Search results for: S. Paszkiewicz

Authors: Iman Taraghi, Sandra Paszkiewicz, Daria Pawlikowska, Anna Szymczyk, Izabela Irska, Rafal Stanik, Amelia Linares, Tiberio A. Ezquerra, Elżbieta Piesowicz

Abstract:

Currently, the massive use of thermoplastic materials in industrial applications causes huge amounts of polymer waste. The poly (ethylene glycol-co-1,4-cyclohexanedimethanol terephthalate) (PET-G) has been widely used in food packaging and polymer foils. In this research, the PET-G foils have been recycled and reused as a matrix to combine with different types of nanofillers such as carbon nanotubes, graphene nanoplatelets, and nanosized carbon black. The mechanical and electrical properties, as well as thermal stability and thermal conductivity of the PET-G, improved along with the addition of the aforementioned nanofillers and hybrid system of them.

Keywords: polymer hybrid nanocomposites, carbon nanofillers, recycling, physical performance

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Authors: S. Paszkiewicz, A. Zubkiewicz, A. Szymczyk, D. Pawlikowska, I. Irska, E. Piesowicz, A. Linares, T. A. Ezquerra

Abstract:

Over the last century, the world has become increasingly dependent on oil as its main source of chemicals and energy. Driven largely by the strong economic growth of India and China, demand for oil is expected to increase significantly in the coming years. This growth in demand, combined with diminishing reserves, will require the development of new, sustainable sources for fuels and bulk chemicals. Biomass is an attractive alternative feedstock, as it is widely available carbon source apart from oil and coal. Nowadays, academic and industrial research in the field of polymer materials is strongly oriented towards bio-based alternatives to petroleum-derived plastics with enhanced properties for advanced applications. In this context, 2,5-furandicarboxylic acid (FDCA), a biomass-based chemical product derived from lignocellulose, is one of the most high-potential biobased building blocks for polymers and the first candidate to replace the petro-derived terephthalic acid. FDCA has been identified as one of the top 12 chemicals in the future, which may be used as a platform chemical for the synthesis of biomass-based polyester. The aim of this study is to synthesize and characterize the multiblock copolymers containing rigid segments of poly(trimethylene 2,5-furanoate) (PTF) and soft segments of poly(tetramethylene oxide) (PTMO) with excellent elastic properties or aliphatic polyesters of polycaprolactone (PCL). Two series of PTF based copolymers, i.e., PTF-block-PTMO-T and PTF-block-PCL-T, with different content of flexible segments were synthesized by means of a two-step melt polycondensation process and characterized by various methods. The rigid segments of PTF, as well as the flexible PTMO/or PCL ones, were randomly distributed along the chain. On the basis of 1H NMR, SAXS and WAXS, DSC an DMTA results, one can conclude that both phases were thermodynamically immiscible and the values of phase transition temperatures varied with the composition of the copolymer. The copolymers containing 25, 35 and 45wt.% of flexible segments (PTMO) exhibited elastomeric property characteristics. Moreover, with respect to the flexible segments content, the temperatures corresponding to 5%, 25%, 50% and 90% mass loss as well as the values of tensile modulus decrease with the increasing content of aliphatic polyether or aliphatic polyester in the composition.

Keywords: furan based polymers, multiblock copolymers, supramolecular structure, functional properties

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Authors: I. Irska, S. Paszkiewicz, D. Pawlikowska, E. Piesowicz, A. Linares, T. A. Ezquerra

Abstract:

