Platinum(II) olefin hydroarylation catalysts: tuning selectivity for the anti-Markovnikov product Tandem catalytic ester hydrogenation and deoxygenation of polyethylene terephthalate

Thesis (Master's)--University of Washington, 2016-06

Reactive processing of polymers:effect of in situ compatibilisation on characteristics of blends of polyethylene terephthalate and ethylene-propylene rubber

Ethylene-propylene rubber (EPR) functionalised with glycidyl methacrylate (GMA) (f-EPR) during melt processing in the presence of a co-monomer, such as trimethylolpropane triacrylate (Tris), was used to promote compatibilisation in blends of polyethylene terephthalate (PET) and f-EPR, and their characteristics were compared with those of PET/f-EPR reactive blends in which the f-EPR was functionalised with GMA via a conventional free radical melt reaction (in the absence of a co-monomer). Binary blends of PETand f-EPR (with two types of f-EPR prepared either in presence or absence of the co-monomer) with various compositions (80/20, 60/40 and 50/50 w/w%) were prepared in an internal mixer. The blends were evaluated by their rheology (from changes in torque during melt processing and blending reflecting melt viscosity, and their melt flow rate), morphology scanning electron microscopy (SEM), dynamic mechanical properties (DMA), Fourier transform infrared (FTIR) analysis, and solubility (Molau) test. The reactive blends (PET/f-EPR) showed a marked increase in their melt viscosities in comparison with the corresponding physical (PET/EPR) blends (higher torque during melt blending), the extent of which depended on the amount of homopolymerised GMA (poly-GMA) present and the level of GMA grafting in the f-EPR. This increase was accounted for by, most probably, the occurrence of a reaction between the epoxy groups of GMA and the hydroxyl/carboxyl end groups of PET. Morphological examination by SEM showed a large improvement of phase dispersion, indicating reduced interfacial tension and compatibilisation, in both reactive blends, but with the Tris-GMA-based blends showing an even finer morphology (these blends are characterised by absence of poly-GMA and presence of higher level of grafted GMA in its f-EPR component by comparison to the conventional GMA-based blends). Examination of the DMA for the reactive blends at different compositions showed that in both cases there was a smaller separation between the glass transition temperatures compared to their position in the corresponding physical blends, which pointed to some interaction or chemical reaction between f-EPR and PET. The DMA results also showed that the shifts in the Tgs of the Tris-GMA-based blends were slightly higher than for the conventional GMA-blends. However, the overall tendency of the Tgs to approach each other in each case was found not to be significantly different (e.g. in a 60/40 ratio the former blend shifted by up to 4.5 °C in each direction whereas in the latter blend the shifts were about 3 °C). These results would suggest that in these blends the SEM and DMA analyses are probing uncorrelatable morphological details. The evidence for the formation of in situ graft copolymer between the f-EPR and PET during reactive blending was clearly illustrated from analysis by FTIR of the separated phases from the Tris-GMA-based reactive blends, and the positive Molau test pointed out to graft copolymerisation in the interface. A mechanism for the formation of the interfacial reaction during the reactive blending process is proposed.

Dynamically mechanical and nano-impact (fatigue) analysis of touch screen thin films deposited on polyethylene terephthalate substrate

Nano-scale touch screen thin film have not been thoroughly investigated in terms of dynamic impact analysis under various strain rates. This research is focused on two different thin films, Zinc Oxide (ZnO) film and Indium Tin Oxide (ITO) film, deposited on Polyethylene Terephthalate (PET) substrate for the standard touch screen panels. Dynamic Mechanical Analysis (DMA) was performed on the ZnO film coated PET substrates. Nano-impact (fatigue) testing was performed on ITO film coated PET substrates. Other analysis includes hardness and the elastic modulus measurements, atomic force microscopy (AFM), Fourier Transform Infrared Spectroscopy (FTIR) and the Scanning Electron Microscopy (SEM) of the film surface.
Ten delta of DMA is described as the ratio of loss modulus (viscous properties) and storage modulus (elastic properties) of the material and its peak against time identifies the glass transition temperature (Tg). Thus, in essence the Tg recognizes changes from glassy to rubber state of the material and for our sample ZnO film, Tg was found as 388.3 K. The DMA results also showed that the Ten delta curve for Tg increases monotonically in the viscoelastic state (before Tg) and decreases sharply in the rubber state (after Tg) until recrystallization of ZnO takes place. This led to an interpretation that enhanced ductility can be achieved by negating the strength of the material.
For the nano-impact testing using the ITO coated PET, the damage started with the crack initiation and propagation. The interpretation of the nano-impact results depended on the characteristics of the loading history. Under the nano-impact loading, the surface structure of ITO film suffered from several forms of failure damages that range from deformation to catastrophic failures. It is concluded that in such type of application, the films should have low residual stress to prevent deformation, good adhesive strength, durable and good resistance to wear.

