‘Laser chemistry’ synthesis,physicochemical properties,and chemical processing of nanostructured carbon foams

Laser ablation of selected coordination complexes can lead to the production of metal-carbon hybrid materials, whose composition and structure can be tailored by suitably choosing the chemical composition of the irradiated targets. This ‘laser chemistry’ approach, initially applied by our group to the synthesis of P-containing nanostructured carbon foams (NCFs) from triphenylphosphine-based Au and Cu compounds, is broadened in this study to the production of other metal-NCFs and P-free NCFs. Thus, our results show that P-free coordination compounds and commercial organic precursors can act as efficient carbon source for the growth of NCFs. Physicochemical characterization reveals that NCFs are low-density mesoporous materials with relatively low specific surface areas and thermally stable in air up to around 600°C. Moreover, NCFs disperse well in a variety of solvents and can be successfully chemically processed to enable their handling and provide NCF-containing biocomposite fibers by a wet-chemical spinning process. These promising results may open new and interesting avenues toward the use of NCFs for technological applications.     

脉冲激光溅射合成八-(甲基硅倍半氧烷)

以脉冲浙江溅射作用于聚甲基硅氧烷,经真空升华,直接得到了一种产物的单晶。经Ｘ－射线晶体衍射测定确定其为具有（ＣＨ３ＳｉＯ１．５）８组成的硅氧烷。该种产物具有多环立体空间构型。结果表明,在脉冲激光的作用下,反应物的链状结构发生解离,并在等离子体条件下进行结构重组,生成了具有立体空间构型的产物。     

Nanofabrication with metallopolymers ‐ recent developments and future perspectives

Synthetic polymers containing metals and metal centers have experienced rapid growth in the last two decades. Metal‐containing polymers have an unprecedented role to play in modern high‐tech applications including nanomanufacturing, sensing, separation and catalysis. Advancement in synthetic strategies for macromolecules has enabled the synthesis of novel, exotic and use‐inspired metallopolymers. Using state‐of‐the‐art design strategies, it is now possible to perform targeted synthesis of macromolecules with varied complexity that contain a range of metal centers either in the backbone or in the side chains of the organic moiety. The presence of an inorganic element (metals and metal centers) in organic moieties has led to a number of new physicochemical properties while implementing novel functionality to the polymer matrix. This review covers nanotechnology influenced by distinctive features of metal‐containing macromolecular systems, particularly in developing flexible, functional materials. © 2013 Society of Chemical Industry     

One-step synthesis of γ-Fe2O3 nanoparticles by laser ablation

A Nd:YAG pulsed laser was used to ablate a 0.5-mm-diameter iron wire in a sealed chamber in a mixed gas flux of N₂ and O₂ to generate pure γ-Fe₂O₃ nanoparticles at atmospheric pressure. Structural characteristics and sizes of the prepared nanoparticles were determined by X-ray diffraction and TEM. The effects of laser power density, total mixed gas pressure and the oxygen ratio on the mean particle size were investigated, respectively. The results showed that the mean particle size decreased with the increase of the laser power density, total gas pressure and the oxygen ratio, respectively. Besides, the nanoparticle formation mechanism by laser ablation of iron wires was also discussed.     

Fabrication of patterned nanostructures with various metal species on Si wafer surfaces by maskless and electroless process

Maskless and electroless fabrication was demonstrated to form patterned nanostructures of various metal species, based upon the process previously developed by the authors. In this process, the metallic nanostructures were formed on the surface of clean, hydrogen terminated p-(1 0 0) Si wafer with pre-patterned nanoscopic defects, which were confirmed to possess higher activity for the reductive deposition reaction of the metal ion species. The deposition was achieved spontaneously and selectively at the defect sites on the wafer surface by immersing into dilute aqueous fluoride solution containing trace amount of metal ion species. By optimizing the formation condition of the patterned defects and composition of the solution, fabrication of patterned nanostructures of various metallic species such as Au, Ag, and Co, was achieved. Formation of the patterned nanostructures to 10 μm² in extent, as well as control of the feature size of the deposits by adjusting the formation condition of the patterned defects were also attempted.     

