Polimerização do glicerol: uma reação simples e versátil para produzir diferentes materiais a partir do coproduto do biodiesel

In this work, it is proposed a simple experiment in polymer science for undergraduates, involving the glycerol polymerization catalyzed by H2SO4 to produce different materials, e.g. from oligomers to crosslinked polymer. The students can investigate the reaction conditions such as time, temperature and catalyst concentration, thus controlling the extent of polymerization and its kinetics. This experiment stimulates students to see polymer science in a broader context, involving diverse topics, such as biodiesel, and processing of a co-product of low value in polymeric materials with potential industrial application.

Uso da cromatografia gasosa bidimensional abrangente (GC×GC) na caracterização de misturas biodiesel/diesel: aplicação ao biodiesel de sebo bovino

The growth of biodiesel market and the implementation of regulations related to biodiesel production and biodiesel/diesel blending has encouraged the development of appropriate analytical methods to control the composition of this type of mixture. In this study, an evaluation of the potential of GC×GC for the characterization of samples of beef tallow biodiesel and the composition of blends of biodiesel/diesel is presented. The methodology was applied to beef tallow biodiesel and its mixtures with petrodiesel, ranging from B2 to B50. Results allowed not only the identification and quantification of the biodiesel esters, but also the biodiesel percentage in biodiesel/diesel blends.

Quantificação de antimônio em garrafas de politereftalato de etileno (PET) brasileiras por fluorescência de raios-X e avaliação quimiométrica para verificar a presença de pet reciclado através do teor de ferro

Antimony is a common catalyst in the synthesis of polyethylene terephthalate used for food-grade bottles manufacturing. However, antimony residues in final products are transferred to juices, soft drinks or water. The literature reports mentions of toxicity associated to antimony. In this work, a green, fast and direct method to quantify antimony, sulfur, iron and copper, in PET bottles by X-ray fluorescence spectrometry is presented. 2.4 to 11 mg Sb kg-1 were found in 20 samples analyzed. The coupling of the multielemental technique to chemometric treatment provided also the possibility to classify PET samples between bottle-grade PET/recycled PET blends by Fe content.

Preparação, caracterização e estudos de biodegradação de blendas à base de PDLLA e PVP

Poly(D,L-lactide), PDLLA, is a polymer with potential applications in medical, environmental, and pharmaceutical areas. Despite its versatility, the hydrophobicity limits its applications. To overcome this problem, one strategy is the preparation of blends with hydrophilic polymers such as poly(vinylpyrrolidone), PVP. In this study, we report the preparation and characterization of blends based on PDLLA and PVP and the biodegradation studies by the Sturm test. It was observed that the components of the blends PDLLA/PVP are thermodynamically immiscible, however the biodegradation is faster than that of pure PDLLA.

Análise exploratória aplicada a espectros de reflexão total atenuada no infravermelho com transformada de Fourier (ATR-FTIR) de blendas de biodiesel/diesel

In this study, hierarchical cluster analysis (HCA) and principal component analysis (PCA) were used to classify blends produced from diesel S500 and different kinds of biodiesel produced by the TDSP methodology. The different kinds of biodiesel studied in this work were produced from three raw materials: soybean oil, waste cooking oil and hydrogenated vegetable oil. Methylic and ethylic routes were employed for the production of biodiesel. HCA and PCA were performed on the data from attenuated total reflectance Fourier transform infrared spectroscopy, showing the separation of the blends into groups according to biodiesel content present in the blends and to the kind of biodiesel used to form the mixtures.

ANÁLISES FÍSICO-QUÍMICAS DE BIOFILMES DE SULFATO DE CONDROITOINA MODIFICADO

Numerous investigations are dedicated to the research and development of new polymer materials destined for innovation in pharmaceutical forms. The application of these technological resources has allowed the commercialization of new therapeutic systems for modified drug release. This investigation aimed to evaluate the association of modified chondroitin sulfate with an insoluble polymer, Eudragit® RS 30 D, widely available in the pharmaceutical market. Isolated films were prepared by the evaporation process using a Teflon® plate. The aqueous dispersions (4% m/v) of synthetic polymer received the addition of modified chondroitin sulfate at different ratios. The interactions of the polymer chains in the blends were physicochemically characterized by means of Fourier transform infrared spectroscopy, thermal analyses, differential scanning calorimetry, thermogravimetry and scanning electron microscopy combined with hydration and assays in alkaline pH. The results showed appropriate properties of the coating materials for solid oral forms intended for drug deliver in specific environments.

