Dimerisation of cyclooctene using Grubbs' catalysts

The dimerisation of cyclooctene (COE) to 1,9-cyclohexadecadiene, a molecule of interest to the fragrance industry, has been achieved using ruthenium catalysts in organic solvents with significantly better selectivities (47-74%) and yields (39-60%) than previously reported (34% and 30%, respectively). Grubbs' first and second generation catalysts, the Hoveyda-Grubbs' catalyst and a phosphonium alkylidene catalyst were tested in a range of organic solvents and ionic liquids (ILs), including 1:1 IL/dichloromethane mixtures and biphasic IL + pentane systems. The best results (74% selectivity, 60% yield) were obtained using Grubbs' first generation catalyst in 1,2-dichloroethane. The formation of trimer, tetramer and other higher molecular mass products were found to be favoured at low catalyst loadings (0.77 mM). Studies of metathesis reactions using 1,9-cyclohexadecadiene as substrate indicated that the monomer-dimer and monomer-trimer reactions are faster than the dimer-dimer reaction. The use of IL media allowed for the recyclability of the catalyst, although a drop in the yield of dimer generally occurred after the first run. Heterogeneized catalysts, where the IL-catalyst system was immobilised onto silica, resulted in fast reactions leading to poor yields of dimer. (C) 2011 Elsevier B.V. All rights reserved.

A more direct way to make catalysts: one-pot ligand-assisted aerobic stripping and electrodeposition of copper on graphite

Electrodeposition of metals onto conductive supports such as graphite potentially provides a lower-waste method to form heterogeneous catalysts than the standard methods such as wet impregnation. Copper electrodeposition onto pressed graphite disc electrodes was investigated from aqueous CuSO4-ethylenediamine solutions by chronoamperometry with scanning electron microscopy used to ascertain the particle sizes obtained by this method. The particle size was studied as a function of pH, CuSO4-ethylenediamine concentration, and electrodeposition time. It was observed that decreasing the pH, copper-ethylenediamine concentration and time each decreased the size of the copper particles observed, with the smallest obtained being around 5-20 nm. Furthermore, electroless aerobic oxidation of copper metal in the presence of ethylenediamine was successfully coupled with the electrodeposition in the same vessel. In this way, deposition was achieved sequentially on up to twenty different graphite discs using the same ethylenediamine solution, demonstrating the recyclability of the ligand. The materials thus prepared were shown to be catalytically active for the mineralisation of phenol by hydrogen peroxide. Overall, the results provide a proof-of-principle that by making use of aerobic oxidation coupled with electrochemical deposition, elemental base metals can be used directly as starting materials to form heterogeneous catalysts without the need to use metal salts as catalyst precursors.

CO2 Capture in Wet and Dry Superbase Ionic Liquids

The solubility of carbon dioxide in five tetraalkylphosphonium superbase ionic liquids, namely the trihexyltetradecylphoshonium phenoxide, trihexyltetradecylphoshonium benzotriazolide, trihexyltetradecylphoshonium benzimidazolide, trihexyltetradecylphoshonium 1,2,3-triazolide, and trihexyltetradecylphoshonium 1,2,4-triazolide was studied experimentally under dry and wet conditions at 22 A degrees C and at atmospheric pressure, using a gravimetric saturation technique. The effects of anion structure and of the presence or absence of water in the solution on the carbon dioxide solubility were then deduced from the data. H-1 and C-13-NMR spectroscopy and ab initio calculations were also conducted to probe the interactions in these solutions, as carbon dioxide and water can compete in the ionic liquid structure during the absorption process. Additionally, the viscosity of selected superbase ionic liquids was measured under dry and wet conditions, in the presence or absence of CO2, to evaluate their practical application in carbon dioxide capture processes. Finally, the recyclability of the trihexyltetradecylphoshonium 1,2,4-triazolide under dry and wet conditions was determined to probe the ability of selected solvents to solubilize chemically a high concentration of carbon dioxide and then release it in a low energy demand process.

A novel recovery process for lipids from microalgæ for biodiesel production using a hydrated phosphonium ionic liquid

The use of a hydrated phosphonium ionic liquid, [P(CH<inf>2</inf>OH)<inf>4</inf>]Cl, for the extraction of microalgæ lipids for biodiesel production, was evaluated using two microalgæ species, Chlorella vulgaris and Nannochloropsis oculata. The ionic liquid extraction was compared to the conventional Soxhlet, and Bligh & Dyer, methods, giving the highest extraction efficiency in the case of C. vulgaris, at 8.1%. The extraction from N. oculata achieved the highest lipid yield for Bligh & Dyer (17.3%), while the ionic liquid extracted 12.8%. Nevertheless, the ionic liquid extraction showed high affinity to neutral/saponifiable lipids, resulting in the highest fatty acid methyl esters (FAMEs)-biodiesel yield (4.5%) for C. vulgaris. For N. oculata, the FAMEs yield of the ionic liquid and Bligh & Dyer extraction methods were similar (>8%), and much higher than for Soxhlet (<5%). The ionic liquid extraction proved especially suitable for lipid extraction from wet biomass, giving even higher extraction yields than from dry biomass, 14.9% and 12.8%, respectively (N. oculata). Remarkably, the overall yield of FAMEs was almost unchanged, 8.1% and 8.0%, for dry and wet biomass. The ionic liquid extraction process was also studied at ambient temperature, varying the extraction time, giving 75% of lipid and 93% of FAMEs recovery after thirty minutes, as compared to the extraction at 100 °C for one day. The recyclability study demonstrated that the ionic liquid was unchanged after treatment, and was successfully reused. The ionic liquid used is best described as [P(CH<inf>2</inf>OH)<inf>4</inf>]Cl·2H<inf>2</inf>O, where the water is not free, but strongly bound to the ions.

