Photocatalytic Activity of Nanostructured Anatase Coatings Obtained by Cold Gas Spray

This article describes a photocatalytic nanostructured anatase coating deposited by cold gas spray (CGS)supported on titanium sub-oxide (TiO22x) coatings obtained by atmospheric plasma spray (APS) onto stainless steel cylinders. The photocatalytic coating was homogeneous and preserved the composition and nanostructure of the starting powder. The inner titanium sub-oxide coating favored the deposition of anatase particles in the solid state. Agglomerated nano-TiO2 particles fragmented when impacting onto the hard surface of the APS TiO22x bond coat. The rough surface provided by APS provided an ideal scenario for entrapping the nanostructured particles, which may be adhered onto the bond coat due to chemical bonding; a possible bonding mechanism is described. Photocatalytic experiments showed that CGS nano-TiO2 coating was active for photodegrading phenol and formic acid under aqueous conditions. The results were similar to the performance obtained by competitor technologies and materials such as dip-coating P25 photocatalysts. Disparity in the final performance of the photoactive materials may have been caused by differences in grain size and the crystalline composition of titanium dioxide.

Development of novel surface coatings based on acrylic copolymers

The present study describes the preparation of Vinyl acetate-Butyl acrylate copolymer lattices of varying compositions and solid contents by semicontinuous emulsion polymerization method. This copolymer lattices were used as binder to develop a new surface coating formulation. The properties of this surface coating were improved by using nano TiO2 colloidal sol as a pigment. Antimicrobial activity of surface coatings was improved by the addition of carboxymethyl chitosan as biocide. Uniformly dispersed tyre crumb was used to give a mat finish to the coating. The mechanical properties adhesive properties, thermal properties etc. of the coatings are presented in thesis.

Photocatalytic activity of nanostructured anatase coatings obtained by cold gas spray

[EN] This article describes a photocatalytic nanostructured anatase coating deposited by cold gas spray (CGS) supported on titanium sub-oxide (TiO22x) coatings obtained by atmospheric plasma spray (APS) onto stainless steel cylinders. The photocatalytic coating was homogeneous and preserved the composition and nanostructure of the starting powder. The inner titanium sub-oxide coating favored the deposition of anatase particles in the solid state. Agglomerated nano-TiO2 particles fragmented when impacting onto the hard surface of the APS TiO22x bond coat. The rough surface provided by APS provided an ideal scenario for entrapping the nanostructured particles, which may be adhered onto the bond coat due to chemical bonding; a possible bonding mechanism is described. Photocatalytic experiments showed that CGS nano-TiO2 coating was active for photodegrading phenol and formic acid under aqueous conditions. The results were similar to the performance obtained by competitor technologies and materials such as dip-coating P25 photocatalysts. Disparity in the final performance of the photoactive materials may have been caused by differences in grain size and the crystalline composition of titanium dioxide.

Metodologie "green" per l'ottenimento di biopolimeri da colture microbiche

Sono stati studiati ed applicati metodi “green” per l’estrazione di poliidrossialcanoati (PHA) da colture microbiche singole (Cupriavidus necator) e miste. Sono stati effettuati esperimenti che prevedono l’utilizzo di surfattanti anionici switchable (SAS) per l’estrazione del polimero, al fine di arrivare ad un protocollo ottimale per l’estrazione di PHB da C.necator che prevede l’uso di NH4 laurato come SAS (100 wt% rispetto al peso dei batteri) per tre ore a 90°C. La sostanza ambifilica agisce distruggendo la membrana cellulare esponendo così i granuli di PHB. Il SAS utilizzato si caratterizza per la possibilità di essere recuperabile tramite aggiunta di CO2 al sistema con una resa del 98%. Per le colture microbiche miste, più refrattarie all’impiego dei surfattanti, sono stati utilizzati dei pre-trattamenti, meccanici e fotocatalitici, al fine di indebolire la membrana batterica. Per il trattamento meccanico sono stati impiegati un omogeneizzatore e un sonicatore ad ultrasuoni; mentre per il trattamento fotocatalitico è stata sperimentata l’azione del nano biossido di titanio (sospensione 1% nano-TiO2) in miscela con i batteri, esposti a radiazioni UV. Dai risultati ottenuti sia il trattamento meccanico che quello fotocatalitico non sono risultati adeguati per i batteri misti. Infine il PHB estratto dalla biomassa batterica è stato purificato con un trattamento fotocatalitico che prevede l’utilizzo di nano-TiO2 1% supportato in tessuti, esposti a luce UV. I risultati di questo post-trattamento mostrano che, anche utilizzando diverse tipologie di tessuto, il PHB viene in parte adsorbito dal tessuto, con la seguente perdita di campione. In conclusione il trattamento del C. necator con i SAS risulta essere un ottimo metodo di estrazione di PHB considerando sia la qualità del polimero estratto sia il riciclo e il riutilizzo del surfattante, mentre per il trattamento delle colture microbiche miste ancora non è stato trovato un protocollo soddisfacente.

