Microstructures made in optical fiber with femtosecond laser

Different types of microstructures including microchannels and microslots were made in optical fibers using femtosecond laser inscription and chemical etching. Integrated with UV-inscribed fiber Bragg gratings, these microstructures have miniature, robustness and high sensitivity features and have been used to implement novel devices for various sensing applications. The fiber microchannels were used to detect the refractive index change of liquid presenting sensitivities up to 7.4 nm/refractive index unit (RIU) and 166.7 dB/RIU based on wavelength and power detection, respectively. A microslot-in-fiber based liquid core waveguide as a refractometer has been proposed and the device was used to measure refractive index, and a sensitivity up to 945 nm/RIU (10-6/pm) was obtained. By filling epoxy in the microslot and subsequent UV light curing, a hybrid waveguide grating structure with polymer core and glass cladding was fabricated. The obtained device was highly thermal responsive, demonstrating a linear coefficient of 211 pm/°C.

Microstructures made in optical fiber with femtosecond laser

Different types of microstructures including microchannels and microslots were made in optical fibers using femtosecond laser inscription and chemical etching. Integrated with UV-inscribed fiber Bragg gratings, these microstructures have miniature, robustness and high sensitivity features and have been used to implement novel devices for various sensing applications. The fiber microchannels were used to detect the refractive index change of liquid presenting sensitivities up to 7.4 nm/refractive index unit (RIU) and 166.7 dB/RIU based on wavelength and power detection, respectively. A microslot-in-fiber based liquid core waveguide as a refractometer has been proposed and the device was used to measure refractive index, and a sensitivity up to 945 nm/RIU (10-6/pm) was obtained. By filling epoxy in the microslot and subsequent UV light curing, a hybrid waveguide grating structure with polymer core and glass cladding was fabricated. The obtained device was highly thermal responsive, demonstrating a linear coefficient of 211 pm/°C.

Effect of II‐VI Semiconductor Nanomaterials and Electron Irradiation on Polystyrene (PS) & Poly(ethylene‐co‐vinyl acetate) (EVA)

Organic-inorganic nanocomposites combine unique properties of both the constituents in one material. Among this group of materials, clay based as well as ZnO, TiO2 nanocomposites have been found to have diverse applications. Optoelectronic devices require polymerinorganic systems to meet certain desired properties. Dielectric properties of conventional polymers like poly(ethylene-co-vinyl acetate) (EVA) and polystyrene (PS) may also be tailor tuned with the incorporation of inorganic fillers in very small amounts. Electrical conductivity and surface resistivity of polymer matrices are found to improve with inorganic nanofillers. II-VI semiconductors and their nano materials have attracted material scientists because of their unique optical properties of photoluminescence, UV photodetection and light induced conductivity. Cadmium selenide (CdSe), zinc selenide (ZnSe) and zinc oxide (ZnO) are some of the most promising members of the IIVI semiconductor family, used in light-emitting diodes, nanosensors, non-linear optical (NLO) absorption etc. EVA and PS materials were selected as the matrices in the present study because they are commercially used polymers and have not been the subject of research for opto-electronic properties with semiconductor nanomaterials