Due to the number of advantages such as high tensile strength, sensitivity to hydrolytic degradation, and biocompatibility poly(lactic acid) (PLA) is one of the most common polyesters for biomedical and pharmaceutical applications. However, PLA is a rigid, brittle polymer with low heat distortion temperature and slow crystallization rate. In order to broaden the range of PLA applications, it is necessary to improve these properties. In recent years a number of new strategies have been evolved to obtain PLA-based materials with improved characteristics, including manipulation of crystallinity, plasticization, blending, and incorporation into block copolymers. Among the other methods, synthesis of aliphatic-aromatic copolyesters has been attracting considerable attention as they may combine the mechanical performance of aromatic polyesters with biodegradability known from aliphatic ones. Given the need for highly flexible biodegradable polymers, in this contribution, a series of aromatic-aliphatic based on poly(butylene terephthalate) and poly(lactic acid) (PBT-b-PLA) copolyesters exhibiting superior mechanical properties were copolymerized with an additional poly(tetramethylene oxide) (PTMO) soft block. The structure and properties of both series were characterized by means of attenuated total reflectance – Fourier transform infrared spectroscopy (ATR-FTIR), nuclear magnetic resonance spectroscopy (¹H NMR), differential scanning calorimetry (DSC), wide-angle X-ray scattering (WAXS) and dynamic mechanical, thermal analysis (DMTA). Moreover, the related changes in tensile properties have been evaluated and discussed. Lastly, the viscoelastic properties of synthesized poly(ester-ether) copolymers were investigated in detail by step cycle tensile tests. The block lengths decreased with the advance of treatment, and the block-random diblock terpolymers of (PBT-ran-PLA)-b-PTMO were obtained. DSC and DMTA analysis confirmed unambiguously that synthesized poly(ester-ether) copolymers are microphase-separated systems. The introduction of polyether co-units resulted in a decrease in crystallinity degree and melting temperature. X-ray diffraction patterns revealed that only PBT blocks are able to crystallize. The mechanical properties of (PBT-ran-PLA)-b-PTMO copolymers are a result of a unique arrangement of immiscible hard and soft blocks, providing both strength and elasticity.

Keywords: aliphatic-aromatic copolymers, multiblock copolymers, phase behavior, thermoplastic elastomers

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Authors: J. C. Colmenares, M. Paszkiewicz-Gawron, D. Lomot, S. R. Pradhan, A. Qayyum

Abstract:

This work is a report of recent selected experiments of photocatalysis intensification using flow microphotoreactors (fabricated by an ultrasound-based technique) for photocatalytic selective oxidation of benzyl alcohol (BnOH) to benzaldehyde (PhCHO) (in the frame of the concept of lignin valorization), and the proof of concept of intensifying a flow selective photocatalytic oxidation process by acoustic cavitation. The synthesized photocatalysts were characterized by using different techniques such as UV-Vis diffuse reflectance spectroscopy, X-ray diffraction, nitrogen sorption, thermal gravimetric analysis, and transmission electron microscopy. More specifically, the work will be on: a Design and development of metal-containing TiO₂ coated microflow reactor for photocatalytic partial oxidation of benzyl alcohol: The current work introduces an efficient ultrasound-based metal (Fe, Cu, Co)-containing TiO₂ deposition on the inner walls of a perfluoroalkoxy alkanes (PFA) microtube under mild conditions. The experiments were carried out using commercial TiO₂ and sol-gel synthesized TiO₂. The rough surface formed during sonication is the site for the deposition of these nanoparticles in the inner walls of the microtube. The photocatalytic activities of these semiconductor coated fluoropolymer based microreactors were evaluated for the selective oxidation of BnOH to PhCHO in the liquid flow phase. The analysis of the results showed that various features/parameters are crucial, and by tuning them, it is feasible to improve the conversion of benzyl alcohol and benzaldehyde selectivity. Among all the metal-containing TiO₂ samples, the 0.5 at% Fe/TiO₂ (both, iron and titanium, as cheap, safe, and abundant metals) photocatalyst exhibited the highest BnOH conversion under visible light (515 nm) in a microflow system. This could be explained by the higher crystallite size, high porosity, and flake-like morphology. b. Designing/fabricating photocatalysts by a sonochemical approach and testing them in the appropriate flow sonophotoreactor towards sustainable selective oxidation of key organic model compounds of lignin: Ultrasonication (US)-assitedprecipitaion and US-assitedhydrosolvothermal methods were used for the synthesis of metal-oxide-based and metal-free-carbon-based photocatalysts, respectively. Additionally, we report selected experiments of intensification of a flow photocatalytic selective oxidation through the use of ultrasonic waves. The effort of our research is focused on the utilization of flow sonophotocatalysis for the selective transformation of lignin-based model molecules by nanostructured metal oxides (e.g., TiO₂), and metal-free carbocatalysts. A plethora of parameters that affects the acoustic cavitation phenomena, and as a result the potential of sonication were investigated (e.g. ultrasound frequency and power). Various important photocatalytic parameters such as the wavelength and intensity of the irradiated light, photocatalyst loading, type of solvent, mixture of solvents, and solution pH were also optimized.