Argamassas de auto-limpeza : da formulação às aplicações

Atualmente assiste-se a um grave problema de salubridade visual das cidades, designadamente no espaço edificado/ construído. A sujidade é uma ameaça que, junto com os graffitis, tem contribuído para a degradação precoce dos espaços urbanos. A fim de se enfrentar este problema, que tem vindo a proliferar nas cidades, um pouco por todo o mundo, a presente dissertação de mestrado ambiciona contribuir para a sistematização da informação existente sobre a produção e caracterização de argamassas de auto-limpeza. As argamassas de auto-limpeza são produzidas por uma de duas formas: com a adição de nanopartículas de dióxido de titânio (TiO2) na sua matriz ou com a aplicação de um filme fino à base de TiO2 na sua superfície. Esta segunda é apontada como a técnica mais eficaz e económica. Salienta-se o facto do TiO2 ser um dos nanomateriais mais utilizados na construção pelas suas propriedades fotocatalíticas que o capacitam como um dos mais exímios fotocatalisadores, aquando da fotocatálise heterogénea. É graças ao processo de fotodegradação química da fotocatálise, que na presença de luz solar e da ação da água, que o TiO2 é ativado, desencadeando reações químicas que aumentam a eficácia e eficiência fotocatalítica. Analisou-se um conjunto de trabalhos de investigação recentes que comprovam que o uso das argamassas de auto-limpeza é adequado e benéfico em intervenções em edifícios novos como em obras de conservação e reabilitação de edifícios antigos. Além de reduzirem os investimentos em obras de limpeza, manutenção/conservação e reabilitação, prolongam a conservação das fachadas e melhoram os níveis da qualidade do ar. Apesar do crescente número de patentes pedidas e concedidas nesta área, as normas aplicáveis ainda não se encontram uniformizadas. Nesse sentido, a experiência do Japão deve ser tida como exemplo para que os restantes países desenvolvam de forma consensual as suas próprias normas e patentes, permitindo, futuramente, conferir maior credibilidade, segurança no uso dos nanomateriais e uma maior permeabilidade no setor da construção. Elencam-se alguns nano-produtos à base de nano TiO2 comercializados que têm vindo a ser aplicados sobretudo na China, Japão e na Alemanha.

Ingegnerizzazione di materiali nanostrutturati fotocataliticamente attivi

Il lavoro oggetto di questa tesi è rivolto alla sintesi e alla caratterizzazione di materiali nanostrutturati costituiti da biossido di titanio e ossido di silicio da utilizzare come fotocatalizzatori per la depurazione delle acque. L’obiettivo è stato quello di realizzare un sistema in fase solida costituito da una matrice inerte, la silice, e una fase fotocataliticamente attiva, la nano-TiO2. Tale sistema si inserisce perfettamente nel settore di ricerca che studia la sintesi colloidale di eterostrutture nano e micro cristalline che combinano materiali diversi in un’unica particella. Il progetto nasce all’interno dell’ISTEC-CNR di Faenza, dove è stato svolto il lavoro.

Sviluppo ed ingegnerizzazione di nuovi sistemi ibridi a base di nanoparticelle inorganiche e bio-tensioattivi

In questo lavoro di tesi è stata investigata la sintesi di compositi a base di nano particelle di biossido di titanio rivestite da un bio-tensioattivo naturale. Il noto fotocatalizzatore (Nano-TiO2) è stato accoppiato ad un bio-tensioattivo dalle riconosciute proprietà antibatteriche, antivirali e anti-tumorali per ottenere un materiale composito multifunzionale. Diverse opzioni di design sono state investigate e la sintesi ottimizzata attraverso una caratterizzazione sistematica dei materiali prodotti, sia sulle sospensioni (DLS, ELS, TEM) sia sui prodotti granulati e calcinati (XRD, FT-IR, SEM, UV-Vis., BET). Per comprendere il ruolo del bio-tensioattivo e i potenziali effetti sinergici che il materiale composito potesse generare, si sono effettuate diverse caratterizzazioni funzionali testando il materiale per la realizzazione di nano-fasi fotocatalitiche da impiegare in processi di adsorbimento/degradazione di inquinanti acquosi, per la realizzazione di rivestimenti tessili antibatterici e come composito utile per l’assorbimento di metalli pesanti.

