Designing atmospheric-pressure plasma sources for surface engineering of nanomaterials

Atmospheric-pressure plasma processing techniques emerge as efficient and convenient tools to engineer a variety of nanomaterials for advanced applications in nanoscience and nanotechnology. This work presents different methods, including using a quasi-sinusoidal high-voltage generator, a radio-frequency power supply, and a uni-polar pulse generator, to generate atmospheric-pressure plasmas in the jet or dielectric barrier discharge configurations. The applicability of the atmospheric-pressure plasma is exemplified by the surface modification of nanoparticles for polymeric nanocomposites. Dielectric measurements reveal that representative nanocomposites with plasma modified nanoparticles exhibit notably higher dielectric breakdown strength and a significantly extended lifetime.

Internal oscillating current-sustained RF plasmas : Parameters, stability, and potential for surface engineering

A new source of low-frequency (0.46 MHz) inductively coupled plasmas sustained by the internal planar "unidirectional" RF current driven through a specially designed internal antenna configuration has been developed. The experimental results of the investigation of the optical and global argon plasma parameters by the optical and Langmuir probes are presented. It is shown that the spatial profiles of the electron density, the effective electron temperature and plasma potential feature a great deal of the radial and axial uniformity compared with conventional sources of inductively coupled plasmas with external at coil configurations. The measurements also reveal a weak azimuthal dependence of the global plasma parameters at low values of the input RF power, which was earlier predicted theoretically. The azimuthal dependence of the global plasma parameters vanishes at high input RF powers. Moreover, under certain conditions, the plasma becomes unstable due to spontaneous transitions between low-density (electrostatic, E) and high-density (electromagnetic, H) operating modes. Excellent uniformity of high-density plasmas makes the plasma reactor promising for various plasma processing applications and surface engineering.

Surface engineering of reduced graphene oxide for controllable ambipolar flash memories

Tunable charge-trapping behaviors including unipolar charge trapping of one type of charge carrier and ambipolar trapping of both electrons and holes in a complementary manner is highly desirable for low power consumption multibit flash memory design. Here, we adopt a strategy of tuning the Fermi level of reduced graphene oxide (rGO) through self-assembled monolayer (SAM) functionalization and form p-type and n-type doped rGO with a wide range of manipulation on work function. The functionalized rGO can act as charge-trapping layer in ambipolar flash memories, and a dramatic transition of charging behavior from unipolar trapping of electrons to ambipolar trapping and eventually to unipolar trapping of holes was achieved. Adjustable hole/electron injection barriers induce controllable Vth shift in the memory transistor after programming operation. Finally, we transfer the ambipolar memory on flexible substrates and study their charge-trapping properties at various bending cycles. The SAM-functionalized rGO can be a promising candidate for next-generation nonvolatile memories.

Ultrasound-assisted surface engineering of pharmaceutical powders

Effective processing of powdered particles can facilitate powder handling and result in better drug product performance, which is of great importance in the pharmaceutical industry where the majority of active pharmaceutical ingredients (APIs) are delivered as solid dosage forms. The purpose of this work was to develop a new ultrasound-assisted method for particle surface modification and thin-coating of pharmaceutical powders. The ultrasound was used to produce an aqueous mist with or without a coating agent. By using the proposed technique, it was possible to decrease the interparticular interactions and improve rheological properties of poorly-flowing water-soluble powders by aqueous smoothing of the rough surfaces of irregular particles. In turn, hydrophilic polymer thin-coating of a hydrophobic substance diminished the triboelectrostatic charge transfer and improved the flowability of highly cohesive powder. To determine the coating efficiency of the technique, the bioactive molecule β-galactosidase was layered onto the surface of powdered lactose particles. Enzyme-treated materials were analysed by assaying the quantity of the reaction product generated during enzymatic cleavage of the milk sugar. A near-linear increase in the thickness of the drug layer was obtained during progressive treatment. Using the enzyme coating procedure, it was confirmed that the ultrasound-assisted technique is suitable for processing labile protein materials. In addition, this pre-treatment of milk sugar could be used to improve utilization of lactose-containing formulations for populations suffering from severe lactose intolerance. Furthermore, the applicability of the thin-coating technique for improving homogeneity of low-dose solid dosage forms was shown. The carrier particles coated with API gave rise to uniform distribution of the drug within the powder. The mixture remained homogeneous during further tabletting, whereas the reference physical powder mixture was subject to segregation. In conclusion, ultrasound-assisted surface engineering of pharmaceutical powders can be effective technology for improving formulation and performance of solid dosage forms such as dry powder inhalers (DPI) and direct compression products.

Nano-hardness Techniques and Its Applications in Mechanical Property Measurements for Surface Engineering

结合纳米硬度技术测量各类薄膜和块体材料表层的纳米压痕硬度、弹性模量、断裂韧性、膜厚、微结构的弯曲变形,采用纳米划痕硬度技术测量各类薄膜和块体材料的粗糙度、临界附着力、摩擦系数、划痕横剖面.纳米硬度计是检测材料表层微米乃至几十纳米力学性能的先进仪器,可广泛应用于表面工程中的质量检测.

