Influence of pesticides on polymer structure during accelerated aging of poly (ethylene terephthalate)

Upotreba ambalaže od poli(etilen tereftalata), PET, u industriji pesticida sve je zastupljenija zahvaljujući dobroj dimenzionoj stabilnosti PET, hemijskoj otpornosti, mehaničkim svojstvima i transparentnosti. Imajući u vidu da se u formulaciji pesticida koriste organski rastvarači i jedinjenja petrohemijskog porekla koja mogu biti i toksična, jasno je da je izbor amabalaže za pakovanje pesticida izuzetno važan. U praksi tu odluku donosi proizvođač pesticida bez validne metode koja bi potvrdila opravdanost izbora određenog pakovanja. Takođe, upotreba pesticida upakovanih u plastičnu ambalažu doprinosi porastu ambalažnog otpada od plastičnih materijala. Na osnovu statističkih analiza o kretanju i postupanju sa ambalažnim otpadom u Evropi iz 2019. godine, oko 75 % ambalažnog otpada od plastičnih materijala se reciklira ili koristi kao energent, dok ostatak (oko 25 %) ukupnih količina ambalažnog otpada biva uskladišteno na deponijama, najčešće kao neadekvatno uskladišten ambalažni otpad bez procene rizika na životnu sredinu i uticaja degradacije polimera i ostataka upakovanih proizvoda koji se mogu zadržati u plastičnom materijalu. Cilj ove disertacije bio je ispitivanje mogućnosti i opravdanosti pakovanja organskih rastvarača i pesticida u obliku koncentrata za emluzije (EC) sa aspekta stabilnosti, sigurnosti i reciklabilnosti PET ambalaže uzimajući u obzir promene na PET ambalaži do kojih dolazi pod dejstvom upakovanih pesticida tokom životnog veka proizvoda. Osnova eksperimentalnog rada u disertaciji bila je metoda CIPAC 1.MT.46 koja se koristi za određivanje stabilnosti pesticida u originalnoj ambalaži i podrazumeva skladištenje pesticida na 54 ± 2 °C tokom 14 dana i simulaciju ponašanja proizvoda tokom dve godine roka trajanja („test starenja“). Promene na PET bocama konstatovane tokom „testa starenja“ (promena mase boca, promena stepena kristaliničnosti, promena dimenzija boca izazvane bubrenjem polimernog materijala, kao i sadržaj apsorbovanog rastvarača/pesticida) ukazale su na promene u strukturi PET boca. Udeo kristalne faze je određen metodom analize slike uz primenu softvera Image Pro Plus kao nedestruktivne metode kojom se brzo i efikasno dobijaju informacije o promeni strukture PET ambalaže tokom „veka trajanja" pesticida. Primenom analize slike detektovane su i izdvojene zone na bocama koje su pretrpele promene tokom „testa starenja”, a merenjem transperentnosti i stepena sivoće izdvojenih zona, izvršena je korelacija dobijenih podataka sa sadržajem udela kristalne faze PET-a. Konvencionalna DSC VI metoda za određivanje udela kristalne faze potvrdila je saglasnost sa rezultatima dobijenih određivanjem udela kristalne faze metodom analize slike. Pored promena u strukturi, eksperimentalni rezultati nakon „testa starenja“ ukazali su na različit stepen difuzije i emisije različitih tipova organskih rastvarača i pesticida kroz PET boce, ali i na značajnu količinu organskih rastvarača/pesticida koji su ostali apsorbovani u PET-u čime je potvrđena opravdanost kategorizacije PET ambalaže za pakovanje pesticida kao opasnog otpada koji zahteva poseban tretman. Na osnovu rezultata promena mase boca tokom „testa starenja“ različitih formulacija pesticida sa aktivnom materijom Cipermetrin (CY) u disertaciji je opisan i postupak stvaranja veštačke neuronske mreže sa opštom regresijom (General regression neural network -GRNN) čijom se primenom može predvideti emisija pesticida kroz PET boce. Na osnovu dobijenih eksperimentalnih podataka (promena mase boca sa pesticidima i vremena skladištenja), obučavanja i testiranja neuronske mreže, analizom „osetljivosti" modela veštačke neuronske