Unsaturated Polyester Resins from Recycled Polyethyleneterephthalate

Tämän diplomityön tarkoituksena oli tutkia miten kuluttajien kierrättämästä polyeteenitereftalaatista ( PET ) voi valmistaa tyydyttymättömiä polyesterihartseja. Työssä valmistettiin yleiskäyttöön soveltuva laminointihartsi sekä 'gel coat' -hartsi jota käytetään esim. veneiden pintamaalina. Yleishartsin depolymerointiin käytettiin propyleeniglykolia ja 'gel coat' -hartsin valmistamiseen neopentyyliglykolia. Polykondensaatiovaiheessa reaktioon lisättiin maleiinihappoa ja lopuksi hartsit liuotettiin styreeniin. Kirjallisuusosassa esitetään eri menetelmiä PET:n depolymeroimiseksi. Lisäksi esitetään eri vaihtoehtoja glykolien, happojen, katalyyttien ja vinyylimonomeerien valitsemiseksi tyydyttymättömien polyesterihartsien valmistuksessa. Analyysimenetelmiä nestemäisten ja kovetettujen hartsien tutkimiseen ja vertailuun käydään läpi kuten myös erilaisia sovelluksia polyesterihartsien käyttämiseksi. Kokeellinen osa todisti että PET-pullojäte voidaan prosessoida hartsiksiilman uusia investointeja prosessilaitteistoon. PET:n glykolyysi kesti viidestäseitsemään tuntia ja polykondensaatiovaihe kahdesta ja puolesta viiteen tuntiin. Hartsien molekyylipainot ja mekaanisten testien tulokset olivat vertailukelpoisia kaupallisten hartsien antamien tulosten kanssa. Glykolyysivaiheen momomeeri- ja oligomeeripitoisuudet mitattiin geelipermeaatiokromatografialla, jotta nähtiin miten pitkälle depolymerisaatio oli edennyt. Tätä tietoa voidaan hyödyntää uusien hartsireseptin suunnittelussa. Polymeeriketjussa jäljellä olevien C=C kaksoissidosten määrä ja niiden isomeraatioaste maleaattimuodosta fumaraattimuotoon mitattiin 1H-NMR -menetelmällä. Tislevesien koostumus määritettiin kaasukromatografialla, ja tulokset kertoivat katalyytin sisältämän kloorin reagoineen glykolien kanssa, johtaen suureen glykolikulutukseen ja muihin ei-toivottuihin sivureaktioihin. Hartsien sietokykyä auringon valolle mitattiin niiden UV-absorption avulla. Kummastakin hartsista valmistettiin 'gel coat' -maalit jotkalaitettiin sääkoneeseen, joka simuloi auringonpaistetta ja vesisadetta vuorotellen. Näistä 'gel coateista' mitattiin niiden kellastumista. Kummastakin hartsista tehdyt valut asetettiin myös sääkoneeseen ja IR-spektreistä ennen jajälkeen koetta nähtiin että C=O ja C-O esterisidoksia oli hajonnut.

A simple model to describe the thixotropic behavior of paints.

We propose a simple rheological model to describe the thixotropic behavior of paints, since the classical hysteresis area, which is usually used, is not enough to evaluate thixotropy. The model is based on the assumption that viscosity is a direct measure of the structural level of the paint. The model depends on two equations: the Cross-Carreau equation to describe the equilibrium viscosity and a second order kinetic equation to express the time dependence of viscosity. Two characteristic thixotropic times are differentiated: one for the net structure breakdown, which is defined as a power law function of shear rate, and an other for the net structure buildup, which is not dependent on the shear rate. The knowledge of both kinetic processes can be used to improve the quality and applicability of paints. Five representative commercial protective marine paints are tested. They are based on chlorinated rubber, acrylic, alkyd, vinyl, and epoxy resins. The temperature dependence of the rheological behavior is also studied with the temperature ranging from 5 ºC to 35 ºC. It is found that the paints exhibit both shear thinning and thixotropic behavior. The model fits satisfactorily the thixotropy of the studied paints. It is also able to predict the thixotropy dependence on temperature. Both viscosity and the degree of thixotropy increase as the temperature decreases.