Desenvolvimento e caracterização de filmes de nano-compósitos de TiO2/WO3 pela técnoca de pulverização catódica

Dissertação para obtenção do Grau de Mestre em Engenharia Física

Caracterização de superfícies nano-estruturadas de interesse catalítico

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para a obtenção do grau de Mestre em Física Laboratorial, Ensino e História da Física

Caracterização do crescimento de filmes ultra-finos e nano-estruturas em superfícies

Dissertação apresentada para obtenção do Grau de Doutor em Engenharia Física, especialidade de Engenharia de Superfícies, pela Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia

Evolution of the surface plasmon resonance of Au:TiO2 nanocomposite thin films with annealing temperature

This paper reports on the changes in the structural and morphological features occurring in a particular type of nanocomposite thin-film system, composed of Au nanoparticles (NPs) dispersed in a host TiO2 dielectric matrix. The structural and morphological changes, promoted by in-vacuum annealing experiments of the as-deposited thin films at different temperatures (ranging from 200 to 800 C), resulted in a well-known localized surface plasmon resonance (LSPR) phenomenon, which gave rise to a set of different optical responses that can be tailored for a wide number of applications, including those for optical-based sensors. The results show that the annealing experiments enabled a gradual increase of the mean grain size of the Au NPs (from 2 to 23 nm), and changes in their distributions and separations within the dielectric matrix. For higher annealing temperatures of the as-deposited films, a broad size distribution of Au NPs was found (sizes up to 100 nm). The structural conditions necessary to produce LSPR activity were found to occur for annealing experiments above 300 C, which corresponded to the crystallization of the gold NPs, with an average size strongly dependent on the annealing temperature itself. The main factor for the promotion of LSPR was the growth of gold NPs and their redistribution throughout the host matrix. On the other hand, the host matrix started to crystallize at an annealing temperature of about 500 C, which is an important parameter to explain the shift of the LSPR peak position to longer wavelengths, i.e. a red-shift.

Studies on Catalysis by Nano Titania Modified with Metals and Nonmetals

Semiconductor photocatalysis has received much attention during last three decades as a promising solution for both energy generation and environmental problems. Heterogeneous photocatalytic oxidation allows the degradation of organic compounds into carbon dioxide and water in the presence of a semiconductor catalyst and UV light source. The •OH radicals formed during the photocatalytic processes are powerful oxidizing agents and can mineralise a number of organic contaminants. Titanium dioxide (TiO2), due to its chemical stability, non-toxicity and low cost represents one of the most efficient photocatalyst. However, only the ultraviolet fraction of the solar radiation is active in the photoexcitation processes using pure TiO2 and although, TiO2 can treat a wide range of organic pollutants the effectiveness of the process for pollution abatement is still low. A more effective and efficient catalyst therefore must be formulated. Doping of TiO2 was considered with the aim of improving photocatalytic properties. In this study TiO2 catalyst was prepared using the sol-gel method. Metal and nonmetal doped TiO2 catalysts were prepared. The photoactivity of the catalyst was evaluated by the photodegradation of different dyes and pesticides in aqueous solution. High photocatalytic degradation of all the pollutants was observed with doped TiO2. Structural and optical properties of the catalysts were characterized using XRD, BET surface area, UV-Vis. DRS, CHNS analysis, SEM, EDX, TEM, XPS, FTIR and TG. All the catalysts showed the anatase phase. The presence of dopants shifts the absorption of TiO2 into the visible region indicating the possibility of using visible light for photocatalytic processes.