A Novel Methodology to Characterize the Constitutive Behaviour of Polyethylene terephthalate for the Stretch Blow Moulding process

The stretch blow moulding (SBM) process is the main method for the mass production of PET containers. And understanding the constitutive behaviour of PET during this process is critical for designing the optimum product and process. However due to its nonlinear viscoelastic behaviour, the behaviour of PET is highly sensitive to its thermomechanical history making the task of modelling its constitutive behaviour complex. This means that the constitutive model will be useful only if it is known to be valid under the actual conditions of interest to the SBM process. The aim of this work was to develop a new material characterization method providing new data for the deformation behaviour of PET relevant to the SBM process. In order to achieve this goal, a reliable and robust characterization method was developed based on an instrumented stretch rod and a digital image correlation system to determine the stress-strain relationship of material in deforming preforms during free stretch-blow tests. The effect of preform temperature and air mass flow rate on the deformation behaviour of PET was also investigated.

Modelling of poly(ethylene terephthalate) in injection stretch-blow moulding

Simulations of the injection stretch-blow moulding process have been developed for the manufacture of poly(ethylene terephthalate) bottles using the commercial finite element package ABAQUS/standard. Initially a simulation of the manufacture of a 330 mL bottle was developed with three different material models (hyperelastic, creep, and a non-linear viscoelastic model (Buckley model)) to ascertain their suitability for modelling poly(ethylene terephthalate). The Buckley model was found to give results for the sidewall thickness that matched best with those measured from bottles off the production line. Following the investigation of the material models, the Buckley model was chosen to conduct a three-dimensional simulation of the manufacture of a 2 L bottle. It was found that the model was also capable of predicting the wall thickness distribution accurately for this bottle. In the development of the three-dimensional simulation a novel approach, which uses an axisymmetric model until the material reaches the petaloid base, was developed. This resulted in substantial savings in computing time. © 2000 IoM Communication Ltd.

Free-stretch-blow Investigation of Poly(ethylene terephthalate) over a Large Process Window

This paper highlights for the first time a full comprehension of the deformation procedure during the injection stretch blow moulding (ISBM) process of poly(ethylene terephthalate) (PET) containers, namely thin-walled rigid bottles. The processes required to form PET bottles are complicated and extensive; any development in understanding the nature of material deformation can potentially improve the bottle optimisation process. Removing the bottle mould and performing free-stretch-blow (FSB) experiments revealed insight into the bottle forming characteristics at various preform temperatures and blowing rates. Process outputs cavity pressure and stretch-rod force were recorded using at instrumented stretch-rod and preform surface strain mapping was determined using a combination of a unique patterning procedure and high speed stereoscopic digital image correlation. The unprecedented experimental analysis reveals that the deformation behaviour varies considerably with contrasting process input parameters. Investigation into the effect on deformation mode, strain rate and final bottle shape provide a basis for full understanding of the process optimisation and therefore how the process inputs may aid development of the preferred optimised container.

Demand for refilled reusable products

The conversion of one-way polyethylene terephthalate (PET) bottles into reusable bottles helps reduce environmental burden. Recently, the Ministry of the Environment in Japan began discussing the introduction of reusable bottles. One of the barriers to introducing the new type of bottle is consumer unwillingness to accept refilled reusable bottles. We administered the questionnaires to consumers in a pilot test on reusable PET bottles organized to analyze the demand for these products. To increase the demand for refilled reusable bottles, it is necessary to supply refilled reusable bottles that are acceptable to consumers who are concerned about container flaws and stains.