Novel furan polymer materials based on the reversible Diels-Alder reaction

A futura e inevitável escassez dos recursos fósseis, juntamente com o aumento imprevisível dos seus preços, levou, nas últimas décadas, a um aumento impressionante de iniciativas dedicadas não só à procura de fontes alternativas de fornecedores de energia, mas também de produtos químicos e polímeros a partir de fontes renováveis, em particular da biomassa vegetal. Entre estes, os polímeros derivados de monómeros furânicos constituem uma classe única de materiais cujas estruturas podem, em princípio, simular virtualmente os seus homólogos actualmente derivados de recursos fósseis. O anel furânico é uma estrutura heterocíclica com um carácter diénico pronunciado, o que torna-o um dieno particularmente apropriado para a reacção de Diels-Alder (DA) com dienófilos como a maleimida. Um dos aspectos mais relevantes da reacção de DA é a sua reversibilidade em função da temperatura, a qual permite que os aductos sejam facilmente revertidos nos seus precursores por aumento da temperatura (reacção de retro-DA). No caso específico da combinação furano-maleimida, a formação do aducto predomina até cerca de 60ºC, enquanto a reacção inversa é dominante acima de 100ºC. A combinação desta característica da reacção de DA com a química de compostos furânicos pode abrir um novo caminho para a preparação de materiais macromoleculares funcionais com base em fontes renováveis e com aplicações promissoras como auto-reparação e reciclabilidade. O principal objectivo desta Tese, é a síntese e caracterização de novos materiais poliméricos termo-reversíveis, aplicando a reacção de DA a monómeros complementares com estruturas dos tipos furânico (o dieno, designado por A) e de maleimida (o dienófilo, designado por B). A primeira etapa neste trabalho envolveu a síntese, purificação e caracterização de novos monómeros furânicos e de maleimida do tipo AA, A3, BB, B3, AB, AB2, cada um com diferentes grupos separadores das funções reactivas. Posteriormente, estes monómeros foram polimerizados e despolimerizados por ciclos de DA/retro-DA utilizando diferentes combinações. A formação e dissociação de todos os aductos de DA foram seguidas por ambas espectroscopias de UV e RMN de 1H. O primeiro sistema de DA estudado foi uma combinação modelo entre reagentes mono-funcionais (-A+-B), nomeadamente o acetato furfurílico (FA) e a N-metilmaleimida (MM), ambos comercialmente disponíveis. O objectivo desta abordagem foi estudar a cinética e o equilíbrio da formação/dissociação dos aductos de DA e obter indicações sobre as condições mais adequadas a serem usadas na preparação dos correspondentes novos materiais macromoleculares. Além disso, pretendia-se verificar a presença ou ausência de reacções secundárias que poderiam intervir em ambas as vias directa e inversa das reacções, mesmo após vários ciclos. A espectroscopia de UV forneceu informação quantitativa sobre a cinética de formação do aducto através da diminuição progressiva da absorvência máxima a 293 nm correspondente ao grupo maleimida, a diferentes temperaturas (35, 50, 65 ºC) Reciprocamente, a correspondente reacção de retro-DA foi seguida a 90 ºC através do aumento do mesmo pico. A reversibilidade destes sistemas foi verificada com sucesso após uma sequência de ciclos de DA/retro-DA. Adicionalmente, verificou-se que os espectros originaram um ponto isosbéstico, provando que estes sistemas não envolvem quaisquer reacções secundárias. Uma vez que foi usado um excesso de FA, as reacções de DA modelo apresentaram um comportamento cinético de pseudo-primeira ordem, com a constante de velocidade k mais alta (2.1x10-5 dm3mol-1s-1) para T=65 ºC. A correspondente energia de activação foi de 39.0 kJ.mol-1. A reacção de retro-DA seguiu um comportamento de primeira ordem, com constante de velocidade de 1.6x10-6 s-1. A evolução deste sistema por RMN de 1H a 65ºC deu-nos informações mais detalhadas sobre a sua evolução estrutural, ou seja, à medida que a intensidade dos picos atribuídos à formação do aducto aumentaram progressivamente ao longo do tempo, os pertencentes aos reagentes iniciais diminuiram proporcionalmente. O “rendimento final”, calculado após 20 dias à temperatura ambiente, foi de aproximadamente 70%. A reacção de retro-DA foi depois seguida a 90ºC, observando-se tal como na espectroscopia de UV, o deslocamento da reacção no sentido da regeneração dos reagentes de partida. A viabilidade de múltiplos ciclos de DA/retro-DA estabelecidos pela espectroscopia de UV foi igualmente confirmada por RMN de 1H. O passo seguinte envolveu o estudo de um sistema de policondensação linear baseado no crescimento gradual por reacção de DA entre um monómero bisfurânico A-A