DETERMINAÇÃO DO TEOR DE BIODIESEL EM DIESEL EMPREGANDO O ENSAIO COLORIMÉTRICO DO ÁCIDO HIDROXÂMICO

The aim of this paper was to use colorimetric assays for hydroxamic acid to quantify the biodiesel content in diesel and compare it with the traditional method (infrared spectroscopy, using the EN 14078 method). Samples were prepared from B2 to B10 with two kinds of diesel - S500 (red) and S50 (yellow) - to obtain two calibration curves. Through statistical methods it was shown that the slopes of the straight lines obtained for the different types of diesel were the same. Thus, the type of diesel did not influence the results of the colorimetric assay for hydroxamic acid. Real samples collected from gas stations were analyzed by both methods (colorimetry and EN 14078). By applying Student's t-test it was concluded that the methods could be considered statistically equivalent. Therefore, it was confirmed that the colorimetric assay for hydroxamic acid is suitable for detecting and quantifying the content of biodiesel in biodiesel/diesel blends and can also be easily adapted to field analyses.

MICROESTRUTURA E PROPRIEDADES DE FILMES DE AMIDO-ÁLCOOL POLIVINÍLICO-ALGINATO ADICIONADOS DE ÓLEOS ESSENCIAIS DE COPAÍBA E CAPIM LIMÃO

AbstractFilms obtained by blends between starch and other polymers and films developed with the addition of an oil can show higher water vapor barriers and improved mechanical properties. Films with starch/PVOH/alginate were obtained by adding copaiba and lemongrass essential oils (EOs). Films without oil served as the control. The microstructure, water vapor permeability (PVA), mechanical properties, and antifungal activity were determined for the films. The effects of the addition of the EOs on the properties of the films were dependent of the concentration and type of oil. The films with 0.5% lemongrass EO were similar to the control films. These films showed a 2.02 × 10-12 g s-1Pa m-1 PVA, 11.43 MPa tensile stress, 13.23% elongation, and 247.95 MPa/mm resistance at perforation. The addition of 1% of copaiba EO increased the PVA from 0.5 × 10-12 to 12.1 × 10-12 g s-1 Pa m-1 and the diffusion coefficient from 0.17 × 10-8 to 7.15 × 10-8m2/day. Films with quantities of EOs displayed fissures and micropores; the control films developed micropores with smaller diameters than films with EOs. The addition of EOs did not change the resulting infrared spectrum of the films. The films with oil displayed a diminished development of the Fusarium sp. culture, and the film without EOs did not display notable differences in the development of the culture. The starch/PVOH/alginate films with 0.5% lemongrass EO were the most suited for the development of a packaging active system.

DESENVOLVIMENTO DE ENSAIO PARA ANÁLISE QUALITATIVA DE BIODIESEL EM MISTURAS DIESEL-BIODIESEL PARA APLICAÇÃO EM POSTOS REVENDEDORES DE COMBUSTÍVEIS

In this study, we developed a method for the visual detection of biodiesel in petrodiesel-biodiesel (BX) blends through the aminolysis of the methyl or ethyl esters of fatty acids that are found in biodiesel and that are absent from diesel and vegetable oils. This method is based on three reactional stages, which produce a dark red and easily visualized complex in the presence of biodiesel. In the absence of biodiesel, there is no dark red coloring, whereas in the presence of diesel or vegetable oil, there is a light red to yellow coloring. This simple, practical, inexpensive, and effective procedure may be applied by petrol stations to guarantee to consumers and resellers the presence of biodiesel in diesel blends, regardless of the BX blend's initial coloring or of the sulfur found in the diesel. In short, it ensures a safe fuel tank fill-up with BX blend.