Growth of arrays of oriented epitaxial platinum nanoparticles with controlled size and shape by natural colloidal lithography

We developed a method for production of arrays of platinum nanocrystals of controlled size and shape using templates from ordered silica bead monolayers. Silica beads with nominal sizes of 150 and 450 nm were self-assembled into monolayers over strontium titanate single crystal substrates. The monolayers were used as shadow masks for platinum metal deposition on the substrate using the three-step evaporation technique. Produced arrays of epitaxial platinum islands were transformed into nanocrystals by annealing in a quartz tube in nitrogen flow. The shape of particles is determined by the substrate crystallography, while the size of the particles and their spacing are controlled by the size of the silica beads in the monolayer mask. As a proof of concept, arrays of platinum nanocrystals of cubooctahedral shape were prepared on (100) strontium titanate substrates. The nanocrystal arrays were characterized by atomic force microscopy, scanning electron microscopy, and synchrotron X-ray diffraction techniques.     

Plasmonic Core–Shell–Satellites with Abundant Electromagnetic Hotspots for Highly Sensitive and Reproducible SERS Detection

In this work, we develop a Ag@Al₂O₃@Ag plasmonic core–shell–satellite (PCSS) to achieve highly sensitive and reproducible surface-enhanced Raman spectroscopy (SERS) detection of probe molecules. To fabricate PCSS nanostructures, we employ a simple hierarchical dewetting process of Ag films coupled with an atomic layer deposition (ALD) method for the Al₂O₃ shell. Compared to bare Ag nanoparticles, several advantages of fabricating PCSS nanostructures are discovered, including high surface roughness, high density of nanogaps between Ag core and Ag satellites, and nanogaps between adjacent Ag satellites. Finite-difference time-domain (FDTD) simulations of the PCSS nanostructure confirm an enhancement in the electromagnetic field intensity (hotspots) in the nanogap between the Ag core and the satellite generated by the Al₂O₃ shell, due to the strong core–satellite plasmonic coupling. The as-prepared PCSS-based SERS substrate demonstrates an enhancement factor (EF) of 1.7 × 10⁷ and relative standard deviation (RSD) of ~7%, endowing our SERS platform with highly sensitive and reproducible detection of R6G molecules. We think that this method provides a simple approach for the fabrication of PCSS by a solid-state technique and a basis for developing a highly SERS-active substrate for practical applications.     

Design and preparation of composite coatings with increased reflectivity under high-energy continuous wave laser ablation

High-energy continuous wave (CW) laser ablation can cause severe damage to structural materials in an extremely short time, which generates considerable concern in terms of material safety. For the purpose of reducing or even eliminating such laser-induced damage, a novel composite coating consisting of a boron-modified phenolic formaldehyde resin incorporating ZrC and SiC has been designed and prepared. The experimental results reveal that ZrC and SiC are rapidly oxidized to ZrO₂ and SiO₂ respectively, leading to the formation of a white ceramic layer consisting of ZrO₂ particles and melted SiO₂. After ablation at 1000 W/cm² for 50 s, elemental analysis indicates that no Si can be found in the central ablation zone because of gasification. A relatively compact ZrO₂ layer is formed through the sintering of adjacent ZrO₂ particles, which effectively improves the reflectivity of the coating from 7.3% (before ablation) to 63.5% (after ablation). The high reflectivity greatly reduces the absorption of laser energy. In addition, no obvious ablation defects are observed in the composite coating. The excellent anti-laser ablation performance of the coating makes it a promising system for protecting a material against the effects of long-term CW laser ablation.     

Study of nanostructure growth with nanoscale apex induced by femtosecond laser irradiation at megahertz repetition rate

Leaf-like nanostructures with nanoscale apex are induced on dielectric target surfaces by high-repetition-rate femtosecond laser irradiation in ambient conditions. We have recently developed this unique technique to grow leaf-like nanostructures with such interesting geometry without the use of any catalyst. It was found to be possible only in the presence of background nitrogen gas flow. In this synthesis method, the target serves as the source for building material as well as the substrate upon which these nanostructures can grow. In our investigation, it was found that there are three possible kinds of nanotips that can grow on target surfaces. In this report, we have presented the study of the growth mechanisms of such leaf-like nanostructures under various conditions such as different laser pulse widths, pulse repetition rates, dwell times, and laser polarizations. We observed a clear transformation in the kind of nanotips that grew for the given laser conditions.     