e um do tipo bismaleimida B-B, seguindo a mesma abordagem que no sistema modelo. O poliaducto linear foi obtido a partir de soluções equimolares dos monómeros, por reacção de DA a 65ºC. O progresso desta polimerização foi seguido por espectroscopia de UV e RMN de 1H e, mais qualitativamente, pelo aumento da viscosidade do meio. A reacção seguiu um comportamento de segunda ordem, com uma constante de velocidade de 9.4x10-6 dm3mol-1s-1, e observou-se novamente um ponto isosbéstico nos dados de UV. Os espectros de RMN apresentaram o padrão esperado, nomeadamente o aumento progressivo dos sinais associados ao aducto e a correspondente diminuição dos grupos furano e maleimida livres. A despolimerização do poliaducto através da reacção de retro-DA foi seguida a 110ºC usando as mesmas técnicas. Os dados de UV mostraram o retorno progressivo da absorção dos grupos de maleimida, seguindo um comportamento cinético de primeira ordem, com constante de velocidade de 2.5x10-6 s-1, até à completa regeneração de ambos os monómeros. Os espectros de RMN providenciaram mais uma vez informação estrutural sobre o progresso da despolimerização, a qual foi acompanhada por uma diminuição progressiva da viscosidade. Adicionalmente, para seguir a retro- DA, adicionou-se um excesso de composto furânico monofuncional, nomeadamente o 2,5-dimetilfurano (DMFu), ao sistema de modo a bloquear as funções maleimida complementares, evitando assim a repolimerização após arrefecimento. Os productos isolados foram então o monómero bisfurânico AA, DMFu que não reagiu e o bisaducto não-polimerizável de BB com DMFu. Este resultado indicou claramente que o polímero foi de facto revertido nos seus monómeros durante a reacção de retro-DA. O terceiro sistema estudado foi outra polimerização linear, seguindo as mesmas condições experimentais que os anteriores, mas com uma estratégia diferente de modo a contornar o problema clássico de assegurar a estequiometria exacta dos monómeros. As estruturas dos monómeros utilizados incorporam ambos os grupos reactivos, i.e, moléculas do tipo A-B. A polimerização prematura destes monómeros intrinsecamente reactivos foi evitada com a protecção do grupo maleimida na forma de um aducto de DA com furano, até a incorporação do substituinte furânico na outra extremidade. Portanto, a policondensação destes monómeros foi iniciada após a desprotecção in situ deste composto mediante aquecimento, seguido de arrefecimento até à temperatura adequada para polimerizar. Os resultados obtidos por UV e RMN sugerem que de facto o uso de monómeros do tipo A-B oferece um melhor sistema linear. Em seguida, foram estudados sistemas de policondensação não-linear por reacção de DA, entre monómeros (um ou ambos) com funcionalidade superior a dois, nomeadamente sistemas do tipo A3+B-B ou A-A+B3, seguindo mais uma vez as mesmas condições experimentais. Uma vez que utilizam monómeros complementares contendo, em média, mais de duas funcionalidades, estes sistemas conduzem a materiais reticulados. Nestes estudos, foram usadas três razões molares de [maleimida]/[furano], nomeadamente 1.0, 0.75 e 0.5, de modo a estudar ambas as situações de não-gelificação e reticulação. Ambos sistemas apresentaram um comportamento regular e boa reciclabilidade quer para gerar situações que possam conduzir à formação de redes a diferentes graus de conversão, ou que possam parar antes da sua obtenção, conforme previsto pela equação de Flory-Stockmayer. Como esperado, a utilização de grupos complementares em quantidades estequiométricas produziu o espessamento mais rápido e a reticulação quase completa; à medida que a quantidade relativa de monómero trifuncional decresceu, as reacções pararam antes da reticulação, ou seja, originaram meios altamente viscosos contendo polímeros solúveis altamente ramificados. As reacções de retro-DA a 110 ºC conduziram à gradual dissolução das partículas de gel (quando presentes), tendo sido comprovado pelos espectros de UV e de RMN de 1H, evidenciado a regeneração dos monómeros. Tal como no sistema do tipo A-A+B-B, a reacção de retro-DA foi seguida adicionando um excesso de DMFu ao sistema reaccional. Como esperado, os produtos finais foram os monómeros furânicos, o DMFu em excesso e o trisaducto ou o bisaducto maleimida-DMFu, o que confirma a eficiência da despolimerização com regeneração dos monómeros iniciais. O último sistema de policondensação por reacção de DA envolveu um monómero assimetricamente substituído do tipo AB2, capaz de originar estruturas macromoleculares hiper-ramificadas que não reticulam. Este estudo preliminar deste sistema foi seguido nas mesmas condições experimentais que os anteriores, apresentando um comportamento com as características esperadas.