Radiopacity and Chemical resistance of Elastomer-Barium sulphate nanocomposites

The Human race of our century is in gluttonous search for novel engineering products which led to a skyrocketed progress in research and fabrication of filled polymers. Recently, a big window has been opened up for speciality polymers especially elastomers with promising properties. Among the many reasons why rubbers are widely used in the process industries, three are considered as important. Firstly, rubbers operate in a variety of environments and possess usable ranges of deformity and durability and can be exploited through suitable and more or less conventional equipment design principles. Secondly, rubber is an eminently suitable construction material for protection against corrosion in the chemical plant and equipment against various corrosive chemicals as, acids and alkalies and if property tailored, can shield ionising radiations as X-rays and gamma rays in medical industry, with minimum maintenance lower down time, negligible corrosion and a preferred choice for aggressive corroding and ionising environment. Thirdly, rubber can readily and hastily, and at a relatively lower cost, be converted into serviceable products, having intricate shapes and dimensions. In a century’s gap, large employment of flexible polymer materials in the different segments of industry has stimulated the development of new materials with special properties, which paved its way to the synthesis of various nanoscale materials. At nano scale, one makes an entry into a world where multidisciplinary sciences meet and utilises the previously unapproached infinitesimal length scale, having dimension which measure upto one billionth of a meter, to create novel properties. The nano fillers augment the elastomers properties in an astonishing fashion due to their multifunctional nature and unprecedented properties have been exhibited by these polymer-nanocomposites just to beat the shortcomings of traditional micro composites. The current research aims to investigate the possibility of using synthesised nano barium sulphate for fabricating elastomer-based nanocomposites and thereby imparting several properties to the rubber. In this thesis, nano materials, their synthesis, structure, properties and applications are studied. The properties of barium sulphate like chemical resistance and radiopacity have been utilized in the present study and is imparted to the elastomers by preparing composites.

Applications for nanomaterials in critical technologies

This thesis is devoted to the development, synthesis, properties, and applications of nano materials for critical technologies, including three areas: (1) Microbial contamination of drinking water is a serious problem of global significance. About 51% of the waterborne disease outbreaks in the United States can be attributed to contaminated ground water. Development of metal oxide nanoparticles, as viricidal materials is of technological and fundamental scientific importance. Nanoparticles with high surface areas and ultra small particle sizes have dramatically enhanced efficiency and capacity of virus inactivation, which cannot be achieved by their bulk counterparts. A series of metal oxide nanoparticles, such as iron oxide nanoparticles, zinc oxide nanoparticles and iron oxide-silver nanoparticles, coated on fiber substrates was developed in this research for evaluation of their viricidal activity. We also carried out XRD, TEM, SEM, XPS, surface area measurements, and zeta potential of these nanoparticles. MS2 virus inactivation experiments showed that these metal oxide nanoparticle coated fibers were extremely powerful viricidal materials. Results from this research suggest that zinc oxide nanoparticles with diameter of 3.5 nm, showing an isoelectric point (IEP) at 9.0, were well dispersed on fiberglass. These fibers offer an increase in capacity by orders of magnitude over all other materials. Compared to iron oxide nanoparticles, zinc oxide nanoparticles didn’t show an improvement in inactivation kinetics but inactivation capacities did increase by two orders of magnitude to 99.99%. Furthermore, zinc oxide nanoparticles have higher affinity to viruses than the iron oxide nanoparticles in presence of competing ions. The advantages of zinc oxide depend on high surface charge density, small nanoparticle sizes and capabilities of generating reactive oxygen species. The research at its present stage of development appears to offer the best avenue to remove viruses from water. Without additional chemicals and energy input, this system can be implemented by both points of use (POU) and large-scale use water treatment technology, which will have a significant impact on the water purification industry. (2) A new family of aliphatic polyester lubricants has been developed for use in micro-electromechanical systems (MEMS), specifically for hard disk drives that operate at high spindle speeds (>15000rpm). Our program was initiated to address current problems with spin-off of the perfluoroether (PFPE) lubricants. The new polyester lubricant appears to alleviate spin-off problems and at the same time improves the chemical and thermal stability. This new system provides a low cost alternative to PFPE along with improved adhesion to the substrates. In addition, it displays a much lower viscosity, which may be of importance to stiction related problems. The synthetic route is readily scalable in case additional interest emerges in other areas including small motors. (3) The demand for increased signal transmission speed and device density for the next generation of multilevel integrated circuits has placed stringent demands on materials performance. Currently, integration of the ultra low-k materials in dual Damascene processing requires chemical mechanical polishing (CMP) to planarize the copper. Unfortunately, none of the commercially proposed dielectric candidates display the desired mechanical and thermal properties for successful CMP. A new polydiacetylene thermosetting polymer (DEB-TEB), which displays a low dielectric constant (low-k) of 2.7, was recently developed. This novel material appears to offer the only avenue for designing an ultra low k dielectric (1.85k), which can still display the desired modulus (7.7Gpa) and hardness (2.0Gpa) sufficient to withstand the process of CMP. We focused on further characterization of the thermal properties of spin-on poly (DEB-TEB) ultra-thin film. These include the coefficient of thermal expansion (CTE), biaxial thermal stress, and thermal conductivity. Thus the CTE is 2.0*10-5K-1 in the perpendicular direction and 8.0*10-6 K-1 in the planar direction. The low CTE provides a better match to the Si substrate which minimizes interfacial stress and greatly enhances the reliability of the microprocessors. Initial experiments with oxygen plasma etching suggest a high probability of success for achieving vertical profiles.

