Plasma-based surface modifications offer many interesting possibilities for the production of high value-added polymeric materials. In this work, different plasma-based synthetic concepts were employed to endow poly(ethylene terephthalate) (PET) fabrics with accessible amine functionalities. These concepts were compared to find out the appropriate engineering methods, which can be further accepted by textile industries to overcome the limited reactivity of PET fabric surfaces, while the bulk characteristics are kept unaffected. Amine functionalities were introduced onto the surface of PET fabrics using either low-pressure ammonia plasma treatment or coating oxygen plasma-treated PET fabric with cationic polyelectrolytes. Two different cationic polyelectrolytes were used in this study namely poly(diallyldimethylammonium chloride) as an example of strong polyelectrolytes and poly(vinyl amine-co-vinyl amide) as an example of weak polyelectrolytes. The modified surfaces were characterized by a combination of various surface-sensitive techniques such as X-ray photoelectron spectroscopy (XPS), electrokinetic measurements and time-dependent contact angle measurements. Furthermore, the amine functionalities introduced by different surface modifications were used for the subsequent immobilization of various classes of anionic dyes to evaluate the efficiency of different surface modifications. Color strength (K/S) and fastness measurements of colored fabrics were also explored. Their results can be taken as a measure of the extent of the interaction between different modified surfaces and anionic dyes. Finally, it was demonstrated that anchoring poly(vinyl amine-co-vinyl amide) layer onto PET fabric surfaces modified with low-pressure oxygen plasma is an efficient approach to improve coloration behavior and to overcome different problems related to PET fabrics coloration, such as coloration of PET/wool blend fabric with a single class of dyes. This is a crucial step towards the substrate independent surface coloration, which becomes dependent on the properties of the top layer rather than chemical structure of the fibers.

Pour comprendre l'origine de la torsion lamellaire dans le poly(triméthylène téréphtalate), PTT, une étude a été entrepris sur la structure des sphérolites à bandes de PTT en utilisant la micro-diffraction des rayons-X sur une source synchrotrone. Nous avons démontré que les pics de diffraction de la maille triclinique de PTT révèlent une variation périodique de l'intensité en fonction de la distance jusqu'au centre sphérolitique lorsque nous effectuons un balayage avec un micro-faisceau de rayons X. Cela indique que la torsion lamellaire est strictement uniforme et régulière. Celte derrière observation est plus compatible avec le modèle expliquant la torsion comme résultat de contraintes surfaciques que des dislocations-vis géantes. En outre, les données expérimentales montrent que les polymères achiraux ne sont pas indifférents par rapport à l'inversion de la chiralité lamellaire, et que le changement de la chiralité est nécessairement accompagné d'un changement de signe du vecteur de croissance. En plus, nous avons observé que l'inclinaison globale de la chaîne (c'est à dire, l'inclinaison du paramètre c de la maille dans le plan perpendiculaire à la direction de la croissance rapide) n'affecte pas la vitesse et le sens de la torsion. Cela remet en question la seconde hypothèse du modèle de Keith et Padden. Par contre, l'inclinaison des segments de la chaine à l'interface du cristal lamellaire peut être identifiée comme le facteur clé déterminant les contraintes superficielles qui provoquent la torsion lamellaire. Avec la variation de l'épaisseur du cristal la chiralité lamellaire change, ce qui dû au changement de l'angle des segments polymères à l'interface. / To address the origin of the lamellar twisting in polytrimethylene terephthalate (PTT) an in-depth micro-focus X-ray scattering study was correlated to the data derived using conventional polarized optical microscopy to study the banded spherulite texture for PTT. It is shown that the diffraction peaks of the triclinic lattice of PTT show a periodical pattern as a function of the distance from the spherulite center when scanned with the micro focus X-ray beam. This indicates that the lamellar twist has a strictly uniform and regular nature. The latter observation is more compatible with the model explaining the twist as a result of unbalanced surface stresses than the giant screw dislocations. Moreover, the data shows that achiral polymers are in fact not indifferent to the inversion of the lamellar handedness, and that a change in handedness is necessarily accompanied by a change in the sign of the growth vector. At the same time, we show that the overall chain tilt (i.e., the inclination of the c-parameter of the unit cell in the plane perpendicular to the fast growth direction) does not affect the rate and sense of twisting. This calls into question the second premise of the KP-mod el. Instead, the local inclination of the terminal segment of the crystalline stem protruding the lamellar surface can be identified as the origin of the surface stresses and forcing the lamellar ribbon to twist. With the variation of the crystal thickness as a function of crystallization temperature the angle and direction of this segment is changed, resulting in a change of the lamellar ribbon chirality.