Synthesis of new vegetable oil-based polymeric materials

A crescente procura de recursos fosseis a que se tem assistido nos ultimos anos, tem resultado num crescimento sem precedentes dos precos, com consequencias imprevisiveis e que levara, no espaco de decadas, ao seu inevitavel esgotamento. A procura de um modelo de desenvolvimento sustentavel, baseado em recursos renovaveis e o grande desafio que se coloca a civilizacao no seculo XXI. A biomassa vegetal, atraves das designadas gBio-refinarias h, e uma alternativa logica para a producao de produtos quimicos e de materiais mas tambem de combustiveis e energia. Os oleos vegetais constituem uma das fracoes da biomassa vegetal, cuja exploracao tem merecido redobrada atencao nos ultimos anos, como fonte de materiais e de combustiveis. Assim, a presente dissertacao tem por objetivo o desenvolvimento de novos materiais polimericos derivados de oleos vegetais, seguindo duas abordagens distintas, nomeadamente a preparacao de polimeros atraves de polimerizacao por etapas e polimerizacao em cadeia (Parte B e C, respetivamente). Em primeiro lugar, foram sintetizados poliesteres alifaticos de cadeia longa a partir de monomeros provenientes do oleo de colza (Capitulo III). A auto-metatese do acido erucico com catalisadores de rutenio, seguida de hidrogenacao da ligacao dupla, originou o acido 1,26-hexacosanodioico, que por sua vez foi convertido em hexacosano-1,26-diol. Subsequentemente, a policondensacao do acido ƒ¿,ƒÖ-dicarboxilico de cadeia longa com o hexacosano-1,26-diol originou o poliester 26,26. O diacido C26 foi tambem polimerizado com outros alcano-diois de cadeia curta, nomeadamente o dodecano-1,12-diol e o butano-1,2-diol, produzindo, respetivamente, os poliesteres 12,26 e 4,26. Estes poliesteres de fontes 100% renovaveis possuem valores de Mn na ordem dos 8-14 kDa e valores de PDI entre 2.1 e 2.7. As propriedades destes poliesteres alifaticos foram avaliadas atraves de varias tecnicas, revelando elevada cristalinidade (com uma estrutura cristalina como a do polietileno) e elevadas temperaturas de fusao (74-104 ‹C), cristalizacao (68-92 ‹C) e degradacao (323-386 ‹C). Em segundo lugar, foram sintetizados polimeros lineares termo-reversiveis a partir de derivados do oleo de ricinio (Capitulo IV). Para tal foram preparados monomeros que incorporam aneis furanicos inseridos atraves do acoplamento tiol-eno, e que posteriormente foram polimerizados pela reacao de Diels-Alder (DA) entre os grupos furano (dieno A) e estruturas complementares do tipo maleimida (dienofilo B). Para as polimerizacoes DA foram consideradas duas abordagens diferentes, nomeadamente (i) o uso de monomeros com dois aneis furanicos terminais em conjunto com uma bismaleimida (sistemas AA+BB) e (ii) a utilizacao de um monomero que incorpora ambos os grupos reativos, furano e maleimida, na sua estrutura (sistema AB). Este estudo demonstrou claramente que ambas as estratégias foram bem sucedidas embora com diferentes resultados em termos da natureza dos produtos obtidos. Estes polímeros lineares apresentam valores relativamente baixos de Tg (-40 to -2 °C) devido à natureza flexível dos grupos separadores das funções reativas, e de Mn (4.5-9.0 kDa) dada a observada tendência de ciclização associada a concentrações baixas de monómero. A aplicação da reação de retro-DA aos polímeros em causa confirmou o seu caráter reversível, ou seja, a possibilidade de promover, em condições controladas, a despolimerização com recuperação dos monómeros de partida. Esta particularidade abre caminhos para materiais macromoleculares originais com aplicações promissoras tais como auto-reparação e reciclabilidade. Em terceiro lugar, sintetizaram-se polímeros não-lineares termo-reversíveis a partir de derivados do óleo de ricínio (Capítulo V). Para tal foram preparados monómeros trifuncionais e posteriormente polimerizados através da reação de DA entre os grupos reativos complementares furano/maleimida. Foram consideradas três abordagens distintas para preparar estes polímeros não-lineares, nomeadamente através da utilização de (i) um monómero bisfurânico em combinação com uma trismaleimida (sistema A2+B3) e (ii) um monómero trisfurânico em conjunto com uma bismaleimida (sistema A3+B2) que originaram materiais ramificados ou reticulados, e ainda (iii) a utilização de monómeros assimetricamente substituídos do tipo A2B ou AB2 capazes de originar estruturas macromoleculares hiper-ramificadas. Todos os sistemas apresentaram valores de Tg perto de 0 °C, o que era de esperar para estes materiais não-lineares. A aplicação da reação de retro-DA comprovou mais uma vez o caráter termo-reversível das polimerizações em causa. Em quarto lugar e último lugar, foram preparados copolímeros de acetato de vinilo (VAc) com monómeros derivados de óleo de girassol (Capítulo VI). Ésteres vinílicos de ácidos gordos (FAVE) foram sintetizados por transvinilação dos ácidos oleico e linoleico com VAc catalisada por um complexo de irídio. Os monómeros vinílicos preparados foram caracterizados e posteriormente homopolimerizados e copolimerizados com VAc através do uso dos grupos vinílicos terminais como função inicial de polimerização. A variação do tipo e quantidade de monómero FAVE e da quantidade de iniciador radicalar originou copolímeros de VAc com valores de Mn na gama de 1.2-3.0 kDa e valores de Tg de -5 a 16 °C. Os copolímeros foram avaliados em testes de cura oxidativa através das insaturações nas suas cadeias alifáticas para formar materiais reticulados, e os resultados sugerem que eles podem ser sistemas efetivos de cura para aplicações como tintas, vernizes e outros tipos de revestimento. Todos os materiais poliméricos preparados ao longo deste trabalho constituem contribuições atrativas para a área dos polímeros oriundos de recursos renováveis e representam uma prova indiscutível de que os óleos vegetais são percursores promissores de materiais macromoleculares com potenciais aplicações.