Transmission properties of high barrier coated paperboard packages

High barrier materiaaleilla pyritään pidentämään pakattujen elintarvikkeiden hyllyikää. Barrierin tärkein tehtävä on elintarvikkeen suojaaminen hapelta ja kosteudelta. Alumiinin käyttöä barriermateriaalina pyritään vähentämään korvaamalla alumiini polymeereillä, jotka täyttävät elintarvikkeiden asettamat korkeat säilyvyysvaatimukset. Etyylivinyylialkoholin (EVOH) hapenläpäisevyys on kuivissa olosuhteissa alhaisin kaupallisista muovilaaduista. EVOH tarjoaa myös erinomaisen suojan muita kaasuja, rasvoja, hajuja ja aromeja vastaan ja sitä on helppo prosessoida. Polyamideilla on erinomainen kaasutiiveys sekä hyvä lujuus ja sitkeys. Eri muovilaatuja sekoittamalla voidaan vähentää hapenläpäisyä ja parantaa prosessointia. Polyolefiineja käytetään yleisesti päällystysmateriaaleina, koska ne suojaavat tuotetta erinomaisesti kosteudelta. Hapenläpäisyllä tarkoitetaan hapen kulkeutumista materiaalin läpi joko permeaation kautta tai reikien ja vuotojen läpi. Kaasun permeoitumiseen materiaalin läpi vaikuttavat materiaalin vapaa tilavuus, kiteisyysaste, orientaatio, substituointi, suhteellinen kosteus, lämpötila, barrierkerroksen paksuus, paine-ero ja permeoituvan molekyylin ominaisuudet. Kokeellisessa osassa analysoitiin ja vertailtiin kartonkipohjaisia mehutölkkejä, joissa käytettävät high barrier materiaalit olivat EVOH ja PA. Kartonkipohjaisia alumiinitölkkejä käytettiin referenssinä. Pakkausten hapenläpäisevyysmittauksissa saatiin samasta näytteestä toistettavia tuloksia, vaikka vuotomittauksissa saadut tulokset eivät olleet vertailukelpoisia hapenläpäisytulosten kanssa. Tölkkien valmistus vaikutti oleellisesti pakkausten tiiveysominaisuuksiin. Hapenläpäisy vuotojen ja reikien läpi oli merkittävämpää kuin hapenläpäisy materiaalin läpi. Pakkausten tiiveysominaisuuksia analysoitiin mittaamalla appelsiinimehun askorbiini-happopitoisuus. Askorbiinihapon hajoaminen mitattiin koetölkkeihin pakatusta appelsiinimehusta, ja lämpötilan, valon ja hapen vaikutusta askorbiinihapon hajoamiseen tutkittiin 12 viikon ajan. Lämpötilalla oli suurin vaikutus askorbiinihapon hajoamiseen huolimatta käytetystä pakkausmateriaalista.

Fotoiniciação de polimerização vinílica

The initiation step of the light-induced polymerization kinetics of vinyl monomers using dye-sensitized photoinitiators to generate active radicals is discussed. The photoredox processes of basic dyes with amines and sulfinates are described as photochemical systems capable of starting free-radical polymerization of vinyl monomers in homogeneous and microheterogeneous media. Photophysical techniques like laser flash photolysis and time-correlated single photon counting are used to investigate the excited-state kinetics of the dyes.