In view of the importance of charge storage in polymer electrets for electromechanical transducer applications, the aim of this work is to contribute to the understanding of the charge-retention mechanisms. Furthermore, we will try to explain how the long-term storage of charge carriers in polymeric electrets works and to identify the probable trap sites. Charge trapping and de-trapping processes were investigated in order to obtain evidence of the trap sites in polymeric electrets. The charge de-trapping behavior of two particular polymer electrets was studied by means of thermal and optical techniques. In order to obtain evidence of trapping or de-trapping, charge and dipole profiles in the thickness direction were also monitored. <br><br> In this work, the study was performed on polyethylene terephthalate (PETP) and on cyclic-olefin copolymers (COCs). PETP is a photo-electret and contains a net dipole moment that is located in the carbonyl group (C = O). The electret behavior of PETP arises from both the dipole orientation and the charge storage. In contrast to PETP, COCs are not photo-electrets and do not exhibit a net dipole moment. The electret behavior of COCs arises from the storage of charges only. <br><br> COC samples were doped with dyes in order to probe their internal electric field. COCs show shallow charge traps at 0.6 and 0.11 eV, characteristic for thermally activated processes. In addition, deep charge traps are present at 4 eV, characteristic for optically stimulated processes. <br><br> PETP films exhibit a photo-current transient with a maximum that depends on the temperature with an activation energy of 0.106 eV. The pair thermalization length (rc) calculated from this activation energy for the photo-carrier generation in PETP was estimated to be approx. 4.5 nm. The generated photo-charge carriers can recombine, interact with the trapped charge, escape through the electrodes or occupy an empty trap. <br><br> PETP possesses a small quasi-static pyroelectric coefficient (QPC): ~0.6 nC/(m²K) for unpoled samples, ~60 nC/(m²K) for poled samples and ~60 nC/(m²K) for unpoled samples under an electric bias (E ~10 V/µm). When stored charges generate an internal electric field of approx. 10 V/µm, they are able to induce a QPC comparable to that of the oriented dipoles. Moreover, we observe charge-dipole interaction. Since the raw data of the QPC-experiments on PETP samples is noisy, a numerical Fourier-filtering procedure was applied. Simulations show that the data analysis is reliable when the noise level is up to 3 times larger than the calculated pyroelectric current for the QPC. <br><br> PETP films revealed shallow traps at approx. 0.36 eV during thermally-stimulated current measurements. These energy traps are associated with molecular dipole relaxations (C = O). On the other hand, photo-activated measurements yield deep charge traps at 4.1 and 5.2 eV. The observed wavelengths belong to the transitions in PETP that are analogous to the π - π* benzene transitions. The observed charge de-trapping selectivity in the photocharge decay indicates that the charge detrapping is from a direct photon-charge interaction. Additionally, the charge de-trapping can be facilitated by photo-exciton generation and the interaction of the photo-excitons with trapped charge carriers. These results indicate that the benzene rings (C6H4) and the dipolar groups (C = O) can stabilize and share an extra charge carrier in a chemical resonance. In this way, this charge could be de-trapped in connection with the photo-transitions of the benzene ring and with the dipole relaxations. <br><br> The thermally-activated charge release shows a difference in the trap depth to its optical counterpart. This difference indicates that the trap levels depend on the de-trapping process and on the chemical nature of the trap site. That is, the processes of charge detrapping from shallow traps are related to secondary forces. The processes of charge de-trapping from deep traps are related to primary forces. Furthermore, the presence of deep trap levels causes the stability of the charge for long periods