Mix design process of polyester polymer mortars modified with recycled GFRP waste materials

In this study, the effect of incorporation of recycled glass fibre reinforced plastics (GFRP) waste materials, obtained by means of shredding and milling processes, on mechanical behaviour of polyester polymer mortars (PM) was assessed. For this purpose, different contents of GFRP recyclates, between 4% up to 12% in weight, were incorporated into polyester PM materials as sand aggregates and filler replacements. The effect of the addition of a silane coupling agent to resin binder was also evaluated. Applied waste material was proceeding from the shredding of the leftovers resultant from the cutting and assembly processes of GFRP pultrusion profiles. Currently, these leftovers as well as non-conform products and scrap resulting from pultrusion manufacturing process are landfilled, with additional costs to producers and suppliers. Hence, besides the evident environmental benefits, a viable and feasible solution for these wastes would also conduct to significant economic advantages. Design of experiments and data treatment were accomplish by means of full factorial design approach and analysis of variance ANOVA. Experimental results were promising toward the recyclability of GFRP waste materials as partial replacement of aggregates and reinforcement for PM materials, with significant improvements on mechanical properties of resultant mortars with regards to waste-free formulations.

Mechanical behaviour analysis of polyester polymer mortars modified with recycled GFRP waste materials

In this study the effect of incorporation of recycled glass-fibre reinforced polymer (GFRP) waste materials, obtained by means of milling processes, on mechanical behaviour of polyester polymer mortars was assessed. For this purpose, different contents of recycled GFRP waste powder and fibres, with distinct size gradings, were incorporated into polyester based mortars as sand aggregates and filler replacements. Flexural and compressive loading capacities were evaluated and found better than unmodified polymer mortars. GFRP modified polyester based mortars also show a less brittle behaviour, with retention of some loading capacity after peak load. Obtained results highlight the high potential of recycled GFRP waste materials as efficient and sustainable reinforcement and admixture for polymer concrete and mortars composites, constituting an emergent waste management solution.

Optimization process of polyester polymer mortars modified with recycled GFRP waste aggregates – application of factorial experiment design-

Glass fibre-reinforced plastics (GFRP), nowadays commonly used in the construction, transportation and automobile sectors, have been considered inherently difficult to recycle due to both: cross-linked nature of thermoset resins, which cannot be remolded, and complex composition of the composite itself, which includes glass fibres, matrix and different types of inorganic fillers. Presently, most of the GFRP waste is landfilled leading to negative environmental impacts and supplementary added costs. With an increasing awareness of environmental matters and the subsequent desire to save resources, recycling would convert an expensive waste disposal into a profitable reusable material. There are several methods to recycle GFR thermostable materials: (a) incineration, with partial energy recovery due to the heat generated during organic part combustion; (b) thermal and/or chemical recycling, such as solvolysis, pyrolisis and similar thermal decomposition processes, with glass fibre recovering; and (c) mechanical recycling or size reduction, in which the material is subjected to a milling process in order to obtain a specific grain size that makes the material suitable as reinforcement in new formulations. This last method has important advantages over the previous ones: there is no atmospheric pollution by gas emission, a much simpler equipment is required as compared with ovens necessary for thermal recycling processes, and does not require the use of chemical solvents with subsequent environmental impacts. In this study the effect of incorporation of recycled GFRP waste materials, obtained by means of milling processes, on mechanical behavior of polyester polymer mortars was assessed. For this purpose, different contents of recycled GFRP waste materials, with distinct size gradings, were incorporated into polyester polymer mortars as sand aggregates and filler replacements. The effect of GFRP waste treatment with silane coupling agent was also assessed. Design of experiments and data treatment were accomplish by means of factorial design and analysis of variance ANOVA. The use of factorial experiment design, instead of the one factor at-a-time method is efficient at allowing the evaluation of the effects and possible interactions of the different material factors involved. Experimental results were promising toward the recyclability of GFRP waste materials as polymer mortar aggregates, without significant loss of mechanical properties with regard to non-modified polymer mortars.