Graphene and Semicondutor or Metallic Nanoparticles for Energy Conversion

The purpose of the present PhD thesis is to investigate the properties of innovative nano- materials with respect to the conversion of renewable energies to electrical and chemical energy. The materials have been synthesized and characterized by means of a wide spectrum of morphological, compositional and photophysical techniques, in order to get an insight into the correlation between the properties of each material and the activity towards different energy conversion applications. Two main topics are addressed: in the first part of the thesis the light harvesting in pyrene functionalized silicon nanocrystals has been discussed, suggesting an original approach to suc- cessfully increase the absorption properties of these nanocrystals. The interaction of these nanocrystals was then studied, in order to give a deeper insight on the charge and energy extraction, preparing the way to implement SiNCs as active material in optoelectronic devices and photovoltaic cells. In addition to this, the luminescence of SiNCs has been exploited to increase the efficiency of conventional photovoltaic cells by means of two innovative architectures. Specifically, SiNCs has been used as luminescent downshifting layer in dye sensitized solar cells, and they were shown to be very promising light emitters in luminescent solar concentrators. The second part of the thesis was concerned on the production of hydrogen by platinum nanoparticles coupled to either electro-active or photo-active materials. Within this context, the electrocatalytic activity of platinum nanoparticles supported on exfoliated graphene has been studied, preparing an high-efficiency catalyst and disclosing the role of the exfoliation technique towards the catalytic activity. Furthermore, platinum nanoparticles have been synthesized within photoactive dendrimers, providing the first proof of concept of a dendrimer-based photocatalytic system for the hydrogen production where both sensitizer and catalyst are anchored to a single scaffold.

Modified nano- and microcellulose based adsorption materials in water treatment

In recent decades, industrial activity growth and increasing water usage worldwide have led to the release of various pollutants, such as toxic heavy metals and nutrients, into the aquatic environment. Modified nanocellulose and microcellulose-based adsorption materials have the potential to remove these contaminants from aqueous solutions. The present research consisted of the preparation of five different nano/microcellulose-based adsorbents, their characterization, the study of adsorption kinetics and isotherms, the determination of adsorption mechanisms, and an evaluation of adsorbents’ regeneration properties. The same well known reactions and modification methods that were used for modifying conventional cellulose also worked for microfibrillated cellulose (MFC). The use of succinic anhydride modified mercerized nanocellulose, and aminosilane and hydroxyapatite modified nanostructured MFC for the removal of heavy metals from aqueous solutions exhibited promising results. Aminosilane, epoxy and hydroxyapatite modified MFC could be used as a promising alternative for H2S removal from aqueous solutions. In addition, new knowledge about the adsorption properties of carbonated hydroxyapatite modified MFC as multifunctional adsorbent for the removal of both cations and anions ions from water was obtained. The maghemite nanoparticles (Fe3O4) modified MFC was found to be a highly promising adsorbent for the removal of As(V) from aqueous solutions due to its magnetic properties, high surface area, and high adsorption capacity . The maximum removal efficiencies of each adsorbent were studied in batch mode. The results of adsorption kinetics indicated very fast removal rates for all the studied pollutants. Modeling of adsorption isotherms and adsorption kinetics using various theoretical models provided information about the adsorbent’s surface properties and the adsorption mechanisms. This knowledge is important for instance, in designing water treatment units/plants. Furthermore, the correspondence between the theory behind the model and properties of the adsorbent as well as adsorption mechanisms were also discussed. On the whole, both the experimental results and theoretical considerations supported the potential applicability of the studied nano/microcellulose-based adsorbents in water treatment applications.