Processo alternativo para remoção de cobre (II) e níquel (II) de soluções aquosas utilizando cápsulas de quitosana - Álcool Polivinílico

Capsules were prepared from chitosan (QTS)-poly(vinyl alcohol) (PVA) blend by saline coacervation and then by formalization. A adsorbent based on chitosan, insoluble on acid solution, was obtained. The morphology, average diameters of QTS/PVA capsules and their pores were studied by using scanning electron microscopy. The entrapment-adsorption of dimethylglioxime and ethylenediaminetetracetate by the capsules were studied. The removal of the ion nickel (II) and copper (II), was more effective than by using unloaded capsules.

Dinámica de reacciones unimoleculares en fase gas: Desviaciones del comportamiento estadístico

The present review summarizes the most relevant results of our research group obtained recently in the field of unimolecular reaction dynamics. The following processes are specifically analyzed: the isomerization, dissociation and elimination in methyl nitrite, the fragmentation reactions of the mercaptomethyl cation, the C-CO dissociation in the acetyl and propionyl radicals, and the decomposition of vinyl fluoride. In all the cases, only state- or energy-selected systems are considered. Special emphasis is paid to the possibility of systems exhibiting non-statistical behavior.

Biossensor enzimático para detecção de fungicidas ditiocarbamatos: estudo cinético da enzima aldeído desidrogenase e otimização do biossensor

Initially, all major factors that affect the rate of the AldH-catalyzed reaction (enzyme concentration, substrate concentration, temperature and pH) were investigated. Optimal activity was observed between pH values of 7.5 and 9.5 in the temperature range of 25 to 50 ºC. Kinetic parameters, such as Km (2.92 µmol L-1) and Vmax (1.33 10-2 µmol min-1) demonstrate a strong enzyme-substrate affinity. The sensors were based on screen-printed electrodes modified with the Meldola Blue-Reinecke salt (MBRS) combination. Operational conditions (NAD+ and substrate contents, enzyme loading and response time) were optimized. Also, two enzyme immobilization procedures were tested: entrapment in poly(vinyl alcohol) bearing styrylpyridinium groups (PVA-SbQ) and crosslinking with glutaraldehyde. Chronoamperometry was employed to observe the biosensor responses during enzymatic hydrolysis of propionaldehyde and also to construct inhibition curves with maneb and zineb fungicides. Best results were found with the following conditions: [NAD+] = 0.25 mmol L-1; [propionaldehyde] = 80 µmol L-1; enzyme loading = 0.8 U per electrode; response time = 10 min, and inhibition time = 10 min. Current intensities around 103 ± 13 nA with the sensors and good stability was obtained for both immobilization procedures. Detection limits, calculated using 10% inhibition were 31.5 µg L-1 and 35 µg L-1 for maneb and zineb, respectively. Results obtained with other MBRS-modified electrodes consisting of mono and bi-enzymic sensors were compared. The ability to catalyze NADH oxidation by MB was also highlighted.

Nanocompósitos eletroativos de poli-o-metoxianilina e polissacarídeos naturais

In this work we take advantage of the polyelectrolyte character of some Brazilian native gums to fabricate electrically conductive, nanostructured films. The gums Sterculia urens, (caraia), Sterculia striata (chicha) or Anadenanthera macrocarpa Benth were assembled in conjunction with poly(o-methoxyaniline) (POMA) in the form of layered nanostructured films using the layer-by-layer (LbL) technique. All the LbL films displayed a well-defined electroactivity, as confirmed via cyclic voltammetry. In comparison to POMA LbL films fabricated with conventional polyelectrolytes (viz. poly(vinyl sulfonic acid)-PVS), the presence of the gums in the LbL films increased remarkably the electrochemical stability of the films.

Effect of the radiolitic sterilization in polyethylene/starch blends

Samples of LDPE/modified starch blends 80/20 m/m before and after exposure to gamma rays were examined by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction. The effect of gamma radiation is clearly seen in the samples irradiated at a dose of 25 kGy. The main alteration in the polymeric material after exposure at the radiation range was a decrease in the mechanical properties, alterations in the chemical structure of the blend with an increase in the carbonyl and vinyl indices and the appearance of new crystalline symmetry generating a crystalline domain not existing before in the blend.