Synthesis, Characterization and Applications of Hybrid Nanocomposites of TiO2 With Conducting Polymers

A nanocomposite is a multiphase solid material where one of the phases has one, two or three dimensions of less than 100 nanometers (nm), or structures having nano-scale repeat distances between the different phases that make up the material. In the broadest sense this definition can include porous media, colloids, gels and copolymers, but is more usually taken to mean the solid combination of a bulk matrix and nano-dimensional phase(s) differing in properties due to dissimilarities in structure and chemistry. The mechanical, electrical, thermal, optical, electrochemical, catalytic properties of the nanocomposite will differ markedly from that of the component materials. Size limits for these effects have been proposed, <5 nm for catalytic activity, <20 nm for making a hard magnetic material soft, <50 nm for refractive index changes, and <100 nm for achieving superparamagnetism, mechanical strengthening or restricting matrix dislocation movement. Conducting polymers have attracted much attention due to high electrical conductivity, ease of preparation, good environmental stability and wide variety of applications in light-emitting, biosensor chemical sensor, separation membrane and electronic devices. The most widely studied conducting polymers are polypyrrole, polyaniline, polythiophene etc. Conducting polymers provide tremendous scope for tuning of their electrical conductivity from semiconducting to metallic region by way of doping and are organic electro chromic materials with chemically active surface. But they are chemically very sensitive and have poor mechanical properties and thus possessing a processibility problem. Nanomaterial shows the presence of more sites for surface reactivity, they possess good mechanical properties and good dispersant too. Thus nanocomposites formed by combining conducting polymers and inorganic oxide nanoparticles possess the good properties of both the constituents and thus enhanced their utility. The properties of such type of nanocomposite are strongly depending on concentration of nanomaterials to be added. Conducting polymer composites is some suitable composition of a conducting polymer with one or more inorganic nanoparticles so that their desirable properties are combined successfully. The composites of core shell metal oxide particles-conducting polymer combine the electrical properties of the polymer shell and the magnetic, optical, electrical or catalytic characteristics of the metal oxide core, which could greatly widen their applicability in the fields of catalysis, electronics and optics. Moreover nanocomposite material composed of conducting polymers & oxides have open more field of application such as drug delivery, conductive paints, rechargeable batteries, toners in photocopying, smart windows, etc.The present work is mainly focussed on the synthesis, characterization and various application studies of conducting polymer modified TiO2 nanocomposites. The conclusions of the present work are outlined below, Mesoporous TiO2 was prepared by the cationic surfactant P123 assisted hydrothermal synthesis route and conducting polymer modified TiO2 nanocomposites were also prepared via the same technique. All the prepared systems show XRD pattern corresponding to anatase phase of TiO2, which means that there is no phase change occurring even after conducting polymer modification. Raman spectroscopy gives supporting evidence for the XRD results. It also confirms the incorporation of the polymer. The mesoporous nature and surface area of the prepared samples were analysed by N2 adsorption desorption studies and the mesoporous ordering can be confirmed by low angle XRD measurementThe morphology of the prepared samples was obtained from both SEM & TEM. The elemental analysis of the samples was performed by EDX analysisThe hybrid composite formation is confirmed by FT-IR spectroscopy and X-ray photoelectron spectroscopyAll the prepared samples have been used for the photocatalytic degradation of dyes, antibiotic, endocrine disruptors and some other organic pollutants. Photocatalytic antibacterial activity studies were also performed using the prepared systemsAll the prepared samples have been used for the photocatalytic degradation of dyes, antibiotic, endocrine disruptors and some other organic pollutants. Photocatalytic antibacterial activity studies were also performed using the prepared systems Polyaniline modified TiO2 nanocomposite systems were found to have good antibacterial activity. Thermal diffusivity studies of the polyaniline modified systems were carried out using thermal lens technique. It is observed that as the amount of polyaniline in the composite increases the thermal diffusivity also increases. The prepared systems can be used as an excellent coolant in various industrial purposes. Nonlinear optical properties (3rd order nonlinearity) of the polyaniline modified systems were studied using Z scan technique. The prepared materials can be used for optical limiting Applications. Lasing studies of polyaniline modified TiO2 systems were carried out and the studies reveal that TiO2 - Polyaniline composite is a potential dye laser gain medium.

