1. Hydrothermal decomposition of virgin and waste polylactic acid with subcritical water under N[sub]2 and air atmospheresMaja Čolnik, Mihael Irgolič, Mojca Škerget, 2025, izvirni znanstveni članek Opis: This study addresses the inherent shortcomings of poly (lactic acid) (PLA), a biodegradable polymer widely used in industries such as packaging and biomedical applications. The principal challenge of PLA resides in its low crystallinity, which detrimentally affects its mechanical properties and thermal stability. Additionally, PLA is prone to water and hydrolysis, which compromises its chemical resistance and can lead to degradation over time. To overcome surmount these limitations, the study focuses on the development of hybrid films through the blending of PLA with poly (l-lactide-co-ethylene adipate) (pLEA) block copolymers. The objective is to augment the crystallinity, mechanical performance, and chemical resistance of the resulting materials. The study employs a range of analytical techniques, including Nuclear Magnetic Resonance (NMR), Fourier Transform Infrared Spectroscopy (FTIR), X-ray Diffraction (XRD), Polarised Light Microscopy (PLM), Differential Scanning Calorimetry (DSC), and Thermogravimetric Analysis (TGA), to thoroughly characterize the copolymers and blend films. By systematically selecting blending ratios and processing methodologies, the study demonstrates enhancements in the properties of the resultant hybrid films compared to neat PLA. Specifically, the structure of films significantly changed from amorphous to crystalline in a short duration - 5 min, of annealing., leading to better tensile strength, modulus and reduced wettability, which are crucial for applications requiring durability and resistance to environmental factors. Films made from 30 wt% of pLEA 97.5/2.5 with 70 % of PLA by fast cooling exhibited outstanding mechanical properties, with a tensile strength 20 MPa higher than that of neat PLA films. Additionally, the chemical resistance may be improved, as evidenced by a decrease in wettability by approximately 15° and a reduction in the polar component of the surface free energy by about 7 mN/m. Hydrophobic, water-repellent materials resist penetration by water and other polar solvents, reducing exposure to corrosive substances and enhancing chemical resistance through barrier protection. Overall, this research addresses the limitations of PLA through innovative copolymerization and blending strategies, offering valuable insights into optimizing the material's properties for various practical applications.
Ključne besede: biopolymers recycling, polylactic acid, subcritical water, lactic acid, carboxylic acids, gaseous products
Objavljeno v DKUM: 01.04.2025; Ogledov: 0; Prenosov: 6
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2. Hydrolytic decomposition of corncobs to sugars and derivatives using subcritical waterMaja Čolnik, Mihael Irgolič, Amra Perva, Mojca Škerget, 2025, izvirni znanstveni članek Opis: Corncobs are a widespread and renewable by-product of corn cultivation that are typically considered waste or low-value material. Corncobs contain hemicellulose, cellulose, and lignin, which can be converted into valuable products using suitable techniques. Subcritical water is increasingly used as a green medium for the extraction of valuable components from biomass, as it has many advantageous properties (high yield, pure extracts, shorter times) compared to other organic solvents. For this reason, subcritical water was used in this study to extract valuable components from corncobs at different temperatures (150–250 °C) and reaction times (10–60 min). During the decomposition of corncobs, numerous valuable products are formed in the aqueous phase depending on the temperature and reaction time. In addition to sugars and their derivatives, phenolic compounds were also formed, which are of great importance in numerous applications. It was found that at low temperatures (150–170 °C) the hemicellulose in the corncobs begins to decompose and, in particular, the sugars (glucose, xylose, arabinose, and galactose) are initially formed in the aqueous phase. Higher temperatures (200 and 250 °C) are more favorable for the decomposition of corncobs into valuable components. The yield of sugars increases with temperature due to the degradation of the cellulose content of the lignocellulosic biomass. At the same time, several new valuable products (furfural, 5-hydroxymethylfurfural (5-HMF), 1,3-dihydroxyacetone, levulinic acid, and formic acid as well as phenolic components) are formed through the degradation of lignin and the further degradation of sugars. The most important products are certainly the furfurals, which are central platform compounds. The highest furfural content was reached at 200 °C and 60 min and accounted for almost half of all components in the aqueous phase (472.01 ± 5.64 mg/g dry extract). These biomass-derived sugars and derivatives can be used in the production of fuels, pharmaceuticals, biodegradable polymers, and surfactants.