of time. / Angesichts der Bedeutung der Ladungsspeicherung in Polymerelektreten für viele Anwendungen, wie z.B. in elektromechanischen Wandler, ist es das Ziel dieser Arbeit, zum Verständnis der zugrundeliegenden Mechanismen der kurz- und langfristigen Ladungsstabilisierung beizutragen sowie mögliche Haftstellen zu identifizieren. Ladungs- und Entladungsprozesse in Elektreten geben Hinweise auf Ladungshaftstellen. Diese Prozesse wurden mit thermischen und optischen Methoden bei gleichzeitiger Messung von Ladungs- und Polarisationprofilen untersucht. Die experimentellen Untersuchungen der vorliegenden Arbeit wurden an Polyethylenterephthalat (PETP) und an Cyclischen-Olefin Copolymeren (COC) durchgeführt. <br><br> PETP ist ein Photoelektret und weist in der Carbonylgruppe (C = O) ein Dipolmoment auf. Die Elektreteigenschaften ergeben sich sowohl aus der Orientierungspolarisation als auch aus der Ladungsspeicherung. Im Gegensatz zu PETP ist COC kein Photoelektret und zeigt auch keine Orientierungspolarisation. Deshalb folgen die Elektreteigenschaften des COC ausschließlich aus der Ladungsspeicherung. Die COC-Proben wurden mit Farbstoffen dotiert, um das innere elektrische Feld zu untersuchen. Diese Systeme zeigen flache Ladungshaftstellen bei 0,6 und 0,11 eV, die durch thermisch stimulierte Prozesse entladen werden sowie tiefe Haftstellen bei 4 eV, die optisch stimuliert werden können. <br><br> PETP-Filme zeigen einen transienten Photostrom mit einem Maximalwert ( jp), der von der Temperatur mit einer Aktivierungsenergie von 0,106 eV abhängt. Der thermische Paarabstand (rc) kann für die Photoladungsgeneration in PETP auf ca. 4,5 nm abgeschätzt werden. Die Photoladungsträger können rekombinieren, mit den gespeicherten Ladungen interagieren, über die Elektroden entkommen oder eine leere Haftstelle einnehmen. <br><br> PETP zeigt einen kleinen quasi-statischen pyroelektrischen Koeffizienten (QPC) von ca. 0,6 nC/(m²K) für nicht polarisierte Proben, ca. 60 nC/(m²K) für polarisierte Proben und ca. 60 nC/(m²K) für nicht polarisierte Proben mit Vorspannung (E ~10 V/µm). Wenn die gespeicherten Ladungen ein internes elektrisches Feld von ca. 10 V/µm generieren können, sind sie in der Lage, einen QPC herbeizuführen, der vergleichbar mit dem von orientierten Dipolen ist. Es ist außerdem möglich, eine Ladungs-Dipol-Wechselwirkung zu beobachten. Da die QPM-Daten von PETP auf Grund des geringen Signals verrauscht sind, wurde ein numerisches Fourier-Filterverfahren angewandt. Simulationen zeigen, dass eine zuverlässige Datenanalyse noch bei einem Signal möglich ist, dessen Rauschen bis zu 3-mal größer ist als der berechnete pyroelektrische Strom. <br><br> Messungen der thermisch stimulierten Entladung von PETP-Filmen ergaben flache Haftstellen bei ca. 0,36 eV, welche mit der Dipolrelaxation der Carbonylgruppe (C = O) assoziiert sind. Messungen der photostimulierten Entladung ergaben tiefe Haftstellen bei 4,1 und 5,2 eV. Die beobachteten Wellenlängen entsprechen Übergängen in PETP analog den π - π* Übergängen in Benzol. Die beobachtete Selektivität bei der photostimulierten Entladung lässt auf eine direkte Wechselwirkung von Photonen und Ladungen schließen. Einen zusätzlichen Einfluß auf die Entladung hat die Erzeugung von Photo-Exzitonen und deren Wechselwirkung mit den gespeicherten Ladungsträgern. Diese Ergebnisse deuten darauf hin, dass die Phenylringe (C6H4) und die Dipolgruppen (C = O) eine zusätzliche Ladung in einer chemischen Resonanz stabilisieren und miteinander teilen können. Daher kann die gebundene Ladung auch durch einen Photoübergang im Benzolring oder durch eine Dipolrelaxation freigesetzt werden. <br><br> Die mittels thermisch stimulierter Entladung bestimmte Tiefe der Haftstellen unterscheidet sich deutlich von den mittels photostimulierter Entladung gemessenen Werten. Flachere Haftstellen werden bei der thermisch stimulierten Entladung gefunden und können sekundären Kräften zugeordnet werden. Die tieferen Haftstellen sind chemischer Natur und können primären Kräften zugeordnet werden. Letztere sind für die Langzeitstabilität der Ladung in Polymerelektreten verantwortlich.