MEMS-based Tunable Optical Filter Arrays for Nano-Spectrometer in the Visible Spectral Range

Optische Spektrometer sind bekannte Instrumente für viele Anwendungen in Life Sciences, Produktion und Technik aufgrund ihrer guten Selektivität und Sensitivität zusammen mit ihren berührungslosen Messverfahren. MEMS (engl. Micro-electro-mechanical system)-basierten Spektrometer werden als disruptive Technologie betrachtet, in der miniaturisierte Fabry-Pérot Filter als sehr attraktiv für die optische Kommunikation und 'Smart Personal Environments', einschließlich des medizinischen Anwendungen, zu nennen sind. Das Ziel dieser Arbeit ist, durchstimmbare Filter-Arrays mit kostengünstigen Technologien herzustellen. Materialien und technologische Prozesse, die für die Herstellung der Filter-Arrays benötigt werden, wurden untersucht. Im Rahmen dieser Arbeit, wurden durchstimmbare Fabry Pérot Filter-Arrays für den sichtbaren Spektralbereich untersucht, die als Nano-Spektrometer eingesetzt werden. Darüber hinaus wurde ein Modell der numerischen Simulation vorgestellt, die zur Ermittlung eines optimales geometrisches Designs verwendet wurde, wobei sich das Hauptaugenmerk der Untersuchung auf die Durchbiegung der Filtermembranen aufgrund der mechanischen Verspannung der Schichten richtet. Die geometrische Form und Größe der Filtermembranen zusammen mit der Verbindungsbrücken sind von entscheidender Bedeutung, da sie die Durchbiegung beeinflussen. Lange und schmale Verbindungsbrücken führen zur stärkeren Durchbiegung der Filtermembranen. Dieser Effekt wurde auch bei der Vergrößerung der Durchmesser der Membran beobachtet. Die Filter mit spiralige (engl. curl-bent) Verbindungsbrücken führten zu geringerer Deformation als die mit geraden oder gebogenen Verbindungsbrücken. Durchstimmbare Si3N4/SiO2 DBR-basierende Filter-Arrays wurden erfolgreich hergestellt. Eine Untersuchung über die UV-NIL Polymere, die als Opferschicht und Haltepfosten-Material der Filter verwendet wurden, wurde durchgeführt. Die Polymere sind kompatibel zu dem PECVD-Verfahren, das für die Spiegel-Herstellung verwendet wird. Die laterale Strukturierung der DBR-Spiegel mittels des RIE (engl. Reactive Ion Etching)-Prozesses sowie der Unterätz-Prozess im Sauerstoffplasma zur Entfernung der Opferschicht und zum Erreichen der Luftspalt-Kavität, wurden durchgeführt. Durchstimmbare Filter-Arrays zeigten einen Abstimmbereich von 70 nm bei angelegten Spannungen von weniger als 20 V. Optimierungen bei der Strukturierung von TiO2/SiO2 DBR-basierenden Filtern konnte erzielt werden. Mit der CCP (engl. Capacitively Coupling Plasma)-RIE, wurde eine Ätzrate von 20 nm/min erreicht, wobei Fotolack als Ätzmaske diente. Mit der ICP (engl. Inductively Coupling Plasma)-RIE, wurden die Ätzrate von mehr als 60 nm/min mit einem Verhältniss der Ar/SF6 Gasflüssen von 10/10 sccm und Fotolack als Ätzmasken erzielt. Eine Ätzrate von 80 bis 90 nm/min wurde erreicht, hier diente ITO als Ätzmaske. Ausgezeichnete geätzte Profile wurden durch den Ätzprozess unter Verwendung von 500 W ICP/300 W RF-Leistung und Ar/SF6 Gasflüsse von 20/10 sccm erreicht. Die Ergebnisse dieser Arbeit ermöglichen die Realisierung eines breiten Spektralbereichs der Filter-Arrays im Nano-Spektrometer.

On the application of nanostructured electrodes prepared by Ti/TiO2/WO3 template : A case study of removing toxicity of indigo using visible irradiation

New assays with HepG2 cells indicate that Indigo Carmine (IC), a dye that is widely used as additive in many food and pharmaceutical industries exhibited cytotoxic effects. This work describes the development of a bicomponent nanostructured Ti/TiO2/WO3 electrode prepared by template method and investigates its efficiency in a photoelectrocatalytic method by using visible light irradiation and applied potential of 1V. After 2h of treatment there are reduction of 97% discoloration, 62% of mineralization and formation of three byproducts assigned as: 2-amine-5-sulfo-benzoic acid, 2,3-dioxo-14-indole-5-sulfonic acid, and 2-amino-α-oxo-5-sulfo-benzeneacetic acid were identified by HPLC-MS/MS. But, cytotoxicity was completely removed after 120min of treatment. © 2013 Elsevier Ltd.