Preparação e caracterização de blendas de quitosana/poli(álcool vinílico) reticuladas quimicamente com glutaraldeído para aplicação em engenharia de tecido

In this study, novel Chitosan/PVA based films were chemically crosslinked by glutaraldehyde, under pH=(4,00 ±0,05), in order to achieve structures tailored for wound tissue engineering applications. Both precursors and developed films were characterized by FTIR, SEM and XRD in order to determine the presence of chemicals groups and nanostructural order, respectively. The results have shown that the glutaraldehyde crosslinking have altered the crystallinity of pure chitosan and the increase on the C=N bands and simultaneous decrease on NH2 bands suggested that Chitosan/GA crosslinking has preference to occur in carbon-2 of the saccharide ring by the Schiff's base reaction. Also, FTIR spectroscopy clearly showed that crosslinking has also taken place with blends of PVA and chitosan. The mechanical properties presented high degree dependence with on the increase of the content of chitosan and glutaraldehyde. The results have indicated that, by controlling the ratio [PVA]/[chitosan] in the blends and the extent of chemical crosslinking, it was possible to tailor the hybrid network produced aiming to obtain properties of interest for the specific application.

Efeitos da incorporação de peneiras moleculares 3A, 4A, 5A e 13X em membranas compósitas de quitosana/poli(vinil álcool)

The composite membranes prepared via incorporation of 12.5% of molecular sieves 3A, 4A, 5A and 13X into chitosan/poly(vinyl alcohol) (1:1). The composite membranes were immersed in the cross-linker sulfuric acid in order to acquire high proton conductivity for applications in electrolytes in PEMCF and DMF. The influence of the molecular sieves on the structural, optical, thermal, mechanical, morphologic and protonic conductivity properties and water/methanol swelling degree of membranes were investigated.

Preparation of PVP hydrogel nanoparticles using lecithin vesicles

Hydrogels micro, sub-micro and nanoparticles are of great interest for drug encapsulation and delivery or as embolotherapic agents. In this work it is described the preparation of nano and sub-microparticles of pre-formed, high molecular weight and monomer free poly(N-vinyl-2-pyrrolidone) encapsulated inside the core of lecithin vesicles. The hydrogel particles are formed with a very narrow diameter distribution, of about 800 nm, and a moderate swelling ratio, of approximately 10.

Atribuição absoluta e geral de isômeros constitucionais por espectrometria de massas: o caso das metilpiperidinas

An absolute method is described via mass spectrometry (MS) for the structural assignment of isomers within the class of methylpiperidines. The method explores both the unimolecular and bimolecular gas phase behavior of structurally diagnostic fragment ions (SDFI). For the methylpiperidnes, the isomeric 2-methyl, 3-methyl and 4-methyl 2-azabutadienyl cations are found to function as SDFI. These fragment ions are expected to be formed from all members within the class, to be stable and to retain the structural information of the precursor molecule, and to not interconvert into one another. To characterize these SDFI, both the collision induced dissociation (CID) in argon and bimolecular ion/molecule chemistry with ethyl vinyl ether were compared.

Efeito da adição de TIO2 nas propriedades térmicas e na cristalinidade do copolímero de etileno/acetato de vinila

We investigated the effect of adding titanium dioxide nanoparticles (TiO2) to ethylene vinyl acetate (EVA) copolymer, containing 28% vinyl acetate groups, on the crystallinity and miscibility of the copolymer. Films of EVA/TiO2 containing 0.25%-1% TiO2, relative to the total weight of EVA, were prepared from their solution. The obtained films were characterized by X-ray diffraction, low-field nuclear magnetic resonance, and differential scanning calorimetry. The addition of TiO2 to the EVA copolymer was proved to cause changes in the crystallinity and mobility of the polymer chains of EVA, due to new intermolecular interactions and nanostructure organization.