers and nanofillers is the high specific surface of the latter. In order that this surface can interact with the matrix material a good dispersion, i.e. a good separation and a homogeneous distribution of the nanoparticles into the polymer, is required. In the present study ultrasonic waves generated by an ultrasonic horn were used to disperse titanium dioxide nanoparticles into epoxy resin. The process parameters, e.g. the ultrasonic amplitude, the dispersion time and the material’s volume, were varied systematically with the aim of achieving an optimum dispersion process. A dispersion model for bead mills was adapted to the ultrasonic process and compared to a second dispersion model in order to find an adequate mathematical expression to correlate the ultrasonic process parameters to the particle sizes in the material and to allow predictions for further experiments.     

Responsible nanotechnology development

Chelated gadolinium ions, e.g., Gd-DTPA, are today used clinically as contrast agents for magnetic resonance imaging (MRI). An attractive alternative contrast agent is composed of gadolinium oxide nanoparticles as they have shown to provide enhanced contrast and, in principle, more straightforward molecular capping possibilities. In this study, we report a new, simple, and polyol-free way of synthesizing 4?C5-nm-sized Gd₂O₃ nanoparticles at room temperature, with high stability and water solubility. The nanoparticles induce high-proton relaxivity compared to Gd-DTPA showing r ₁ and r ₂ values almost as high as those for free Gd³⁺ ions in water. The Gd₂O₃ nanoparticles are capped with acetate and carbonate groups, as shown with infrared spectroscopy, near-edge X-ray absorption spectroscopy, X-ray photoelectron spectroscopy and combined thermogravimetric and mass spectroscopy analysis. Interpretation of infrared spectroscopy data is corroborated by extensive quantum chemical calculations. This nanomaterial is easily prepared and has promising properties to function as a core in a future contrast agent for MRI.     

Quasi-elastic scattering of neutrons by a water dispersion of nanodiamonds

Data on quasi-elastic neutron scattering by a water dispersion of nanodiamonds and a pure water as a supporting system has been analyzed. The observed difference in the quasi-elastic neutron scattering spectra is interpreted using two different approaches developed to date for describing the behavior of a solvent in the cases of low and moderate concentrations of carbon nanoparticles (for example, fullerenes, nanotubes, ultradispersed diamonds). Within the first approach, it is assumed that the influence of dissolved nanoparticles leads to an insignificant change in the properties of the solvent. Within the second approach, the properties of the solvent are assumed to be invariable as compared to those of the pure liquid, except for a narrow boundary region of the order of two to three atomic layers near the surface of nanoparticles, where the properties of the solvent change drastically. The explanation of the effect within the second approach seems to be more reliable despite the apparent complication of the mathematical treatment of the experiment.     

Evaluation of boron industrial solid waste in composite materials

Boron industrial solid waste is used as reinforcement for preparing composite materials. This waste has boron trioxide which holds unique properties may affect the surface or interface of the composite. The prepared composites are characterized in order to determine the dispersion and the structure by means of inverse gas chromatography (IGC), Fourier transform infrared spectroscopy, thermal gravimetric analysis, scanning electron microscopy (SEM) and X-ray diffraction (XRD). There is a strong relation between the dispersion of reinforcement and the properties of newly formed composite. The dispersive component of the surface energies of the composites and components are determined by IGC. This parameter is difficult to measure by other methods and it is related to the wettability and adhesive characters of solid materials. The effect of compounding ratios of reinforcement is also examined. Furthermore, XRD diffractograms and SEM images of composites showed well dispersion. Thermal analysis revealed that the addition of the boron industrial solid waste to the polymer increased the thermal stability of pure polymer. Infrared spectra of the composites indicated that the composites were formed from the waste reinforcement and the polymer matrix.