Orientadores: Felix Guillermo Reyes Reyes, Maria Teresa de Alvarenga Freire / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-16T23:01:27Z (GMT). No. of bitstreams: 1 Dutra_CamilaBraga_D.pdf: 1974104 bytes, checksum: 7a0aae96f3654e27fb7d553ee756e522 (MD5) Previous issue date: 2010 / Doutorado / Doutor em Ciência de Alimentos

Submitted by Luciana Ferreira (lucgeral@gmail.com) on 2016-06-01T09:08:49Z No. of bitstreams: 2 Dissertação - Georgeo Dias Fernandes - 2016.pdf: 4550829 bytes, checksum: c89172b3acd5d16ace7d0bf283fc8446 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2016-06-01T09:10:55Z (GMT) No. of bitstreams: 2 Dissertação - Georgeo Dias Fernandes - 2016.pdf: 4550829 bytes, checksum: c89172b3acd5d16ace7d0bf283fc8446 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Made available in DSpace on 2016-06-01T09:10:55Z (GMT). No. of bitstreams: 2 Dissertação - Georgeo Dias Fernandes - 2016.pdf: 4550829 bytes, checksum: c89172b3acd5d16ace7d0bf283fc8446 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Previous issue date: 2016-01-28 / Traditional construction methods are questioned, because of low productivity, waste, rework, low standardization, among other things. Because of these problems and taking into account environmental aspects, new building systems that make use of reusable or recyclable materials from other industries are analyzed to verify its efficiency in technical and economic level. In this context, the aim of the dissertation is to describe the technical development and assess costs and benefits of the constructive system sandwich panels, molded on site, which reuses bottles of polyethylene terephthalate (PET) to make up the core of the walls and slabs. Concerning the technical development was described experiments and tests carried out for the conformation of the construction system, with the configuration of its characteristics and peculiarities, discussed the results of the tests performed, including the early to define the structural safety of the walls and slabs together with the presentation of the theoretical model calculation and performance evaluation for the validation. In the economic aspect, there was a comparison between the traditional construction system and the studied system. The cost direct was examined and observed the benefits with the help of value attributes expected to prefabricated options construction, drawn by Cook (2013), namely: direct costs (material and labor), time (schedule), design flexibility, work time management, quality, delivery and conference in work, subcontractors activities in work, work safety, exercise stress testing, health, environmental impact, LEED certification, rubble and dispensing, public relations, marketing, maintenance (life cycle). With the help of estimators engineers, through interviews, the steps we investigated, activities, productivity and resources needed to execute a project in the traditional building system, building system in masonry traditional system and building system analyzed. Was elaborated cost composition of spreadsheets and productivity for hypothetical situations of conventional and innovative construction system of sealing walls with slabs of residential buildings and walls and structural slabs works until two floors. The mapping process was designed, in which to extract the consideration of potential benefits or otherwise of the building system. Technical descriptions highlight the possibility of constructive feasibility of sandwich panels, with core of PET bottles, molded on site. And the evaluation of costs and benefits demonstrates its value, not so much due to the direct cost, but in terms of building system management benefits. / Os métodos construtivos tradicionais são questionados em função da baixa produtividade, desperdícios, retrabalhos e baixa padronização, dentre outros aspectos. Em virtude destes problemas e levando em conta aspectos ambientais, novos sistemas construtivos, que fazem uso de materiais reutilizáveis ou recicláveis de outras indústrias, são analisados visando verificar sua eficiência em nível técnico-econômico. Diante desse contexto, o objetivo da dissertação é descrever o desenvolvimento técnico e avaliar custo e benefício do sistema construtivo em painéis sanduíche, moldados no local, que reutiliza garrafas de politereftalato de etileno (PET) para compor o núcleo das paredes e lajes. Relativo ao desenvolvimento técnico, descrevem-se os experimentos e ensaios realizados para a conformação do sistema construtivo, apresentando a configuração das suas características e peculiaridades. Em seguida, discutem-se os resultados dos ensaios executados, compreendendo os iniciais para definição da segurança estrutural das paredes e lajes conjuntamente com a apresentação do modelo teórico de