Effects of irradiation energy and nanoparticle concentrations on the structure and morphology of laser sintered magnesia with alumina and iron oxide nanoparticles

The laser sintering mechanism of composites based on magnesia and oxide nanoparticles was studied in terms of nanoparticle concentration and laser energy fluence. Iron oxide and aluminum oxide nanoparticles were mechanically mixed with magnesia (MgO) powder (5, 7 and 10 wt%) and the compacted pellets were irradiated with the fundamental output (1064 nm) of a pulsed Nd:YAG laser at 2.5 and 3.0 J/cm². Crystal structure, elemental composition and morphology were characterized by X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy. X-ray diffraction results confirmed the crystalline phases and spinel formation by addition of oxide nanoparticles and laser sintering. X-ray photoelectron spectroscopy analysis confirmed their surface composition and chemical states of the corresponding elements. Morphological changes were observed due to the laser fluence and the oxide nanoparticle concentrations. Results show that a coarsening mechanism was predominant with a high energy fluence and concentration of oxide nanoparticles.     

A Novel Strategy for the Controlled Synthesis of Silver Halide/Polyaniline Nanocomposites with Different Polyaniline Morphologies

Silver halide/polyaniline nanocomposites with different polyaniline morphologies, i.e., nanotubes and nanofibers, were successfully synthesized simply based on the general chemical oxidation polymerization process of aniline in halide acid aqueous solution (i.e., HCl or HBr) with the presence of dodecylbenzenesulfonic acid (DBSA)‐stabilized silver nanoparticles (NPs) as the precursors of silver halide NPs (i.e., AgCl or AgBr). X‐ray diffraction (XRD) and FT‐IR results confirmed the structures of resultant silver halide/polyaniline nanocomposites. TEM and SEM images demonstrated that AgCl or AgBr NPs were well‐dispersed and embedded in the polyaniline matrix. The reasons for the new strategy for the preparation of silver halide/polyaniline nanocomposites were based on two key points: the first was the high reactivity of silver NPs with HCl or HBr to generate AgCl/AgBr NPs. Second, with the assistance of DBSA, polyaniline could be synthesized with various nanostructures, i.e., nanotubes and nanofibers.

     

Additively-manufactured multiphase coatings with laser protection ability for the repairing of MoSi2-SiC/SiC coated C/C composites

The Si-SiC-MoSi₂ and Si-SiC coatings were proposed to repair the damaged MoSi₂-SiC/SiC coated C/C composites by laser directed energy deposition. Laser ablation was used to assess the repair effect. Results showed that both the repaired coatings with dense structure could restore the geometric size of damaged area. Compared with the Si-SiC-MoSi₂ coating, the Si-SiC repaired coating with higher laser reflectivity and more free Si could reduce the heat generation and enhance the heat dissipation during ablation, which lowered the maximum temperature by 347.49 K and 810.77 K under 300 W and 500 W ablation for 7 s separately, beneficial to avoid the secondary laser damage of the repaired area.     

Ablation behavior of C/SiC with YSZ and ZrB2 coatings under high-energy laser irradiation

Carbon fiber-reinforced silicon carbide (C/SiC) composites are important candidates for laser protection materials. In this study, ablation mechanism of C/SiC coated with ZrO₂/Mo and ZrB₂–SiC/ZrO₂/Mo under laser irradiation was studied. ZrB₂–SiC multiphase ceramic and ZrO₂ ceramic were successfully coated on C/SiC composite by atmospheric plasma spraying technology with Mo as transition layer. Phase evolution and morphology of composite were investigated by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Moreover, ablation behavior of the composite was investigated by laser confocal microscopy. Results showed that ablation mechanism of C/SiC composite was controlled by phase transformation, thermal reaction, and thermal diffusion, with solid–liquid transition of ZrB₂ and ZrO₂ being dominant factor. Endothermic reaction and good thermal diffusivity of coatings were also important factors affecting ablation performance. Reflectivity effect of ZrO₂ coating was limited under high-energy laser irradiation. Compared with ZrO₂/Mo single-phase-monolayer coating, designed ZrB₂–SiC/ZrO₂/Mo coating showed better ablation performance, and breakdown time of C/SiC increased from 10 to 40 s. The depletion of liquid phase in molten pool was identified as an important factor responsible for rapid failure of C/SiC. The coating failed when the entire liquid phase was consumed within molten pool, followed by rapid damage of C/SiC substrate. Results of this study can provide theoretical guidance and research ideas for design and application of laser protective materials.     