mreže, dobijeni su pouzdani podaci o proceni emisije pesticida kroz PET ambalažu tokom vremena skladištenja.The use of poly (ethylene terephthalate), PET packaging in the pesticide industry is a consequence of good dimensional stability of PET, chemical resistance, mechanical properties and transparency. Bearing in mind that organic solvents and compounds of petrochemical origin are used in the formulation of pesticides, which can also be toxic, the choice of packaging for pesticide packaging is extremely important. In practice, this decision is made by the pesticide manufacturer without a valid method that would confirm the justification of the choice of a particular package. Also, the use of pesticides packed in plastic packaging contributes to the increase of packaging waste from plastic materials. Based on statistical analyzes on the movement and treatment of packaging waste in Europe in 2019, about 75% of packaging waste from plastic materials is recycled or used as energy, while the rest (about 25%) of total packaging waste is stored in landfills, most often as inadequately stored packaging waste without an environmental risk assessment and the impact of degradation of polymers and residues of packaged products that can be retained in the plastic material. The aim of this dissertation was to examine the possibility and justification of packaging organic solvents and pesticides in the form of emulsion concentrates (EC) from the aspect of stability, safety and recyclability of PET packaging, taking into account changes in PET packaging that occur under the action of packaged pesticides. The basis of experimental work in the dissertation was the method CIPAC 1.MT.46 which is used to determine the stability of pesticides in the original packaging and involves storing pesticides at 54 ± 2 ° C for 14 days and simulates the behavior of the product during two years ("aging test“). Changes in PET bottles observed during the "aging test" (change in the bottle weight, change in the degree of crystallinity, change in the bottle size caused by swelling of the polymer material, as well as the content of absorbed solvent / pesticide) indicated changes in the structure of PET bottles. The crystalline phase was determined by the image analysis method using Image Pro Plus software as a non-destructive method that quickly and VIII efficiently provides information on changes in the structure of PET packaging during the "shelflife" of pesticides. "Aging test", and by measuring the transparency and degree of grayness of the isolated zones, the obtained data were correlated with the content of the crystalline phase of PET. In addition to the changes in the structure, the experimental results after the "aging test" showed a different degree of diffusion and emission of different types of organic solvents and pesticides through PET bottles, but also a significant amount of organic solvents/pesticides that remained absorbed in PET, confirmed justification of categorization of PET packaging for pesticide packaging as hazardous waste that requires special treatment. Based on the results of the bottle mass change during the "aging test" of different pesticide formulations with the active substance Cypermethrin (CI), the dissertation describes the procedure of creating artificial neural networks with general regression (General regression neural network-GRNN) which can predict pesticide emissions through PET bottles. Based on the obtained experimental data (change in weight of pesticide bottles and storage time), training and testing of neural networks, analysis of "sensitivity" of artificial neural network models, reliable data on pesticide emissions through PET packaging during storage time were obtained