Fabrication and Characterization of Chalcogenide nano composite based materials for Photonic device applications

In this context,in search of new materials based on chalcogenide glasses,we have developed a novel technique for fabrication of chalcogenide nano composites which are presented in this theis.The techniques includes the dissolution of bulk chalcogenide glasses in amine solvent.This solution casting method allows to retain the attractive optical properties of chalcogenide glasses enabling new fabrication routes for realization of large area thick-thin films with less cost. Chalcogenide glass fiber geometry opens new possibilities for a large number of applications in optics,like remote temperature measurements ,CO2 laser power delivery, and optical sensing and single mode propagation of IR light.We have fabricated new optical polymer fibers doped with chalcogenide glasses which can be used for many optical applications.The present thesis also describes the structural,thermal and optical characterization of certain chalocogenide based materials prepared for different methods and its applications.

Comparison of push-in and push-out tests for measuring interfacial shear strength in nano-reinforced composite materials

The influence of the carbon nanotubes (CNTs) content on the fiber/matrix interfacial shear strength (IFSS) in glass/fiber epoxy composites was measured by means of push-in and push-out tests. Both experimental methodologies provided equivalent values of the IFSS for each material. It was found that the dispersion of CNTs increased in IFSS by 19% in average with respect to the composite without CNTs. This improvement was reached with 0.3 wt.% of CNTs and increasing the CNT content up to 0.8 wt.% did not improve the interface strength.

Active site engineering for heterogeneous catalysis using emerging nano-structured materials

The growing concern about the depletion of oil has spurred worldwide interest in finding alternative feedstocks for important petrochemical commodities and fuels. On the one hand, the enormous re-serves found (208 trillion cubic feet proven1), environmental sustainability and lower overall costs point to natural gas as the primary source for energy and chemicals in the near future.2 Nowadays the transformation of methane into useful chemicals and liquid fuels is only feasible via synthesis gas, a mixture of molecular hydrogen and carbon monoxide, that is further transformed to methanol or to hydrocarbons under moderate reaction conditions (150-350 °C and 10-100 bar).3 For a major cost reduction and in order to valorize small natural gas sources, either more efficient "syngas to products" catalysts should be produced or the manner in which methane is initially activated should be changed, ideally by developing catalysts able to directly oxidize methane to interesting products such as methanol. On the other hand, from the point of view of CO2 emissions, the use of the re-maining fossil resources will further contribute to global warming. In this scenario, the development of efficient routes for the transformation of CO2 into useful chemicals and fuels would represent a considerable step forward towards sustainability. Indeed, the environmental and economic incen-tives to develop processes for the conversion of CO2 into fuels and chemicals are great. However, for such conversions to become economically feasible, considerable research is necessary. In this lecture we will summarize our recent efforts into the design of new catalytic systems, based on MOFs and COFs, to address these challenges. Examples include the development of new Fe based FTS catalysts, electrocatalysts for the selective conversion of CO2 into syngas, the development of efficient catalysts for the utilization of formic acid as hydrogen storage vector and the development of new enzyme inspired systems for the direct transformation of methane to methanol under mild reaction conditions. References (1) http://www.clearonmoney.com/dw/doku.php?id=public:natural_gas_reserves. (2) Derouane, E. G.; Parmon, V.; Lemos, F.; Ribeiro, F. R. Sustainable Strategies for the Up-grading of Natural Gas: Fundamentals, Challenges, and Opportunities; Springer, 2005. (3) Rofer-DePoorter, C. K. Chemical Reviews. ACS Publications 1981, pp 447–474.