Tumour Cell Membrane Poration and Ablation by Pulsed Low-Intensity Electric Field with Carbon Nanotubes

Electroporation is a physical method to increase permeabilization of cell membrane by electrical pulses. Carbon nanotubes (CNTs) can potentially act like “lighting rods” or exhibit direct physical force on cell membrane under alternating electromagnetic fields thus reducing the required field strength. A cell poration/ablation system was built for exploring these effects of CNTs in which two-electrode sets were constructed and two perpendicular electric fields could be generated sequentially. By applying this system to breast cancer cells in the presence of multi-walled CNTs (MWCNTs), the effective pulse amplitude was reduced to 50 V/cm (main field)/15 V/cm (alignment field) at the optimized pulse frequency (5 Hz) of 500 pulses. Under these conditions instant cell membrane permeabilization was increased to 38.62%, 2.77-fold higher than that without CNTs. Moreover, we also observed irreversible electroporation occurred under these conditions, such that only 39.23% of the cells were viable 24 h post treatment, in contrast to 87.01% cell viability without presence of CNTs. These results indicate that CNT-enhanced electroporation has the potential for tumour cell ablation by significantly lower electric fields than that in conventional electroporation therapy thus avoiding potential risks associated with the use of high intensity electric pulses.     

Shuttling Gold Nanoparticles into Tumoral Cells with an Amphipathic Proline‐Rich Peptide

Golden bullets : The amphipathic proline‐rich cell‐penetrating peptide sweet arrow peptide (SAP) is able to transport 12 nm gold nanoparticles efficiently into HeLa cells, as observed by three microscopy techniques: transmission electron microscopy (TEM), confocal laser scanning microscopy (CLSM) and transmission X‐ray microscopy (TXM). Multiconjugation to such nanoparticles may provide a convenient method for unifying the key drug properties of high activity, capacity to home onto targets and delivery to therapeutic places of action.

     

Pulsed laser ablation in liquid synthesis of ZnO/TiO2 nanocomposite catalyst with enhanced photovoltaic and photocatalytic performance

In this work, we employed an impurity-free nanoparticle synthesis technique, known as pulsed laser ablation in liquid (PLAL), to integrate titanium dioxide nanoparticles (TiO₂ NPs) into zinc oxide nanorods (ZnO NRs) with varying relative proportions. The main objective of this integration was to enhance the charge carrier separation of photo-generated electron hole pairs during solar irradiation. For the synthesis process, an Nd:YAG laser at 532 nm wavelength was applied as an ablation source, along with deionized water as a solvent medium in which the precursor materials were dispersed prior to laser irradiation. The nanocomposites were characterized by X-ray diffraction (XRD), UV–vis absorption and in-situ Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HR-TEM) and field emission scanning electron microscopy (FE-SEM). The synthesized nanocomposites were primarily utilised in two applications: firstly, as a catalyst in the degradation of methyl orange (MO) and secondly, as photo-anode in dye sensitized solar cell (DSSC). Our research has demonstrated that optimal performance was obtained for the nanocomposite containing 10% and 90% (by weight) TiO₂ NPs and ZnO respectively, which we define as the ideal nanocomposite. Relative to pure ZnO, the photo-conversion efficiency of the ideal composite was improved substantially by 63.73%, whilst the photo-degradation rate was enhanced by 3 fold. The oxidation state and the microstructural of the segregated ideal nanocomposite confirms that oxygen vacancy defects were created when perfect surface integration occurs between TiO₂ and ZnO. Nonetheless, we believe that the performance enhancement is predominantly due to the excellent charge carrier separation and fast interfacial electron flow in this nanocomposite.     