Ključne besede: corncobs, subcritical water, biomass, valuable compounds, sugar derivates
Objavljeno v DKUM: 07.02.2025; Ogledov: 0; Prenosov: 9
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3. Degradation of waste tetra pak packaging with hydrothermal treatment in sub-/supercritical waterMihael Irgolič, Maja Čolnik, Petra Kotnik, Mojca Škerget, 2024, izvirni znanstveni članek Ključne besede: hydrothermal degradation, waste packing, tetra pak, subcritical water, subcritical waste, chemical recycling, one-stage process, two-stage process, product analysis
Objavljeno v DKUM: 16.07.2024; Ogledov: 88; Prenosov: 29
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4. Comparative study of hydrothermal decomposition of virgin and recycled polypropyleneMihael Irgolič, Maja Čolnik, Petra Kotnik, Lidija Čuček, Mojca Škerget, 2023, izvirni znanstveni članek Opis: Plastics are widely used due to their versatile properties and numerous applications. However, the proper management of plastic waste is a major challenge, even though it is recyclable. The process of repeated recycling can cause the quality of the material to decrease as unwanted contaminants and pollutants increase. This can affect the chemical recycling of plastics at the end of their life and the recovery of secondary products that can be used in other applications. In this study, the chemical degradation of virgin polypropylene (vPP) and recycled polypropylene (rPP) was investigated in supercritical water at a temperature of 450 °C and a reaction time of 15 to 240 min. The oil phase was the primary decomposition product and was obtained in high yield, which reached a maximum after 30 min of reaction time and was 96.9 % for vPP and 94.5 % for rPP. The results of our study show that there are some differences in the product composition depending on which material (vPP or rPP) is chemically recycled.
Ključne besede: virgin polypropylene, plastics, chemical degradation, chemical recycled
Objavljeno v DKUM: 18.04.2024; Ogledov: 235; Prenosov: 6
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5. Hidrotermična razgradnja večslojne odpadne embalaže : magistrsko deloMihael Irgolič, 2022, magistrsko delo Opis: V letu 2020 smo v Sloveniji pridelali več kot milijon ton odpadkov. Skoraj 30 % odpadkov predstavlja odpadna embalaža raznih produktov. Poznamo različne vrste embalaže: papirnato, stekleno, kovinsko, plastično, leseno in večslojno. Večslojni embalaži lahko rečemo tudi sestavljena. Ena izmed najpogosteje uporabljenih in dobro poznanih večslojnih embalaž je tudi tetrapak embalaža. Tetrapak embalaža je sestavljena iz papirja/kartona, polietilena (PE) in aluminija. Problem recikliranja tetrapak embalaže je v tem, da njenih sestavnih delov ni mogoče enostavno ločiti z mehanskimi metodami.
Uporaba pod- in nadkritičnih fluidov v različnih kemijskih procesih je vse pogostejša. Zaradi svoje dostopnosti in nizke cene je kot medij za uporabo v nadkritičnih procesih vse pogosteje uporabljena voda. V tem magistrskem delu smo preučevali razgradnjo odpadne tetrapak embalaže s pod- in nadkritično vodo v visokotlačnem in visokotemperaturnem šaržnem reaktorju pri temperaturi od 300 °C do 450 °C ter v časovnem obdobju med 15 in 60 min. Reakcije smo izvajali v eni in v dveh stopnjah. Razmerje odpadni materil/voda je bilo 1 g/10 mL. Nastale produkte v štirih fazah (plinski, vodni, oljni in trdni) smo analizirali s različnimi tehnikami (FTIR, TC, GC/MS, HPLC).
