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Applicability of various thermoanalytical methods for analyzing plastics and corresponding microplastics
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Scientists studied how everyday plastic items—bottle caps, cigarette filters, and tire fragments—break down when heated, since these are common sources of microplastics in our environment. They found that tiny microplastic particles actually degrade somewhat differently than larger plastic pieces, and identified specific chemicals released during breakdown (like acetic acid from cigarette filter material), which helps scientists better predict what harmful substances these plastics might release as they degrade in nature. This matters because understanding exactly how and what microplastics break down into can help researchers assess potential risks to human health and the environment.
Plastični materiali so zaradi svoje široke uporabnosti med najpogostejšimi viri mikroplastike (MP) v okolju. Kljub obstojnosti in kemijski stabilnosti teh materialov ta nastaja kot posledica mehanske obrabe, razgradnje zaradi izpostavljenosti UV svetlobi in toplotnih obremenitev, pri čemer se sproščajo delci različnih velikosti in kemijskih lastnosti. Razumevanje termičnega obnašanja plastičnih materialov je zato ključno za oceno njihove stabilnosti, mehanizmov razgradnje ter nastajanja hlapnih produktov, ki vplivajo na okolje in zdravje organizmov. V magistrskem delu sem s kombinacijo tehnik termične analize preučevala termične lastnosti treh izbranih plastičnih materialov, katerih glavna sestavina so polimeri: polietilen visoke gostote (HDPE), acetilceluloza (CA) in pnevmatika, ki je kompozit naravne in sintetične gume (NR/SBR/BR). Izbrani materiali predstavljajo pogoste vire MP, saj izvirajo iz odpadnih zamaškov, cigaretnih filtrov in delcev, ki nastanejo z obrabo pnevmatik. S termogravimetrijo (TGA) sem določila temperaturna območja razpada ter primerjala vpliv hitrosti segrevanja, mase vzorca in velikosti delcev na stopnjo razpada. Ugotovila sem, da se mikroplastika razkraja nekoliko drugače kot večji koščki materiala, kar potrjuje vpliv specifične površine na potek razgradnje. Diferenčna dinamična kalorimetrija (DSC) je dopolnila rezultate TGA analize z vpogledom v entalpijo procesov, ki spremljajo razpad v inertni in oksidativni atmosferi. Za določitev kinetičnih parametrov sem uporabila izokonverzijski metodi Kissinger-Akahira-Sunose (KAS) in Ozawa-Flynn-Wall (OFW), ki omogočata izračun aktivacijskih energij (Ea) pri različnih stopnjah pretvorbe. Pri HDPE so bile vrednosti Ea skozi celoten razpad podobne, medtem ko sta imeli CA in guma bolj kompleksno kinetično razgradnjo, skladno z njuno kemijsko sestavo. Za identifikacijo hlapnih produktov razpada sem uporabila sklopljeni tehniki TGA-FTIR in TGA-IST16-GC-MS. TGA-FTIR je omogočila spremljanje funkcionalnih skupin v nastajajočih plinih, TGA-IST16-GC-MS pa je zagotovila ločevanje in natančnejšo identifikacijo posameznih spojin. S TGA-FTIR sem analizirala vse tri vzorce, medtem ko sem s TGA-IST16-GC-MS analizirala le zelene zamaške in cigaretne filtre. Najizrazitejši signali so bili pri HDPE alifatski ogljikovodiki, pri CA pa ocetna kislina, kar je skladno z njunimi mehanizmi razgradnje. Kombinacija obeh metod se je izkazala kot učinkovita pri razumevanju kemijskih procesov, ki potekajo med termičnim razpadom polimerov.
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