cálculo, bem como os de avaliação de desempenho para validação. No aspecto econômico, faz-se um comparativo entre o sistema construtivo tradicional e o sistema estudado. A relação custo direto foi examinada e observou-se os benefícios com a ajuda dos atributos de valor esperados para opções pré-fabricadas de construção, quais sejam: custo direto (material e mão de obra), tempo (cronograma), flexibilidade de projeto, tempo de administração de obra, qualidade, entregas e conferência em obra, atividades de subempreiteiros em obra, segurança do trabalho, ergometria, condições de saúde, impacto ambiental, certificação LEED, entulho e descarte, relações públicas, marketing e manutenção (ciclo de vida). Com a ajuda de engenheiros orçamentistas, por meio de entrevistas, investigaram-se as etapas, atividades, produtividade e recursos necessários para executar um projeto no sistema construtivo tradicional, sistema construtivo em alvenaria estrutural e no sistema construtivo analisado. Elaboraram-se planilhas de composição de custo e produtividade para as situações hipotéticas do sistema construtivo inovador e convencional de paredes de vedação com lajes de edifícios habitacionais e para paredes e lajes estruturais de obras até dois pavimentos. O mapeamento dos processos foi delineado, no qual foram extraídas as considerações sobre possíveis benefícios ou não do sistema construtivo. As descrições técnicas evidenciam a possibilidade da viabilidade construtiva de painéis sanduíche, com núcleo de garrafas PET, moldados no local. Já o a avaliação de custo e benefício demonstrou seu valor, nem tanto em função do custo direto, mas, em termos de benefícios de gestão do sistema construtivo.

[pt] O acelerado desenvolvimento tecnológico tem provocado uma obsolescência precoce dos produtos. Com o aumento dos produtos com vida útil cada vez menor, cresce o número de resíduos gerados e chega-se ao esgotamento da capacidade dos sistemas tradicionais de disposição de resíduos. Com isso, alternativas são estudadas para a destinação final dos bens, a fim de minimizar o impacto ambiental gerado pelos mesmos. Aliado a esse aspecto, devem ser consideradas as legislações referentes às questões ambientais e a crescente sensibilidade ecológica, com a propagação do conceito do desenvolvimento sustentável e os novos princípios de proteção ambiental (como o EPR - Extended Product Responsability). O processo de reciclagem é também uma importante fonte de renda e de postos de trabalho, especialmente, para os extratos mais pobres da sociedade. É neste contexto que a Logística Reversa vem se desenvolvendo, com processos de retorno dos bens aos seus ciclos produtivos, quando possível, ou à sua destinação final. Este trabalho pretende apresentar, em linhas gerais, a logística reversa relacionada à reciclagem de resíduos plásticos. Para isso, foi diagnosticado o canal reverso de distribuição da reciclagem dos resíduos plásticos de Poliestireno e Polietileno Tereftalato, analisando oito empresas integrantes deste canal no Estado do Rio de Janeiro por meio de entrevistas. Além dessas empresas, foram abordadas no estudo uma recicladora de PET em São Paulo com dados extraídos via internet e uma empresa que está realizando uma nova experiência em coleta automática de recicláveis. / [en] The accelerated technological development produces an early obsolescence of the products. With the increase the number of products with its useful life progressively smaller, the number of generated residues grows bringing to the exhaustion the capacity of the tradicional systems of disposition of residues. Given this scenario, alternatives are studied for the final destination of the goods, in order to minimize the resulting environmental impact. In addition, the legislations concerned with environmental subjects, the growing ecological sensibility with the sustainable development and the new beginnings of environmental protection (like EPR - Extended Product Responsability) are requiring reduced environment impacts. In this context, Reverse Logistics is developing processes to direct the goods back to production, whenever possible, or to final destination. This work intends to present in general lines the reverse logistics related to recycling plastics residues. This work has diagnosed the reverse distribution channel in the recycling of plastic residues of Polystyrene and Polyethylene Terephthalate. Eight companies located in the State of Rio de Janeiro which operate in this channel have been chosen for interviewing. In addition, two other companies have been included in the research, one located in the State of São Paulo, and recycling PET, was evaluated through the Internet, and another operating with a new type of automatic collection was evaluated through published reports.