Reusability assessment of thermoset polymeric composite wastes as reinforcement and filler replacement for polymer concrete materials

The development and applications of thermoset polymeric composites, namely fiber reinforced polymers (FRP), have shifted in the last decades more and more into the mass market [1]. Production and consume have increased tremendously mainly for the construction, transportation and automobile sectors [2, 3]. Although the many successful uses of thermoset composite materials, recycling process of byproducts and end of lifecycle products constitutes a more difficult issue. The perceived lack of recyclability of composite materials is now increasingly important and seen as a key barrier to the development or even continued used of these materials in some markets.

New end-use application for GFRP recyclates as reinforcement for concrete-polymer materials’

Glass fibre-reinforced plastics (GFRP), nowadays commonly used in the construction, transportation and automobile sectors, have been considered inherently difficult to recycle due to both: cross-linked nature of thermoset resins, which cannot be remolded, and complex composition of the composite itself, which includes glass fibres, matrix and different types of inorganic fillers. Presently, most of the GFRP waste is landfilled leading to negative environmental impacts and supplementary added costs. With an increasing awareness of environmental matters and the subsequent desire to save resources, recycling would convert an expensive waste disposal into a profitable reusable material. There are several methods to recycle GFR thermostable materials: (a) incineration, with partial energy recovery due to the heat generated during organic part combustion; (b) thermal and/or chemical recycling, such as solvolysis, pyrolisis and similar thermal decomposition processes, with glass fibre recovering; and (c) mechanical recycling or size reduction, in which the material is subjected to a milling process in order to obtain a specific grain size that makes the material suitable as reinforcement in new formulations. This last method has important advantages over the previous ones: there is no atmospheric pollution by gas emission, a much simpler equipment is required as compared with ovens necessary for thermal recycling processes, and does not require the use of chemical solvents with subsequent environmental impacts. In this study the effect of incorporation of recycled GFRP waste materials, obtained by means of milling processes, on mechanical behavior of polyester polymer mortars was assessed. For this purpose, different contents of recycled GFRP waste materials, with distinct size gradings, were incorporated into polyester polymer mortars as sand aggregates and filler replacements. The effect of GFRP waste treatment with silane coupling agent was also assessed. Design of experiments and data treatment were accomplish by means of factorial design and analysis of variance ANOVA. The use of factorial experiment design, instead of the one-factor-at-a-time method is efficient at allowing the evaluation of the effects and possible interactions of the different material factors involved. Experimental results were promising toward the recyclability of GFRP waste materials as aggregates and filler replacements for polymer mortar, with significant gain of mechanical properties with regard to non-modified polymer mortars.

Design of experiments applied to the mix design process of polymer mortar materials modified with GFRP recyclates

In this work, the effect of incorporation of recycled glass fibre reinforced plastics (GFRP) waste materials, obtained by means of shredding and milling processes, on mechanical behavior of polyester polymer mortar (PM) materials was assessed. For this purpose, different contents of GFRP recyclates (between 4% up to 12% in mass), were incorporated into polyester PM materials as sand aggregates and filler replacements. The effect of silane coupling agent addition to resin binder was also evaluated. Applied waste material was proceeding from the shredding of the leftovers resultant from the cutting and assembly processes of GFRP pultrusion profiles. Currently, these leftovers, jointly with unfinished products and scrap resulting from pultrusion manufacturing process, are landfilled, with supplementary added costs. Thus, besides the evident environmental benefits, a viable and feasible solution for these wastes would also conduct to significant economic advantages. Design of experiments and data treatment were accomplish by means of full factorial design approach and analysis of variance ANOVA. Experimental results were promising toward the recyclability of GFRP waste materials as aggregates and reinforcement for PM materials, with significant improvements on mechanical properties with regard to non-modified formulations.