Lämpöpumppujärjestelmät integroidussa kylmä- ja lämpötehon tuotossa

Tässä työssä tutkittiin lämpöpumppujärjestelmiä, joilla tuotetaan samaan aikaan kylmä- ja lämpötehoa. Höyryn puristus lämpöpumppu on yleisimmin käytetty lämpöpumpputyyppi ja sen pääkomponentit ovat kompressori, lauhdutin, paisuntaventtiili ja höyrystin. Lämpöpumppu tuottaa samaan aikaan kylmätehoa höyrystimellä ja lämpötehoa lauhduttimella. Lämpöpumpun toiminta-arvoihin vaikuttaa valittujen lämpötilatasojen lisäksi voimakkaasti valitun kiertoaineen termodynaamiset ominaisuudet sekä kompressorin painesuhteeseen verrannollinen isentrooppihyötysuhde. Uusissa lämpöpumpuissa käytetään HFC yhdisteitä sekä sekoituksia kiertoaineina, mutta myös luonnolliset aineet, kuten ammoniakki, ovat lupaavia korvikkeita CFC yhdisteille. Sopivia sovelluskohteita kylmä- ja lämpötehon yhteistuotannolle ovat kauppa- ja asuinrakennukset, hotellit, toimistot, elintarviketeollisuus ja -myymälät sekä vierekkäiset jää- ja uimahallit ja hiihtoputket. Kylmä- ja lämpötehon yhteistuotannolla voitaisiin saavuttaa merkittäviä säästöjä ja päästövähennyksiä. Esimerkiksi jäähallien kylmäkoneiden lauhdelämmön hyödyntämisessä olisi Suomessa potentiaalia 6-10 miljoonan euron vuotuisiin säästöihin. Kylmä- ja lämpötehon yhteistuotanto voidaan toteuttaa hyödyntämällä kylmäkoneen lauhdelämpöä toisella lämpöpumpulla. Toinen vaihtoehto on käyttää eri tilojen samanaikaiseen lämmittämiseen ja jäähdyttämiseen HPS lämpöpumppua tai moniyksikköistä lämpöpumppua.

Performance impact of the application of castor oil biodiesel in diesel engines

The use of renewable fuels, such as the biodiesel, can ease the demand of fossil fuel for the power generation and transportation fields in rural area. In this work, the performance impact of the application of castor oil biodiesel is evaluated with an automotive and a stationary diesel engine. The application of B20 and B10 biodiesel blends and pre-heated net biodiesel is considered. The viability of the employment of B10 and B20 blends to mobility and power generation was observed from dynamometric bench tests, where this blends performed similar to fossil diesel. With the pre-heated net biodiesel, however, a brake torque loss and a specific consumption increase were observed with relation to diesel fuel.

Gelatin as an additive in bio-based barrier films

The main objective of the present study was to verify the approach on starch-gelatin blending for the paperboard coating formulations with enhanced barrier and mechanical properties. Based on that, another objective was to find out, how the approach will function with wood-based polysaccharides (CMC, EHEC and HPC) by analyzing their barrier properties and convertibility. The last objective was to find out, if pigments can be used in the composition of polysaccharide-protein blends without causing any negative effect on stated properties. The whole process chain of the barrier coating development was studied in the research. The methodology applied included pilot-scale coating and converting trials for the evaluation of mechanical properties of obtained coatings, namely their exposure to cracking with the loss of barrier properties. The results obtained indicated that the combination of starch with gelatin, in fact, improves the grease barrier properties and flexibility of starch-based coatings, thereby confirming the offered approach. The similar results were obtained for CMC, exhibited elevated barrier properties and surface coverage, proving that the approach also functions with wood-based polysaccharides. The introduction of equal amounts of talc gave various effects at different gelatin dosages on barrier properties of wood-based polysaccharides. Mainly, the elevation of grease barrier properties was observed. The convertibility of talc-filled coatings was not sufficient.