Polyethylene (PE) resins being non-polar in nature and having a high degree of crystallinity have limited miscibility and compatibility when blended with polar polymers. The miscibility and compatibility of these blends are generally worsened when they are prepared by direct injection moulding without a precompounding process. Such situations are commonly encountered in particular by polymer converters when blending colour and/or additive concentrates, commonly known as masterbatches. Typically, masterbatches are mixtures containing high loading of pigments and/or additives predispersed in a suitable solid vehicle (commonly known as carrier) such as a polyethylene resin. These masterbatches are usually used for the colouration of a wide range of polymers and the carrier used must therefore be compatible with these matrix (host) polymers. The preliminary stage of this study involved the investigation of the properties of blends based on high density polyethylene (HDPE) and a range of engineering thermoplastics (ABS, PC, PBT, PA6), prepared by injection moulding. Five different types of compatibilisers namely, ethylene-vinyl acetate (EVA) copolymer, ethylene-methyl acrylate (EMA) copolymer, ethylene-glycidyl methacrylate (E-GMA) copolymer, ethylene-methyl acrylateglycidyl methacrylate (E-MA-GMA) terpolymer and maleic anhydride grafted HDPE (HDPE-g-MAH) copolymer were evaluated with respect to their efficiencies in compatibilising HDPE with the four engineering polymers. The pre-compounded HDPE/compatibiliser binary blends at 2 different blend ratios (1:1 and 3:1) were added at 15 wt% concentration to each engineering thermoplastics and test samples were produced directly by injection moulding. Results of mechanical testing and characterisation of the blends showed that glycidyl methacrylate compatibilisers, E-MA-GMA, in particular have the most universal compatibilising effectiveness for a range of engineering thermoplastics including ABS, PC, PBT, and PA6. Blends compatibilised with E-MA-GMA compatibiliser had the best notched impact performance irrespective of matrix polymer type. The presence of an acrylic ester (methyl acrylate) comonomer in E-MA-GMA resulted in increased polarity of the ii compatibiliser leading to improved miscibility with the polar matrix polymers demonstrated by fine blend morphologies, melting point depression and reduction in crystallinity of the HDPE dispersed phase. The second stage of this study involved the reactive modification of HDPE using a low molecular weight di-functional solid diglycidyl ether of bisphenol A (DGEBA) type epoxy resin compatibilised with HDPE-g-MAH in an attempt to improve its compatibility with ABS, PBT and PA6. The maleic anhydride moieties in HDPE-g-MAH served as reactive sites for anchoring the epoxy moieties while the HDPE backbone was miscible with the HDPE resin. An excessive amount of reactive groups resulted in the formation of crosslinked gels while the addition of EVA co-compatibiliser helped in the reduction of gel content and further improved the dispersion of the epoxy. The effectiveness of epoxy grafted HDPE (with and without EVA co-compatibiliser) in compatibilising ABS/HDPE, PBT/HDPE, and PA6/HDPE was investigated by injection moulding of 5 wt% functionalised HDPE with these matrix polymers into test bars for mechanical testing, and characterisation by differential scanning calorimtery (DSC) and optical microscopy. The reactively functionalised HDPE blends, improved the mechanical properties of ABS and PA6 blends especially with EVA as co-compatibiliser. However, the mechanical properties of PBT blends were unmodified by the functionalised HDPE which was believed to be due to end-capping of the PBT chain-ends by ungrafted epoxy resins.