Ink-jet printing of graphene for flexible electronics: An environmentally-friendly approach

Mechanical flexibility is considered an asset in consumer electronics and next-generation electronic systems. Printed and flexible electronic devices could be embedded into clothing or other surfaces at home or office or in many products such as low-cost sensors integrated in transparent and flexible surfaces. In this context inks based on graphene and related two-dimensional materials (2DMs) are gaining increasing attention owing to their exceptional (opto)electronic, electrochemical and mechanical properties. The current limitation relies on the use of solvents, providing stable dispersions of graphene and 2DMs and fitting the proper fluidic requirements for printing, which are in general not environmentally benign, and with high boiling point. Non-toxic and low boiling point solvents do not possess the required rheological properties (i.e., surface tension, viscosity and density) for the solution processing of graphene and 2DMs. Such solvents (e.g., water, alcohols) require the addition of stabilizing agents such as polymers or surfactants for the dispersion of graphene and 2DMs, which however unavoidably corrupt their properties, thus preventing their use for the target application. Here, we demonstrate a viable strategy to tune the fluidic properties of water/ethanol mixtures (low-boiling point solvents) to first effectively exfoliate graphite and then disperse graphene flakes to formulate graphene-based inks. We demonstrate that such inks can be used to print conductive stripes (sheet resistance of ~13 kΩ/□) on flexible substrates (polyethylene terephthalate), moving a step forward towards the realization of graphene-based printed electronic devices.

Effect of Packaging Materials and Storage on Major Volatile Compounds in Three Australian Native Herbs

Lemon myrtle, anise myrtle, and Tasmanian pepper leaf are commercial Australian native herbs with a high volatile or essential oil content. Packaging of the herbs in high- or low-density polyethylene (HDPE and LDPE) has proven to be ineffective in preventing a significant loss of volatile components on storage. This study investigates and compares the effectiveness of alternate high-barrier property packaging materials, namely, polyvinylidene chloride coated polyethylene terephthalate/casted polypropylene (PVDC coated PET/CPP) and polyethylene terephthalate/polyethylene terephthalate/aluminum foil/linear low-density polyethylene (PET/PET/Foil/LLDPE), in prevention of volatile compound loss from the three native herbs stored at ambient temperature for 6 months. Concentrations of major volatiles were monitored using gas chromatography?mass spectrometry (GC-MS) techniques. After 6 months of storage, the greatest loss of volatiles from lemon myrtle was observed in traditional LDPE packaging (87% loss) followed by storage in PVDC coated PET/CPP (58% loss) and PET/PET/Foil/LLDPE (loss of 23%). The volatile loss from anise myrtle and Tasmanian pepper leaf stored in PVDC coated PET/CPP and PET/PET/Foil/LLDPE packaging was <30%. This study clearly indicates the importance of selecting the correct packaging material to retain the quality of herbs with high volatile content.

Análise técnica do uso de resíduos de poli (tereftalato de etileno) (PET) na indústria têxtil

O aumento no volume de rejeitos industriais e a contínua produção de resíduos de naturezas diversas causam muitas preocupações no âmbito ambiental. Neste contexto, o descarte de embalagens e garrafas de poli(tereftalato de etileno) (PET) tem se tornado um grande problema por conta da pequena atenção que se dá à sua destinação final. Assim sendo, essa pesquisa propõe a análise técnica da utilização de resíduos de PET, oriundos de reciclagem primária, como matéria-prima para a indústria têxtil. Fios de PET reciclado foram comparados aos fios comerciais de poliéster através de diversos ensaios como, por exemplo, resistência à tração e ensaios para solidificação da cor. Ao mesmo tempo, a microscopia eletrônica de varredura (MEV) foi usada para a investigação da morfologia dos fios e melhor interpretação dos resultados. Pôde ser verificado que os fios de PET reciclado apresentam satisfatório desempenho, embora a resistência mecânica e a solidez a cor à luz sejam inferiores àquelas dos fios convencionais de poliéster.

A solid-state dye-sensitized solar cell based on a novel ionic liquid gel and ZnO nanoparticles on a flexible polymer substrate.

This paper describes a new strategy to make a full solid-state, flexible, dye-sensitized solar cell (DSSC) based on novel ionic liquid gel, organic dye, ZnO nanoparticles and carbon nanotube (CNT) thin film stamped onto a polyethylene terephthalate (PET) substrate. The CNTs serve both as the charge collector and as scaffolds for the growth of ZnO nanoparticles, where the black dye molecules are anchored. It opens up the possibility of developing a continuous roll to roll processing for THE mass production of DSSCs.

Transparent nanostructured electrode by centrifuge coating

We employ a new solution-based coating process, centrifuge coating, to fabricate nanostructured conductive layers over large areas. This coating procedure allows fast quenching of the metastable dispersed state of nanomaterials, which minimizes material wastes by mitigate the effects of particle re-aggregation. Using this method, we fabricate SWNT coatings on different substrates such as PET (polyethylene terephthalate), PDMS (polydimethylsiloxane), and an acrylic elastomer. The effects of the choice of solvents on the morphology and subsequent performance of the coating network are studied. © 2012 IEEE.