Valorization of Winery Waste: Prokupac Grape Seed as a Source of Nutritionally Valuable Oil

Valorization of winery waste is a promising solution for waste management with additional benefit of bioactive compounds isolation. The aim of this study was to analyze the nutritional and bioactive potential of oil derived from Serbian autochthonous grape seed variety Prokupac and to compare it with known international grape varieties. Additionally, two extraction methods (ultrasound assisted extraction and cold pressing) were used in order to determine their influence on physico-chemical and nutritive characteristics of grape seed oil. Different methods, including determination of physicochemical properties, content of bioactive compounds, oxidative stability and antioxidative capacity were used for the characterization of grape seed oils. Results indicated that the higher yield was obtained by ultrasound assisted extraction compared to cold pressing. The application of ultrasound assisted extraction resulted in increased α-tocopherol content and better antioxidant capacity and oxidative stability of oil. Significant differences in bioactive composition were observed for Prokupac seed oil compared to the other grape varieties. Oil extracted from Prokupac grape seed had the lowest content of polyunsaturated and the highest content of saturated fatty acids, the highest content of α-tocopherol and consequently, the best antioxidative capacity. Prokupac grape seed has a great potential for isolation of nutritive and bioactive valuable oil

ArheoPackPro! – programski sistem za unos, obradu i interpretaciju digitalne arheološke dokumentacije

U ovom radu prikazan je programski paket ArheoPackPro!, sistem koji je nastao tokom arheoloških iskopavanja na praistorijskom nalazištu Vinča, koji arheloškim ekipama omogućava kompletan unos i obradu podataka prikupljenih na terenu. Do sada je postojala velika praznina između novih kompjuterskih tehnologija i zastarelih metoda čuvanja i obrade materijala s arheoloških lokaliteta. Dobijeni podaci bili su kombinacija raznovrsnih elemenata, od slike i crteza, preko velike količine specifičnih numeričkih vrednosti i tekstuelnih opisa. S mogućnostima koje pružaju današnji kompjuterski sistemi, ArheoPackPro! bi trebalo da zameni proces unosa i obrade ovakve dokumentacije, a samim tim ubrza rad na terenu, proširi i poveća kvalitet dobijene dokumentacije, kao i da uvede do sada nedostupne metode za obradu ovako unetog terenskog materijala. ArheoPackPro! je programski paket baziran na modularnom sistemu i pristupu. Ovo znači da svaki element sistema komunicira i razmenjuje podatke s ostalim elementima, ali je u isto vreme i nezavisan. Ovakav pristup ostavlja mogućnost za stalno dodavanja novih opcija, kao i za proširivanje i doradu već postojećih u okviru ArheoPackPro! sistema

Influence of pesticides on polymer structure during accelerated aging of poly (ethylene terephthalate)