The master's thesis focuses on preparation of blown films from polylactid acid (PLA) which was blended with selected polyesteres – poly(butylene adipate-co-terephtalate) (PBAT), polycaprolactone (PCL) and polybutylene succinate (PBS) – and thermoplastic starch (TPS) in amount of 30% in order to soften PLA films. The influence of the aditives on static and mechanical tensile properties, on structure, morphology and thermal properties of the films was determined and the obtained parameters were compared to properties of films prepared from neat PLA and high density polyethylene (HDPE). The results showed that the additives increased crystalinity of PLA and thus significantly influenced the properties of the films. In contrast to the film from neat PLA, softening in terms of lowering glass transition temperature occured only by adding PBS and TPS, in terms of increasing ductility only by adding PBAT. All PLA films showed nearly constant elastic modulus up to the beginning of glass transition enabling their potential application till 50 °C. Preparation of the film with TPS was problematic and the film showed the worst mechanical properties. Preparation of other films was without any problems. The most promising additive from the tested ones was PBAT which showed comparable mechanical properties as the film from HDPE.

Elevated reaction temperatures are crucial for the efficient enzymatic degradation of polyethylene terephthalate (PET). A disulfide bridge was introduced to the polyester hydrolase TfCut2 to substitute its calcium binding site. The melting point of the resulting variant increased to 94.7°C (wild-type TfCut2: 69.8 °C) and its half-inactivation temperature to 84.6 °C (TfCut2: 67.3 °C). The variant D204C-E253C-D174R obtained by introducing further mutations at vicinal residues showed a temperature optimum between 75 and 80 °C compared to 65 and 70 °C of the wild-type enzyme. The variant caused a weight loss of PET films of 25.0 +/- 0.8% (TfCut2: 0.3 +/-0.1%) at 70 °C after a reaction time of 48 h. The results demonstrate that a highly efficient and calcium-independent thermostable polyester hydrolase can be obtained by replacing its calcium binding site with a disulfide bridge.

The enzymatic degradation of polyethylene terephthalate (PET) occurs at mild reaction conditions and may find applications in environmentally friendly plastic waste recycling processes. The hydrolytic activity of the homologous polyester hydrolases LC cutinase (LCC) from a compost metagenome and TfCut2 from Thermobifida fusca KW3 against PET films was strongly influenced by the reaction medium buffers tris(hydroxymethyl)aminomethane (Tris), 3-(N-morpholino)propanesulfonic acid (MOPS), and sodium phosphate. LCC showed the highest initial hydrolysis rate of PET films in 0.2 M Tris, while the rate of TfCut2 was 2.1-fold lower at this buffer concentration. At a Tris concentration of 1 M, the hydrolysis rate of LCC decreased by more than 90% and of TfCut2 by about 80%. In 0.2 M MOPS or sodium phosphate buffer, no significant differences in the maximum initial hydrolysis rates of PET films by both enzymes were detected. When the concentration of MOPS was increased to 1 M, the hydrolysis rate of LCC decreased by about 90%. The activity of TfCut2 remained low compared to the increasing hydrolysis rates observed at higher concentrations of sodium phosphate buffer. In contrast, the activity of LCC did not change at different concentrations of this buffer. An inhibition study suggested a competitive inhibition of TfCut2 and LCC by Tris and MOPS. Molecular docking showed that Tris and MOPS interfered with the binding of the polymeric substrate in a groove located at the protein surface. A comparison of the Ki values and the average binding energies indicated MOPS as the stronger inhibitor of the both enzymes.