Surface engineering of silica nanoparticles for oral insulin delivery: characterization and cell toxicity studies

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Safety by design: production of engineering surface modified nanomaterials

This PhD thesis focused on nanomaterial (NM) engineering for occupational health and safety, in the frame of the EU project “Safe Nano Worker Exposure Scenarios (SANOWORK)”. Following a safety by design approach, surface engineering (surface coating, purification process, colloidal force control, wet milling, film coating deposition and granulation) were proposed as risk remediation strategies (RRS) to decrease toxicity and emission potential of NMs within real processing lines. In the first case investigated, the PlasmaChem ZrO2 manufacturing, the colloidal force control applied to the washing of synthesis rector, allowed to reduce ZrO2 contamination in wastewater, performing an efficient recycling procedure of ZrO2 recovered. Furthermore, ZrO2 NM was investigated in the ceramic process owned by CNR-ISTEC and GEA-Niro; the spray drying and freeze drying techniques were employed decreasing NM emissivity, but maintaining a reactive surface in dried NM. Considering the handling operation of nanofibers (NFs) obtained through Elmarco electrospinning procedure, the film coating deposition was applied on polyamide non-woven to avoid free fiber release. For TiO2 NF the wet milling was applied to reduce and homogenize the aspect ratio, leading to a significant mitigation of fiber toxicity. In the Colorobbia spray coating line, Ag and TiO2 nanosols, employed to transfer respectively antibacterial or depolluting properties to different substrates, were investigated. Ag was subjected to surface coating and purification, decreasing NM toxicity. TiO2 was modified by surface coating, spray drying and blending with colloidal SiO2, improving its technological performance. In the extrusion of polymeric matrix charged with carbon nanotube (CNTs) owned by Leitat, the CNTs used as filler were granulated by spray drying and freeze spray drying techniques, allowing to reduce their exposure potential. Engineered NMs tested by biologists were further investigated in relevant biological conditions, to improve the knowledge of structure/toxicity mechanisms and obtain new insights for the design of safest NMs.

Resolidification behaviour of laser surface-melted metals and alloys

The solidification behaviour is described of two pure metals (Bi and Ni) and two eutectic alloys (A1-Ge and AI-Cu) under nonequilibrium conditions, in particular the microsecond pulsed laser surface melting. The resolidification behaviour of bismuth shows that epitaxial regrowth is the dominant mechanism. For mixed grain size, regrowth of larger grains dominates the microstructure and can result in the development of texture. In the case of nickel, epitaxial growth has been noted. For lower energy pulse-melted pool, grain refinement takes place, indicating nucleation of fresh nickel grains. The A1-Ge eutectic alloy indicates the nucleation and columnar growth of a metastable monoclinic phase from the melt-substrate interface at a high power density laser irradiation. An equiaxed microstructure containing the same monoclinic phase is obtained at a lower power density laser irradiation. It is shown that the requirement of solution partition acts as a barrier to eutectic regrowth from the substrate. The laser-melted pool of A1-Cu eutectic alloy includes columnar growth of c~-A1 and 0-A12Cu phase followed by the dendritic growth of A12Cu phase with ct-Al forming at the interdendritic space. In addition, a banded microstructure was observed in the resolidified laser-melted pool.

Performance modulation of α-MnO2 nanowires by crystal facet engineering

Modulation of material physical and chemical properties through selective surface engineering is currently one of the most active research fields, aimed at optimizing functional performance for applications. The activity of exposed crystal planes determines the catalytic, sensory, photocatalytic, and electrochemical behavior of a material. In the research on nanomagnets, it opens up new perspectives in the fields of nanoelectronics, spintronics, and quantum computation. Herein, we demonstrate controllable magnetic modulation of α-MnO 2 nanowires, which displayed surface ferromagnetism or antiferromagnetism, depending on the exposed plane. First-principles density functional theory calculations confirm that both Mn- and O-terminated α-MnO2(1 1 0) surfaces exhibit ferromagnetic ordering. The investigation of surface-controlled magnetic particles will lead to significant progress in our fundamental understanding of functional aspects of magnetism on the nanoscale, facilitating rational design of nanomagnets. Moreover, we approved that the facet engineering pave the way on designing semiconductors possessing unique properties for novel energy applications, owing to that the bandgap and the electronic transport of the semiconductor can be tailored via exposed surface modulations.

Stress induced phase transition in monomolecular perfluroalkylsilane film self assembled on aluminium surface

We control the stiffnesses of two dual double cantelevers placed in series to control penetration into a perflurooctyltrichlorosilane monolayer self assembled on aluminium and silicon substrates. The top cantilever which carries the probe is displaced with respect to the bottom cantilever which carries the substrate, the difference in displacement recorded using capacitors gives penetration. We further modulate the input displacement sinusoidally to deconvolute the viscoelastic properties of the monolayer. When the intervention is limited to the terminal end of the molecule there is a strong viscous response in consonance with the ability of the molecule to dissipate energy by the generation of gauche defects freely. When the intervention reaches the backbone, at a contact mean pressure of 0.2GPa the damping disappears abruptly and the molecule registers a steep rise in elastic modulus and relaxation time constant, with increasing contact pressure. We offer a physical explanation of the process and describe this change as due to a phase transition from a liquid like to a solid like state.

In Situ Synthesis of Nanocrystalline Intermetallic Compound Layer During Surface Mechanical Attrition Treatment of Zirconium

The surface mechanical attrition treatment (SMAT) technique was developed to synthesize a nanocrystalline (NC) layer on the surface of metallic materials for upgrading their overall properties and performance. In this paper, by means of SMAT to a pure zirconium plate at the room temperature, repetitive multidirectional peening of steel shots (composition (wt%): 1C, 1.5Cr, base Fe) severely deformed the surface layer. A NC surface layer consisting of the intermetallic compound FeCr was fabricated on the surface of the zirconium. The microstructure characterization of the surface layer was performed by using X-ray diffraction analysis, optical microscopy, scanning and transmission electron microscopy observations. The NC surface layer was about 25 mu m thick and consisted of the intermetallic compound FeCr with an average grain size of 25 +/- 10 nm. The deformation-induced fast diffusion of Fe and Cr from the steel shots into Zr occurred during SMAT, leading to the formation of intermetallic compound. In addition, the NC surface layer exhibited an ultrahigh nanohardness of 10.2 GPa.