Experimental study on polyester based concretes filled with glass fibre reinforced plastic recyclates – a contribution to composite materials sustainability

The development and applications of thermoset polymeric composites, namely fibre reinforced plastics (FRP), have shifted in the last decades more and more into the mass market [1]. Despite of all advantages associated to FRP based products, the increasing production and consume also lead to an increasing amount of FRP wastes, either end-of-lifecycle products, or scrap and by-products generated by the manufacturing process itself. Whereas thermoplastic FRPs can be easily recycled, by remelting and remoulding, recyclability of thermosetting FRPs constitutes a more difficult task due to cross-linked nature of resin matrix. To date, most of the thermoset based FRP waste is being incinerated or landfilled, leading to negative environmental impacts and supplementary added costs to FRP producers and suppliers. This actual framework is putting increasing pressure on the industry to address the options available for FRP waste management, being an important driver for applied research undertaken cost efficient recycling methods. [1-2]. In spite of this, research on recycling solutions for thermoset composites is still at an elementary stage. Thermal and/or chemical recycling processes, with partial fibre recovering, have been investigated mostly for carbon fibre reinforced plastics (CFRP) due to inherent value of carbon fibre reinforcement; whereas for glass fibre reinforced plastics (GFRP), mechanical recycling, by means of milling and grinding processes, has been considered a more viable recycling method [1-2]. Though, at the moment, few solutions in the reuse of mechanically-recycled GFRP composites into valueadded products are being explored. Aiming filling this gap, in this study, a new waste management solution for thermoset GFRP based products was assessed. The mechanical recycling approach, with reduction of GFRP waste to powdered and fibrous materials was applied, and the potential added value of obtained recyclates was experimentally investigated as raw material for polyester based mortars. The use of a cementless concrete as host material for GFRP recyclates, instead of a conventional Portland cement based concrete, presents an important asset in avoiding the eventual incompatibility problems arisen from alkalis silica reaction between glass fibres and cementious binder matrix. Additionally, due to hermetic nature of resin binder, polymer based concretes present greater ability for incorporating recycled waste products [3]. Under this scope, different GFRP waste admixed polymer mortar (PM) formulations were analyzed varying the size grading and content of GFRP powder and fibre mix waste. Added value of potential recycling solution was assessed by means of flexural and compressive loading capacities of modified mortars with regard to waste-free polymer mortars.

Recyclable Short Fibre Reinforced Plastics PP/Nylon and HDPE/Nylon composites

The study shows that standard plastics like polypropylene and high density polyethylene can be reinforced by adding nylon short fibres. Compared to the conventional glass reinforced thermoplastics this novel class of reinforced thermoplastics has the major advantage of recyclability. Hence such composites represent a new spectrum of recyclable polymer composites. The fibre length and fibre diameter used for reinforcement are critical parameters While there is a critical fibre length below which no effective reinforcement takes place, the reinforcement improves when the fibre diameter decreases due to increased surface area.While the fibres alone give moderate reinforcement, chemical modification of the matrix can further improve the strength and modulus of the composites. Maleic anhydride grafting in presence of styrene was found to be the most efficient chemical modification. While the fibre addition enhances the viscosity of the melt at lower shear rates, the enhancement at higher shear rate is only marginal. This shows that processing of the composite can be done in a similar way to that of the matrix polymer in high shear operations such as injection moulding. Another significant observation is the decrease in melt viscosity of the composite upon grafting. Thus chemical modification of matrix makes processing of the composite easier in addition to improving the mechanical load bearing capacity.For the development of a useful short fibre composite, selection of proper materials, optimum design with regard to the particular product and choosing proper processing parameters are most essential. Since there is a co-influence of many parameters, analytical solutions are difficult. Hence for selecting proper processing parameters 'rnold flow' software was utilized. The orientation of the fibres, mechanical properties, temperature profile, shrinkage, fill time etc. were determined using the software.Another interesting feature of the nylon fibre/PP and nylon fibre/HDPE composites is their thermal behaviour. Both nylon and PP degrade at the same temperature in single steps and hence the thermal degradation behaviour of the composites is also being predictable. It is observed that the thermal behaviour of the matrix or reinforcement does not affect each other. Almost similar behaviour is observed in the case of nylon fibre/HDPE composites. Another equally significant factor is the nucleating effect of nylon fibre when the composite melt cools down. In the presence of the fibre the onset of crystallization occurs at slightly higher temperature.When the matrix is modified by grafting, the onset of crystallization occurs at still higher temperature. Hence it may be calculated that one reason for the improvement in mechanical behaviour of the composite is the difference in crystallization behaviour of the matrix in presence of the fibre.As mentioned earlier, a major advantage of these composites is their recyclability. Two basic approaches may be employed for recycling namely, low temperature recycling and high temperature recycling. In the low temperature recycling, the recycling is done at a temperature above the melting point of the matrix, but below that of the fibres while in the high temperature route. the recycling is done at a temperature above the melting points of both matrix and fibre. The former is particularly interesting in that the recycled material has equal or even better mechanical properties compared to the initial product. This is possible because the orientation of the fibre can improve with successive recycling. Hence such recycled composites can be used for the same applications for which the original composite was developed. In high temperature recycling, the composite is converted into a blend and hence the properties will be inferior to that of the original composite, but will be higher than that of the matrix material alone.