Enostopenjsko hidrotermično razgradnjo odpadne tetrapak embalaže smo izvedli pri temperaturi 425 °C oz. 450 °C in reakcijskem času 15 min ali 60 min. Ugotovili smo, da z višanjem temperature in daljšanjem reakcijskega časa narašča izkoristek oljne faze. Najvišji izkoristek oljne faze smo dobili pri temperaturi 450 °C in reakcijskem času 60 min in je znašal 60,7 %. V drugem delu smo izvedli dvostopenjsko hidrotermično razgradnjo odpadne tetrapak embalaže. Prvo stopnjo smo izvedli v podkritični vodi pri temperaturi 250 °C oz. 300 °C in reakcijskem času 30 oz. 60 min. Najvišji izkoristek vodne faze (18,0 %) smo določili pri temperaturi razgradnje 250 °C in reakcijskem času 60 min, najvišji izkoristek oljne faze (35,1 %) pa pri temperaturi razgradnje 300 °C in času 60 min. Drugo stopnjo razgradnje, kjer smo uporabili trdni preostanek iz prve stopnje, smo opravili pri temperaturi 425 oz. 450 °C in reakcijskem času 15 min. Najvišji izkoristek oljne faze po obeh stopnjah skupaj (65,5 %) dobimo pri vzorcu, ki smo ga v prvi stopnji razgradili pri temperaturi 300 °C in reakcijskem času 60 min, v drugi stopnji pa pri temperaturi 450 °C in reakcijskem času 15 min.
Oljni fazi smo določili kemijsko sestavo in ugotovili, da je sestavljena iz nasičenih in nenasičenih alifatskih ogljikovodikov, aromatskih spojin, ketonov, alkoholov in amidov. Analizirali smo tudi vodno fazo, v kateri so bili prisotni; glukoza, fruktoza, celobioza, gliceraldehid, anhidrid glukoze, levulinska kislina, furfural in 5-hidroksimetilfurfural. Plinska faza je vsebovala CO2 in ogljikovodike med C1-C6. Po razgradnji tetrapaka je kot trdni preostanek nastal aluminijev prah obdan s tanko plastjo PE.
Ključne besede: hidrotermična razgradnja, večslojna embalaža, tetrapak, odpadna embalaža, nadkritični fluidi, nadkritična voda
Objavljeno v DKUM: 08.07.2022; Ogledov: 809; Prenosov: 18
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6. Adsorpcija kovinskih ionov na žlindro : diplomsko delo univerzitetnega študijskega programa I. stopnjeMihael Irgolič, 2019, diplomsko delo Opis: Onesnaževanje z odpadnimi vodami predstavlja velik delež onesnaževanja narave. V teh odpadnih vodah se pogosto nahajajo tudi težke kovine, ki jih moramo zaradi ogrožanja okolja, živali in ljudi iz vode odstraniti. Kot poceni metoda za odstranjevanje težkih kovin iz vode, se je uveljavila adsorpcija. V iskanju učinkovitih ter poceni adsorbentov, se je dobro izkazala tudi žlindra, ki je stranski produkt pri proizvodnji jekla. V diplomskem delu predstavljamo rezultate raziskave adsorpcijskih lastnosti bele žlindre. Žlindri smo najprej določili specifično površino BET, volumen por, premer por, velikost delcev in zeta potencial. Nadalje smo preučevali vpliv pH in koncentracije na adsorpcijo železovih, bakrovih in svinčevih ionov. Hkrati smo preučili še medsebojni vpliv izbranih ionov na adsorpcijo.
Preučevali smo učinkovitost in kapaciteto adsorpcije in iz rezultatov ugotovili, da pH minimalno vpliva na adsorpcijo bakra in železa, svinec pa ima adsorpcijski maksimum pri pH 7. Pri preiskovanju vpliva koncentracije smo ugotovili, da učinkovitost adsorpcije s koncentracijo narašča za svinec, na baker in železo pa skoraj ne vpliva, saj je bila učinkovitost v območju koncentracij od 1 mM do 13 mM 100 %. Medsebojni vpliv ionov daje pozitivne rezultate na učinek adsorpcije.
Ključne besede: adsorpcija, žlindra, težke kovine, zeta potencial, BET
Objavljeno v DKUM: 17.09.2019; Ogledov: 1646; Prenosov: 114
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