Upotreba ambalaže od poli(etilen tereftalata), PET, u industriji pesticida sve je zastupljenija zahvaljujući dobroj dimenzionoj stabilnosti PET, hemijskoj otpornosti, mehaničkim svojstvima i transparentnosti. Imajući u vidu da se u formulaciji pesticida koriste organski rastvarači i jedinjenja petrohemijskog porekla koja mogu biti i toksična, jasno je da je izbor amabalaže za pakovanje pesticida izuzetno važan. U praksi tu odluku donosi proizvođač pesticida bez validne metode koja bi potvrdila opravdanost izbora određenog pakovanja. Takođe, upotreba pesticida upakovanih u plastičnu ambalažu doprinosi porastu ambalažnog otpada od plastičnih materijala. Na osnovu statističkih analiza o kretanju i postupanju sa ambalažnim otpadom u Evropi iz 2019. godine, oko 75 % ambalažnog otpada od plastičnih materijala se reciklira ili koristi kao energent, dok ostatak (oko 25 %) ukupnih količina ambalažnog otpada biva uskladišteno na deponijama, najčešće kao neadekvatno uskladišten ambalažni otpad bez procene rizika na životnu sredinu i uticaja degradacije polimera i ostataka upakovanih proizvoda koji se mogu zadržati u plastičnom materijalu. Cilj ove disertacije bio je ispitivanje mogućnosti i opravdanosti pakovanja organskih rastvarača i pesticida u obliku koncentrata za emluzije (EC) sa aspekta stabilnosti, sigurnosti i reciklabilnosti PET ambalaže uzimajući u obzir promene na PET ambalaži do kojih dolazi pod dejstvom upakovanih pesticida tokom životnog veka proizvoda. Osnova eksperimentalnog rada u disertaciji bila je metoda CIPAC 1.MT.46 koja se koristi za određivanje stabilnosti pesticida u originalnoj ambalaži i podrazumeva skladištenje pesticida na 54 ± 2 °C tokom 14 dana i simulaciju ponašanja proizvoda tokom dve godine roka trajanja („test starenja“). Promene na PET bocama konstatovane tokom „testa starenja“ (promena mase boca, promena stepena kristaliničnosti, promena dimenzija boca izazvane bubrenjem polimernog materijala, kao i sadržaj apsorbovanog rastvarača/pesticida) ukazale su na promene u strukturi PET boca. Udeo kristalne faze je određen metodom analize slike uz primenu softvera Image Pro Plus kao nedestruktivne metode kojom se brzo i efikasno dobijaju informacije o promeni strukture PET ambalaže tokom „veka trajanja" pesticida. Primenom analize slike detektovane su i izdvojene zone na bocama koje su pretrpele promene tokom „testa starenja”, a merenjem transperentnosti i stepena sivoće izdvojenih zona, izvršena je korelacija dobijenih podataka sa sadržajem udela kristalne faze PET-a. Konvencionalna DSC VI metoda za određivanje udela kristalne faze potvrdila je saglasnost sa rezultatima dobijenih određivanjem udela kristalne faze metodom analize slike. Pored promena u strukturi, eksperimentalni rezultati nakon „testa starenja“ ukazali su na različit stepen difuzije i emisije različitih tipova organskih rastvarača i pesticida kroz PET boce, ali i na značajnu količinu organskih rastvarača/pesticida koji su ostali apsorbovani u PET-u čime je potvrđena opravdanost kategorizacije PET ambalaže za pakovanje pesticida kao opasnog otpada koji zahteva poseban tretman. Na osnovu rezultata promena mase boca tokom „testa starenja“ različitih formulacija pesticida sa aktivnom materijom Cipermetrin (CY) u disertaciji je opisan i postupak stvaranja veštačke neuronske mreže sa opštom regresijom (General regression neural network -GRNN) čijom se primenom može predvideti emisija pesticida kroz PET boce. Na osnovu dobijenih eksperimentalnih podataka (promena mase boca sa pesticidima i vremena skladištenja), obučavanja i testiranja neuronske mreže, analizom „osetljivosti" modela veštačke neuronske mreže, dobijeni su pouzdani podaci o proceni emisije pesticida kroz PET ambalažu tokom vremena skladištenja.The use of poly (ethylene terephthalate), PET packaging in the pesticide industry is a consequence of good dimensional stability of PET, chemical resistance, mechanical properties and transparency. Bearing in mind that organic solvents and compounds of petrochemical origin are used in the formulation of pesticides, which can also be toxic, the choice of packaging for pesticide packaging is extremely important. In practice, this decision is made by the pesticide manufacturer without a valid method that would confirm the justification of the choice of a particular package. Also, the use of pesticides packed in plastic packaging contributes to the increase of packaging waste from plastic materials. Based on statistical analyzes on the movement and treatment of packaging waste in Europe in 2019, about 75% of packaging waste from plastic materials is recycled or used as energy, while the rest (about 25%) of total packaging waste is stored in landfills, most often as inadequately stored packaging waste without an environmental risk assessment and the impact of degradation of polymers and residues of packaged products that can be retained in the plastic material. The aim of this dissertation was to examine the possibility and justification of packaging organic solvents and pesticides in the form of emulsion concentrates (EC) from the aspect of stability, safety and recyclability of PET packaging, taking into account changes in PET packaging that occur under the action of packaged pesticides. The basis of experimental work in the dissertation was the method CIPAC 1.MT.46 which is used to determine the stability of pesticides in the original packaging and involves storing pesticides at 54 ± 2 ° C for 14 days and simulates the behavior of the product during two years ("aging test“). Changes in PET bottles observed during the "aging test" (change in the bottle weight, change in the degree of crystallinity, change in the bottle size caused by swelling of the polymer material, as well as the content of absorbed solvent / pesticide) indicated changes in the structure of PET bottles. The crystalline phase was determined by the image analysis method using Image Pro Plus software as a non-destructive method that quickly and VIII efficiently provides information on changes in the structure of PET packaging during the "shelflife" of pesticides. "Aging test", and by measuring the transparency and degree of grayness of the isolated zones, the obtained data were correlated with the content of the crystalline phase of PET. In addition to the changes in the structure, the experimental results after the "aging test" showed a different degree of diffusion and emission of different types of organic solvents and pesticides through PET bottles, but also a significant amount of organic solvents/pesticides that remained absorbed in PET, confirmed justification of categorization of PET packaging for pesticide packaging as hazardous waste that requires special treatment. Based on the results of the bottle mass change during the "aging test" of different pesticide formulations with the active substance Cypermethrin (CI), the dissertation describes the procedure of creating artificial neural networks with general regression (General regression neural network-GRNN) which can predict pesticide emissions through PET bottles. Based on the obtained experimental data (change in weight of pesticide bottles and storage time), training and testing of neural networks, analysis of "sensitivity" of artificial neural network models, reliable data on pesticide emissions through PET packaging during storage time were obtained