Development of Best Practices for Ship Recycling Processes

Ship recycling has been considered as the best means to dispose off an obsolete ship. The current state of art of technology combined with the demands of sustainable developments from the global maritime industrial sector has modified the status of erstwhile ‘ship breaking’ involving ship scrap business to a modern industry undertaking dismantling of ships and recycling/reusing the dismantled products in a supply chain of pre owned product market by following the principles of recycling. Industries will have to formulate a set of best practices and blend them with the engineering activities for producing better quality products, improving the productivity and for achieving improved performances related to sustainable development. Improved performance by industries in a sustainable development perspective is accomplished only by implementing the 4E principles, ie.,. ecofriendliness, engineering efficiency, energy conservation and ergonomics in their core operations. The present study has done a comprehensive investigation into various ship recycling operations for formulating a set of best practices.Being the ultimate life cycle stage of a ship, ship recycling activities incorporate certain commercial procedures well in advance to facilitate the objectives of dismantling and recycling/reusing of various parts of the vessel. Thorough knowledge regarding these background procedures in ship recycling is essential for examining and understanding the industrial business operations associated with it. As a first step, the practices followed in merchant shipping operations regarding the decision on decommissioning have been and made available in the thesis. Brief description about the positioning methods and important preparations for the most feasible ship recycling method ie.,. beach method have been provided as a part of the outline of the background information. Available sources of guidelines, codes and rules & regulations for ship recycling have been compiled and included in the discussion.Very brief summary of practices in major ship recycling destinations has been prepared and listed for providing an overview of the global ship recycling activities. The present status of ship recycling by treating it as a full fledged engineering industry has been brought out to establish the need for looking into the development of the best practices. Major engineering attributes of ship as a unique engineering product and the significant influencing factors on her life cycle stage operations have been studied and added to the information base on ship recycling. Role of ship recycling industry as an important player in global sustainable development efforts has been reviewed by analysing the benefits of ship recycling. A brief synopsis on the state of art of ship recycling in major international ship recycling centres has also been incorporated in the backdrop knowledgebase generation on ship recycling processes.Publications available in this field have been reviewed and classified into five subject categories viz., Infrastructure for recycling yards and methods of dismantling, Rules regarding ship recycling activities, Environmental and safety aspects of ship recycling, Role of naval architects and ship classification societies, Application of information technology and Demand forecasting. The inference from the literature survey have been summarised and recorded. Noticeable observations in the inference include need of creation of a comprehensive knowledgebase on ship recycling and its effective implementation in the industry and the insignificant involvement of naval architects and shipbuilding engineers in ship recycling industry. These two important inferences and the message conveyed by them have been addressed with due importance in the subsequent part of the present study.As a part of the study the importance of demand forecasting in ship recycling has been introduced and presented. A sample input for ship recycling data for implementation of computer based methods of demand forecasting has been presented in this section of the thesis.The interdisciplinary nature of engineering processes involved in ship recycling has been identified as one of the important features of this industry. The present study has identified more than a dozen major stake holders in ship recycling having their own interests and roles. It has also been observed that most of the ship recycling activities is carried out in South East Asian countries where the beach based ship recycling is done in yards without proper infrastructure support. A model of beach based ship recycling has been developed and the roles, responsibilities and the mutual interactions of the elements of the system have been documented as a part of the study Subsequently the need of a generation of a wide knowledgebase on ship recycling activities as pointed out by the literature survey has been addressed. The information base and source of expertise required to build a broad knowledgebase on ship recycling operations have been identified and tabulated. Eleven important ship recycling processes have been identified and a brief sketch of steps involved in these processes have been examined and addressed in detail. Based on these findings, a detailed sequential disassembly process plan of ship recycling has been prepared and charted. After having established the need of best practices in ship recycling initially, the present study here identifies development of a user friendly expert system for ship recycling process as one of the constituents of the proposed best practises. A user friendly expert system has been developed for beach based ship recycling processes and is named as Ship Recycling Recommender (SRR). Two important functions of SRR, first one for the ‘Administrators’, the stake holders at the helm of the ship recycling affairs and second one for the ‘Users’, the stake holders who execute the actual dismantling have been presented by highlighting the steps involved in the execution of the software. The important output generated, ie.,. recommended practices for ship dismantling processes and safe handling information on materials present onboard have been presented with the help of ship recycling reports generated by the expert system. A brief account of necessity of having a ship recycling work content estimation as part of the best practices has been presented in the study. This is supported by a detailed work estimation schedule for the same as one of the appendices.As mentioned earlier, a definite lack of involvement of naval architect has been observed in development of methodologies for improving the status of ship recycling industry. Present study has put forward a holistic approach to review the status of ship recycling not simply as end of life activity of all ‘time expired’ vessels, but as a focal point of integrating all life cycle activities. A new engineering design philosophy targeting sustainable development of marine industrial domain, named design for ship recycling has been identified, formulated and presented. A new model of ship life cycle has been proposed by adding few stages to the traditional life cycle after analysing their critical role in accomplishing clean and safe end of life and partial dismantling of ships. Two applications of design for ship recycling viz, recyclability of ships and her products and allotment of Green Safety Index for ships have been presented as a part of implementation of the philosophy in actual practice.