On crack evolution with texturization of bonding layer in thermal barrier coating

The interface morphology of the bonding layer has a considerable effect on the damage and failure of sandwich-structured thermal barrier coatings. This work investigated the comprehensive effects of a grooved texture produced using laser ablation on the local surface strain, interfacial stress and strain, and crack behavior of the bonding layer in a thermal barrier coating system. The distribution and evolution of the local surface strain was obtained using the digital image correlation method. The interfacial stress, and the strain between the ceramic and bonding layers, were determined through a simulation of the plane-strain model, and the morphology and propagation of cracks were observed in thermal barrier coatings under an external tensile load. The results indicated that the local surface strain of the thermal barrier coating increased with the texturization of the bonding layer, whereas the fluctuation decreased. There were two inflection points in the local surface strain–time curves, corresponding to the initiation of surface cracks and that of interfacial transverse cracks. The surface cracks were initiated earlier than those without the texturization of the bonding layer. However, the behavior of the interfacial cracks was more complicated. If the roughness of the texture, defined as Rc, was small, the surface cracks propagated vertically to the interface between the ceramic and bonding layers, and turned into transverse cracks, leading to a separation of the ceramic layer. If Rc was greater than 22 μm, the surface cracks went further down to the interface between the bonding layer and substrate, and propagated horizontally, resulting in the separation of both the ceramic and bonding layers. Meanwhile, interfacial cracking and separation were deferred. A large roughness resulted in good cohesion between the ceramic and bonding layers, and a high stiffness for the coating, which improved the damage resistance and extended the life of the coating.     

Comparison of the Performance of a Pulsed Disc and Doughnut Column with a Pulsed Sieve Plate Liquid Extraction Column

Abstract

The hydrodynamic and mass‐transfer performance of a 75 mm diameter pulsed disc and doughnut column (PDD) and a pulsed sieve‐plate column (PSP) are presented and compared for a toluene–acetone–water system under similar operating conditions. It was found that the pulsed disc and doughnut column flooded earlier than the pulsed sieve‐plate column, indicating that the total throughput per unit cross‐sectional area through the pulsed disc and doughnut column was less. At similar operating conditions (i.e., flowrates, pulse frequency, and amplitude), the mass‐transfer performance of the pulsed disc and doughnut column was higher, and its holdup higher. The mass‐transfer performance of the PSP column, when compared at similar holdup to the PDD, was found to be higher, and so it is concluded that it is a more efficient column for this system.     

Grinding of alumina ceramic with microtextured brazed diamond end grinding wheels

Brazed monolayer diamond grinding wheels have advantages of a high abrasive bonding strength, high protrusion, and a large chip disposal space. However, it is difficult to prepare ordered and fine-grained brazed diamond grinding wheels. This study presents a new method for grain-arranged, brazed diamond grinding wheels with microtextures with similar performance to ordered and fine-grained brazed diamond grinding wheels. First, coarse diamond grains (18/20 mesh) were orderly brazed to fabricate the end grinding wheels. Next, a series of microtextures were ablated on the diamond grains using a pulsed laser, and two types of textured end grinding wheels—TG-G (ablated microgrooves only) and TG-GH (ablated microgrooves and microholes)—were prepared. Then, an experiment involving the grinding of alumina ceramics was performed, and the grinding characteristics and grinding mechanism were analyzed. The results indicated that compared with untextured diamond end grinding wheels (TG), the textured diamond grinding wheels (TG-G and TG-GH) significantly reduced the grinding force and the roughness of the machined surface. The local stress concentration at the microtextures promoted the formation of microcracks in the diamond grains of TG-G and TG-GH, and the self-sharpness of the grinding wheel was significantly improved. The brittle fracture mode of ceramic materials in grinding included intergranular fracture and transgranular fracture. Ironing pressure action was a key material-removal mechanism. It had an important influence on the cutting force and plasticity characteristics of the TG machined surface. For the surfaces processed by TG-G and TG-GH, the effect of ironing was weakened, while shearing played a more important role. The TG-GH grinding wheel ablated with microgrooves and microholes was superior to the TG-G grinding wheel ablated with only microgrooves, with regard to the grinding force, roughness, and self-sharpening.