Keywords: heterogeneous photo-catalysis, metal-free carbonaceous materials, selective redox flow sonophotocatalysis, titanium dioxide

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Authors: Marta Paszkiewicz, Justyna Łuczak, Martyna Marchelek, Adriana Zaleska-Medynska

Abstract:

In recent years, photocatalytical processes have been intensively investigated for destruction of pollutants, hydrogen evolution, disinfection of water, air and surfaces, for the construction of self-cleaning materials (tiles, glass, fibres, etc.). Titanium dioxide (TiO2) is the most popular material used in heterogeneous photocatalysis due to its excellent properties, such as high stability, chemical inertness, non-toxicity and low cost. It is well known that morphology and microstructure of TiO2 significantly influence the photocatalytic activity. This characteristics as well as other physical and structural properties of photocatalysts, i.e., specific surface area or density of crystalline defects, could be controlled by preparation route. In this regard, TiO2 particles can be obtained by sol-gel, hydrothermal, sonochemical methods, chemical vapour deposition and alternatively, by ionothermal synthesis using ionic liquids (ILs). In the TiO2 particles synthesis ILs may play a role of a solvent, soft template, reagent, agent promoting reduction of the precursor or particles stabilizer during synthesis of inorganic materials. In this work, the effect of the ILs anion type on morphology and photoactivity of TiO2 is presented. The preparation of TiO2 microparticles with spherical structure was successfully achieved by solvothermal method, using tetra-tert-butyl orthotitatane (TBOT) as the precursor. The reaction process was assisted by an ionic liquids 1-butyl-3-methylimidazolium bromide [BMIM][Br], 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF4] and 1-butyl-3-methylimidazolium haxafluorophosphate [BMIM][PF6]. Various molar ratios of all ILs to TBOT (IL:TBOT) were chosen. For comparison, reference TiO2 was prepared using the same method without IL addition. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Brenauer-Emmett-Teller surface area (BET), NCHS analysis, and FTIR spectroscopy were used to characterize the surface properties of the samples. The photocatalytic activity was investigated by means of phenol photodegradation in the aqueous phase as a model pollutant, as well as formation of hydroxyl radicals based on detection of fluorescent product of coumarine hydroxylation. The analysis results showed that the TiO2 microspheres had spherical structure with the diameters ranging from 1 to 6 µm. The TEM micrographs gave a bright observation of the samples in which the particles were comprised of inter-aggregated crystals. It could be also observed that the IL-assisted TiO2 microspheres are not hollow, which provides additional information about possible formation mechanism. Application of the ILs results in rise of the photocatalytic activity as well as BET surface area of TiO2 as compared to pure TiO2. The results of the formation of 7-hydroxycoumarin indicated that the increased amount of ·OH produced at the surface of excited TiO2 for samples TiO2_ILs well correlated with more efficient degradation of phenol. NCHS analysis showed that ionic liquids remained on the TiO2 surface confirming structure directing role of that compounds.

Keywords: heterogeneous photocatalysis, IL-assisted synthesis, ionic liquids, TiO2

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