Paper for printed electronics and functionality

Mass-produced paper electronics (large area organic printed electronics on paper-based substrates, “throw-away electronics”) has the potential to introduce the use of flexible electronic applications in everyday life. While paper manufacturing and printing have a long history, they were not developed with electronic applications in mind. Modifications to paper substrates and printing processes are required in order to obtain working electronic devices. This should be done while maintaining the high throughput of conventional printing techniques and the low cost and recyclability of paper. An understanding of the interactions between the functional materials, the printing process and the substrate are required for successful manufacturing of advanced devices on paper. Based on the understanding, a recyclable, multilayer-coated paper-based substrate that combines adequate barrier and printability properties for printed electronics and sensor applications was developed in this work. In this multilayer structure, a thin top-coating consisting of mineral pigments is coated on top of a dispersion-coated barrier layer. The top-coating provides well-controlled sorption properties through controlled thickness and porosity, thus enabling optimizing the printability of functional materials. The penetration of ink solvents and functional materials stops at the barrier layer, which not only improves the performance of the functional material but also eliminates potential fiber swelling and de-bonding that can occur when the solvents are allowed to penetrate into the base paper. The multi-layer coated paper under consideration in the current work consists of a pre-coating and a smoothing layer on which the barrier layer is deposited. Coated fine paper may also be used directly as basepaper, ensuring a smooth base for the barrier layer. The top layer is thin and smooth consisting of mineral pigments such as kaolin, precipitated calcium carbonate, silica or blends of these. All the materials in the coating structure have been chosen in order to maintain the recyclability and sustainability of the substrate. The substrate can be coated in steps, sequentially layer by layer, which requires detailed understanding and tuning of the wetting properties and topography of the barrier layer versus the surface tension of the top-coating. A cost competitive method for industrial scale production is the curtain coating technique allowing extremely thin top-coatings to be applied simultaneously with a closed and sealed barrier layer. The understanding of the interactions between functional materials formulated and applied on paper as inks, makes it possible to create a paper-based substrate that can be used to manufacture printed electronics-based devices and sensors on paper. The multitude of functional materials and their complex interactions make it challenging to draw general conclusions in this topic area. Inevitably, the results become partially specific to the device chosen and the materials needed in its manufacturing. Based on the results, it is clear that for inks based on dissolved or small size functional materials, a barrier layer is beneficial and ensures the functionality of the printed material in a device. The required active barrier life time depends on the solvents or analytes used and their volatility. High aspect ratio mineral pigments, which create tortuous pathways and physical barriers within the barrier layer limit the penetration of solvents used in functional inks. The surface pore volume and pore size can be optimized for a given printing process and ink through a choice of pigment type and coating layer thickness. However, when manufacturing multilayer functional devices, such as transistors, which consist of several printed layers, compromises have to be made. E.g., while a thick and porous top-coating is preferable for printing of source and drain electrodes with a silver particle ink, a thinner and less absorbing surface is required to form a functional semiconducting layer. With the multilayer coating structure concept developed in this work, it was possible to make the paper substrate suitable for printed functionality. The possibility of printing functional devices, such as transistors, sensors and pixels in a roll-to-roll process on paper is demonstrated which may enable introducing paper for use in disposable “onetime use” or “throwaway” electronics and sensors, such as lab-on-strip devices for various analyses, consumer packages equipped with product quality sensors or remote tracking devices.

Avaliação físico-química de cafés torrados e moídos, de diferentes marcas comerciais, da região sul de Minas Gerais

A manutenção das características sensoriais de uma determinada marca de café torrado e moído, a cada produção de um novo lote, tem sido uma das maiores dificuldades enfrentadas pelas torrefadoras, devido à heterogeneidade da matéria-prima utilizada na elaboração dos blends. A composição química do café cru é responsável pelos atributos sensoriais da bebida, que são formados durante o processo de torração e variações nestes componentes acarretam bebidas diferenciadas. Com base neste fato, amostras de onze marcas comerciais de café torrado e moído, comercializadas na região Sul de Minas Gerais, foram coletadas nos meses de janeiro, abril e julho, e avaliadas quanto aos teores de extrato aquoso, extrato etéreo e cafeína. Os resultados demonstraram existir diferenças entre as marcas avaliadas e as épocas de coleta; cuja interação foi significativa para todas as variáveis analisadas. Apenas o teor de cafeína não apresentou diferença entre as marcas, durante o mês de janeiro. Os resultados obtidos para extrato aquoso, extrato etéreo e cafeína encontram-se dentro dos limites estipulados pela legislação vigente. Foram observadas diferenças nos valores das variáveis estudadas para uma mesma marca, em função da época de coleta, demonstrando a necessidade de maior padronização da matéria-prima utilizada e do processo de elaboração de blends para a fabricação do café torrado e moído.

