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.

An experimental study on recycling and reuse of pultruded composite material wastes

Glass fibre-reinforced plastics (GFRP) have been considered inherently difficult to recycle due to both: cross-linked nature of thermoset resins, which cannot be remoulded, and complex composition of the composite itself. 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. In this study, efforts were made in order to recycle grinded GFRP waste, proceeding from pultrusion production scrap, into new and sustainable composite materials. For this purpose, GFRP waste recyclates, were incorporated into polyester based mortars as fine aggregate and filler replacements at different load contents and particle size distributions. Potential recycling solution was assessed by mechanical behaviour of resultant GFRP waste modified polymer mortars. Results revealed that GFRP waste filled polymer mortars present improved flexural and compressive behavior over unmodified polyester based mortars, thus indicating the feasibility of the GFRP industrial waste reuse into concrete-polymer composite materials.

A case study undertaken recycling & reuse of glass fiber reinforced thermoset polumer wastes of composite materials industry

Glass fibre-reinforced plastics (GFRP) have been considered inherently difficult to recycle due to both: crosslinked nature of thermoset resins, which cannot be remoulded, and complex composition of the composite itself. 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. In this study, efforts were made in order to recycle grinded GFRP waste, proceeding from pultrusion production scrap, into new and sustainable composite materials. For this purpose, GFRP waste recyclates, were incorporated into polyester based mortars as fine aggregate and filler replacements at different load contents and particle size distributions. Potential recycling solution was assessed by mechanical behaviour of resultant GFRP waste modified polymer mortars. Results revealed that GFRP waste filled polymer mortars present improved flexural and compressive behaviour over unmodified polyester based mortars, thus indicating the feasibility of the GFRP industrial waste reuse into concrete-polymer composite materials.

Desenvolvimento de uma cola biodegradável

Este documento especifica o trabalho realizado no estágio, que decorreu na Colquímica, sediada em Valongo. Este trabalho teve como objetivo colaborar no desenvolvimento de uma cola com características biodegradáveis. O estágio foi orientado pela Engenheira Cristina Frutuoso, no que diz respeito à orientação por parte da Colquímica, e pelo Professor Dr. Gilberto Pinto e Alfredo Crispim, ISEP. O trabalho foi dividido em duas instâncias, sendo a primeira direcionada para a formulação de uma cola com características biodegradáveis e a segunda para a realização do teste de Sturm, um teste de biodegradabilidade capaz de quantificar a quantidade de CO2 produzido pelo processo de biodegradação. Inicialmente foram desenvolvidas e estudadas dez formulações através das variações de resinas e óleo plastificante e estudado o seu comportamento reológico relacionado à variação de viscosidade em função da temperatura. Com base nos resultados obtidos verificou-se que a melhor formulação seria a A8. Estudaram-se as propriedades mecânicas da formulação escolhida e decidiu-se que esta estaria apta a ser usada no fecho de caixas de cartão de produtos ultra congelados assim como no fecho de caixas de cartão de detergentes em pó com peso até 3 Kg. Depois de escolhida a formulação deu-se início ao teste de Sturm, teste meramente orientativo. Durante dezassete dias avaliou-se a quantidade de CO2 produzida durante o processo de biodegradação. Após avaliação dos resultados verificou-se que a taxa de biodegradação para a amostra foi de 0,055 g de CO2. Com a finalidade de confirmar os resultados obtidos no teste de Sturm foi efetuada uma réplica do ensaio, a qual se encontra a decorrer sendo os resultados facultados, posteriormente, à empresa.