Arheopackpro!: A software package for processing and interpretation of digital archeological documentation

U ovom radu prikazan je programski paket ArheoPackPro!, sistem koji je nastao tokom arheoloških iskopavanja na praistorijskom nalazištu Vinča, koji arheološkim ekipama omogućava kompletan unos i obradu podataka prikupljenih na terenu. Do sada je postojala velika praznina između novih kompjuterskih tehnologija i zastarelih metoda čuvanja i obrade materijala s arheoloških lokaliteta. Dobijeni podaci bili su kombinacija raznovrsnih elemenata, od slike i crteža, preko velike količine specifičnih numeričkih vrednosti i tekstualnih opisa. S mogućnostima koje pružaju današnji kompjuterski sistemi, ArheoPackPro! bi trebalo da zameni proces unosa i obrade ovakve dokumentacije, a samim tim ubrza rad na terenu, proširi i poveća kvalitet dobijene dokumentacije, kao i da uvede do sada nedostupne metode za obradu ovako unetog terenskog materijala. ArheoPackPro! je programski paket baziran na modularnom sistemu i pristupu. Ovo znači da svaki element sistema komunicira i razmenjuje podatke s ostalim elementima, ali je u isto vreme i nezavisan. Ovakav pristup ostavlja mogućnost za stalno dodavanja novih opcija, kao i za proširivanje i doradu već postojećih u okviru ArheoPackPro! sistema.We present the software package ArheoPackPro!, a system conceived and tested during archaeological excavations at the site of Vinca. The system is built on a modular basis. The backbone of the system is EDM log book where alt the information on different aspects of archaeological fieldwork is linked to

Praćenje uticaja hlorbenzena na ubrzano starenje poli(etilen tereftalatnih) bočica metodom analize slike