Production and characterization of novel thermoplastic (nano)composite materials for additive manufacturing applications

The increasing environmental global regulations have directed scientific research towards more sustainable materials, even in the field of composite materials for additive manufacturing. In this context, the presented research is devoted to the development of thermoplastic composites for FDM application with a low environmental impact, focusing on the possibility to use wastes from different industrial processes as filler for the production of composite filaments for FDM 3D printing. In particular carbon fibers recycled by pyro-gasification process of CFRP scraps were used as reinforcing agent for PLA, a biobased polymeric matrix. Since the high value of CFs, the ability to re-use recycled CFs, replacing virgin ones, seems to be a promising option in terms of sustainability and circular economy. Moreover, wastes from different agricultural industries, i.e. wheat and rice production processes, were valorised and used as biofillers for the production of PLA-biocomposites. The integration of these agricultural wastes into PLA bioplastic allowed to obtain biocomposites with improved eco-sustainability, biodegradability, lightweight, and lower cost. Finally, the study of novel composites for FDM was extended towards elastomeric nanocomposite materials, in particular TPU reinforced with graphene. The research procedure of all projects involves the optimization of production methods of composite filaments with a particular attention on the possible degradation of polymeric matrices. Then, main thermal properties of 3D printed object are evaluated by TGA, DSC characterization. Additionally, specific heat capacity (CP) and Coefficient of Linear Thermal Expansion (CLTE) measurements are useful to estimate the attitude of composites for the prevention of typical FDM issues, i.e. shrinkage and warping. Finally, the mechanical properties of 3D printed composites and their anisotropy are investigated by tensile test using distinct kinds of specimens with different printing angles with respect to the testing direction.

Non-linear modelling of microwave devices embedding nano-ferroelectric materials for real-time reconfigurable transmitarray

In this thesis work a nonlinear model for Interdigitated Capacitors (IDCs) based on ferroelectric materials, is proposed. Through the properties of materials such as Hafnium-Zirconium Oxide (HfZrO2), it is possible to realize tunable radiofrequency (RF) circuits. In particular, the model proposed in this thesis describes the use of an IDC, realized on a High-Resistivity silicon substrate, as a phase shifter for beam-steering applications. The model is obtained starting from already present experimental measurements, through which it is possible to identify a circuit model. The model is tested for both low power values and other power values using Harmonic Balance simulations, which show an excellent convergence of the model up to 40 dBm of input power. Furthermore, an array composed by two patches operating both at 2.55 GHz, which exploits the tunable properties of the HfZrO-based IDC is proposed. At 0dBm the model shows a 47° phase shift with polarization -1 V and 1 V which leads to a 11° steering of the main lobe of the array.

Free-standing urethane/urea elastomer films undoped and doped with ferro-nano-particles

We report on an experimental study of the structures presented by urethane/urea elastomeric films without and with ferromagnetic nanoparticles incorporated. The study is made by using the X-ray diffraction, nuclear magnetic resonance (NMR), optical, atomic and magnetic force (MFM) microscopy techniques, and mechanical assays. The structure of the elastomeric matrix is characterized by a distance of 0.46 nm between neighboring molecular segments, almost independent on the stretching applied. The shear casting performed in order to obtain the elastomeric films tends to orient the molecules parallel to the flow direction thus introducing anisotropy in the molecular network which is reflected on the values obtained for the orientational order parameter and its increase for the stretched films. In the case of nanoparticles-doped samples, the structure remains nearly unchanged although the local order parameter is clearly larger for the undoped films. NMR experiments evidence modifications in the molecular network local ordering. Micrometer size clusters were observed by MFM for even small concentration of magnetic particles.

Chromic materials for responsive surface-enhanced resonance Raman scattering systems: a nanometric pH sensor

The use of chromic materials for responsive surface-enhanced resonance Raman scattering (SERRS) based nanosensors is reported. The potential of nano-chromic SERRS is demonstrated with the use of the halochrome methyl yellow to fabricate an ultrasensitive pH optical sensor. Some of the challenges of the incorporation of chromic materials with metal nanostructures are addressed through the use of computational calculations and a comparison to measured SERRS and surface-enhanced Raman scattering (SERS) spectra is presented. A strong correlation between the measured SERRS and the medium's proton concentration is demonstrated for the pH range 2-6. The high sensitivity achieved by the use of resonance Raman conditions is shown through responsive SERRS measurements from only femtolitres of volume and with the concentration of the reporting molecules approaching the single molecule regime.