Modification of commercial poly-lactide for extrusion coated food packaging applications

Poly-L-lactide (PLLA) is a widely used sustainable and biodegradable alternative to replace synthetic non-degradable plastic materials in the packaging industry. Conversely, its processing properties are not always optimal, e.g. insufficient melt strength at higher temperatures (necessary in extrusion coating processes). This thesis reports on research to improve properties of commercial PLLA grade (3051D from NatureWorks), to satisfy and extend end-use applications, such as food packaging by blending with modified PLLA. Adjustment of the processability by chain branching of commercial poly-L-lactide initiated by peroxide was evaluated. Several well-defined branched structures with four arms (sPLLA) were synthesized using pentaerythritol as a tetra-functional initiator. Finally, several block copolymers consisting of polyethylene glycol and PLLA (i.e. PEGLA) were produced to obtain a well extruded material with improved heat sealing properties. Reactive extrusion of poly-L-lactide was carried out in the presence of 0.1, 0.3 and 0.5 wt% of various peroxides [tert-butyl-peroxybenzoate (TBPB), 2,5-dimethyl-2,5-(tert-butylperoxy)-hexane (Lupersol 101; LOL1) and benzoyl peroxide (BPO)] at 190C. The peroxide-treated PLLAs showed increased complex viscosity and storage modulus at lower frequencies, indicating the formation of branched/cross linked architectures. The material property changes were dependent on the peroxide, and the used peroxide concentration. Gel fraction analysis showed that the peroxides, afforded different gel contents, and especially 0.5 wt% peroxide, produced both an extremely high molar mass, and a cross linked structure, not perhaps well suited for e.g. further use in a blending step. The thermal behavior was somewhat unexpected as the materials prepared with 0.5 wt% peroxide showed the highest ability for crystallization and cold crystallization, despite substantial cross linking. The peroxide-modified PLLA, i.e. PLLA melt extruded with 0.3 wt% of TBPB and LOL1 and 0.5 wt% BPO was added to linear PLLA in ratios of 5, 15 and 30 wt%. All blends showed increased zero shear viscosity, elastic nature (storage modulus) and shear sensitivity. All blends remained amorphous, though the ability of annealing was improved slightly. Extrusion coating on paperboard was conducted with PLLA, and peroxide-modified PLLA blends (90:10). All blends were processable, but only PLLA with 0.3 wt% of LOL1 afforded a smooth high quality surface with improved line speed. Adhesion levels between fiber and plastic, as well as heat seal performance were marginally reduced compared with pure 3051D. The water vapor transmission measurements (WVTR) of the blends containing LOL1 showed acceptable levels, only slightly lower than for comparable PLLA 3051D. A series of four-arm star-shaped poly-L-lactide (sPLLA) with different branch length was synthesized by ring opening polymerization (ROP) of L-lactide using pentaerythritol as initiator and stannous octoate as catalyst. The star-shaped polymers were further blended with its linear resin and studied for their melt flow and thermal properties. Blends containing 30 wt% of sPLLA with low molecular weight (30 wt%; Mwtotal: 2500 g mol-1 and 15000 g mol-1) showed lower zero shear viscosity and significantly increased shear thinning, while at the same time slightly increased crystallization of the blend. However, the amount of crystallization increased significantly with the higher molecular weight sPLLA, therefore the star-shaped structure may play a role as nucleating agent. PLLA-polyethylene glycol–PLLA triblock copolymers (PEGLA) with different PLLA block length were synthesized and their applicability as blends with linear PLLA (3051D NatureWorks) was investigated with the intention of improving heat-seal and adhesion properties of extrusion-coated paperboard. PLLA-PEG-PLLA was obtained by ring opening polymerization (ROP) of L-lactide using PEG (molecular weight 6000 g mol-1) as an initiator, and stannous octoate as catalyst. The structures of the PEGLAs were characterized by proton nuclear magnetic resonance spectroscopy (1H-NMR). The melt flow and thermal properties of all PEGLAs and their blends were evaluated using dynamic rheology, and differential scanning calorimeter (DSC). All blends containing 30 wt% of PEGLAs showed slightly higher zero shear viscosity, higher shear thinning and increased melt elasticity (based on tan delta). Nevertheless, no significant changes in thermal properties were distinguished. High molecular weight PEGLAs were used in extrusion coating line with 3051D without problems.