Poly(ethylene terephthalate) (PET) is a material widely used for various kinds of packaging, because of its superior barrier properties, low price and simple processing. Apart from aqueous products, it is being used as a packaging material for organic solvent based products, eg. for medicinal purposes, or for pesticides. In this work the influence of chlorobenzene on the properties of PET bottles was investigated. The bottles (50 ml) were filled with chlorobenzene and were subject to aging at 54 °C for 15 days. Afterwards, the bottles were characterized by a method of image analysis, using the Image-Pro Plus programme, where the dimension alterations were defined, together with the zones where the material was damaged. The change of mass of the bottles was also established. The results show that the bottles that were subject to chlorobenzene have acquired over 5% of the mass during the experiment, whilst the control samples - empty ones or the ones filled with water, showed no significant change in mass. The zones of the largest alteration of dimension were established, and it was concluded that these are present around the screw thread and at the peripheral zones of the bottom, i.e. where the highest strains are present. It has also been shown that the zone of increased crystallinity, that stems from the PET structure ordering as a result of solvent penetration, is present around points of irregular structure, and these points act as entry points for solvent penetration into the material as opposed to the absorption through the whole bottle surface.Poli(etilen tereftalat) (PET) je materijal koji se koristi za izradu različitih vrsta ambalaže zbog svojih dobrih barijerinih svojstava, niske cene i jednostavne prerade. Osim proizvoda na bazi vode, PET je često materijal koji se koristi kao ambalaža za proizvode rastvorene u organskim rastvaračima, kao što su medicinski proizvodi ili pesticidi. U ovom radu ispitivanje uticaj hlorbenzena na bočice od PET-a (50 ml), tako što su bočice punjene hlorbenzenom i izlagane ubrzanom starenju na 54 °C tokom 15 dana. Bočice su potom karakterisane metodom analize slike, korišćenjem programa Image-Pro Plus pomoću koga je određena promena dimenzija boca tokom ovog eksperimenta i definisane zone oštećenja boce. Takođe je merenjem određena i promena mase bočica. Pokazalo se da pod dejstvom hlorbenzena dolazi do povećanja mase bočice od preko 5%, za razliku od kontrolnih uzoraka koji nisu punjeni ili su bili punjeni vodom kod kojih ne dolazi do porasta mase tokom eksperimenta. Definisane su i zone promene dimenzije boce, gde se vidi da su one najveće na delu boce gde se nalazi navoj za zapušač i u perifernim delovima dna boce gde su najveći zaostali naponi. Pokazalo se i da se oblast povećane kristaliničnosti koja je posledica uređivanja strukture PET-a pod dejstvom rastvarača koji je materijal apsorbovao javlja oko tačaka gde postoji nepravilnost strukture i da kroz ta mesta dolazi do penetracije hlorbenzena, a ne ravnomerno kroz celu strukturu materijala

CHITAS - a mouse tracking system in a web environment

Eye tracking may be very effective and has great potential in user interface optimisation. The main disadvantage of tracking what a user is looking at is the need for complex and expensive equipment, and a controlled laboratory environment. Mouse tracking is a widely applicable alternative to eye tracking. This paper presents the architecture of CHITAS (Computer-Human Interaction Tracking and Analytics System) which enables information to be gathered about mouse movement in a web environment, and analytical processing of the collected data

Migration of cypermethrin to and through the PET containers and artificial neural network-based estimation of its emission

Nowadays, the extensive use of pesticides in crops production puts a significant challenge to minimize its side effects along with safe production, storage, and after-use treatment. This paper reports results related to the emission of certain pesticide formulations through the PET containers, as well as, their mitigation to the PET containers during their storage. The influence of storage time on cypermethrin migration to and through the PET was studied in short-term Collaborative International Pesticides Analytical Council test lasting up to 30 days. The PET containers were filled with pure xylene and pesticide formulations, where the amount of active substance, cypermethrin (CY), varied from 5 to 20 wt%, while the amount of emulsifier was kept constant. The results indicate that pesticide formulations diffuse to PET containers with an average increase of its initial mass up to 1.5%. The most intensive diffusion is in the first 24 months of storage, after its rate significantly decreases. It should be noted that the diffusion studied pesticide formulations are also very dependent on CY concentration. Besides the migration to the PET containers, it was also found that pesticide formulation was emitted through the PET containers in the first 17 to 24 months of storage depending on CY concentration. Emission rates were also dependent on CY concentration and were in the range of 15.3 to 38.0 mg/month center dot container. The emission through the PETcontainers was successfully predicted using artificial neural networks with R-2 = 0.94 and the mean absolute percentage error (MAPE) of only 6.2% on testing

Segmentirana zaštita korisničkih podataka u modernim poslovnim sistemima

U ovom radu analiziraju se postojeća i predlaže se novorešenje problema vezanog za zaštitu korisničkih podatakamodernih poslovnih sistema. Nova metoda se zasnovana naupotrebi složenih i slučajnih dodatnih vrednosti priindividualnom generisanju heš vrednosti za lozinku koju je uneokorisnik kao i upotreba segmentnog hešovanja za šifrovanjelozinke uz standardnu metodu hešovanja SHA512. Lozinka senakon šifrovanja deli u dva dela i delovi se čuvaju u dve zasebnebaze podataka koje se nalaze na različitim platformama