Effects of Soil Compaction and Organic Carbon Content on Preferential Flow in Loamy Field Soils

Abstract: Preferential flow and transport through macropores affect plant water use efficiency and enhance leaching of agrochemicals and the transport of colloids, thereby increasing the risk for contamination of groundwater resources. The effects of soil compaction, expressed in terms of bulk density (BD), and organic carbon (OC) content on preferential flow and transport were investigated using 150 undisturbed soil cores sampled from 15 × 15–m grids on two field sites. Both fields had loamy textures, but one site had significantly higher OC content. Leaching experiments were conducted in each core by applying a constant irrigation rate of 10 mm h−1 with a pulse application of tritium tracer. Five percent tritium mass arrival times and apparent dispersivities were derived from each of the tracer breakthrough curves and correlated with texture, OC content, and BD to assess the spatial distribution of preferential flow and transport across the investigated fields. Soils from both fields showed strong positive correlations between BD and preferential flow. Interestingly, the relationships between BD and tracer transport characteristics were markedly different for the two fields, although the relationship between BD and macroporosity was nearly identical. The difference was likely caused by the higher contents of fines and OC at one of the fields leading to stronger aggregation, smaller matrix permeability, and a more pronounced pipe-like pore system with well-aligned macropores.

Re-Use Assessment of Thermoset Composite Wastes as Aggregate and Filler Replacement for Concrete-Polymer Composite Materials: A case study regarding GFRP pultrusion wastes

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 the cross-linked nature of thermoset resins, which cannot be remoulded, and the complex composition of the composite itself, which includes glass fibres, polymer matrix and different types of inorganic fillers. Hence, to date, most of the thermoset based GFRP waste is being incinerated or landfilled leading to negative environmental impacts and additional costs to producers and suppliers. 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. In this study, the effect of the incorporation of mechanically recycled GFRP pultrusion wastes on flexural and compressive behaviour of polyester polymer mortars (PM) was assessed. For this purpose, different contents of GFRP recyclates (0%, 4%, 8% and 12%, w/w), with distinct size grades (coarse fibrous mixture and fine powdered mixture), were incorporated into polyester PM as sand aggregates and filler replacements. The effect of the incorporation of a silane coupling agent was also assessed. Experimental results revealed that GFRP waste filled polymer mortars show improved mechanical behaviour over unmodified polyester based mortars, thus indicating the feasibility of GFRP waste reuse as raw material in concrete-polymer composites.

Uso Sustentável de Vapor

Em 2006, a IEA (Agência Internacional de Energia), publicou alguns estudos de consumos mundiais de energia. Naquela altura, apontava na fabricação de produtos, um consumo mundial de energia elétrica, de origem fóssil de cerca 86,16 EJ/ano (86,16×018 J) e um consumo de energia nos sistemas de vapor de 32,75 EJ/ano. Evidenciou também nesses estudos que o potencial de poupança de energia nos sistemas de vapor era de 3,27 EJ/ano. Ou seja, quase tanto como a energia consumida nos sistemas de vapor da U.E. Não se encontraram números relativamente a Portugal, mas comparativamente com outros Países publicitados com alguma similaridade, o consumo de energia em vapor rondará 0,2 EJ/ano e por conseguinte um potencial de poupança de cerca 0,02 EJ/ano, ou 5,6 × 106 MWh/ano ou uma potência de 646 MW, mais do que a potência de cinco barragens Crestuma/Lever! Trata-se efetivamente de muita energia; interessa por isso perceber o onde e o porquê deste desperdício. De um modo muito modesto, pretende-se com este trabalho dar algum contributo neste sentido. Procurou-se evidenciar as possibilidades reais de os utilizadores de vapor de água na indústria reduzirem os consumos de energia associados à sua produção. Não estão em causa as diferentes formas de energia para a geração de vapor, sejam de origem fóssil ou renovável; interessou neste trabalho estudar o modo de como é manuseado o vapor na sua função de transporte de energia térmica, e de como este poderá ser melhorado na sua eficiência de cedência de calor, idealmente com menor consumo de energia. Com efeito, de que servirá se se optou por substituir o tipo de queima para uma mais sustentável se a jusante se continuarem a verificarem desperdícios, descarga exagerada nas purgas das caldeiras com perda de calor associada, emissões permanentes de vapor para a atmosfera em tanques de condensado, perdas por válvulas nos vedantes, purgadores avariados abertos, pressão de vapor exageradamente alta atendendo às temperaturas necessárias, “layouts” do sistema de distribuição mal desenhados, inexistência de registos de produção e consumos de vapor, etc. A base de organização deste estudo foi o ciclo de vapor: produção, distribuição, consumo e recuperação de condensado. Pareceu importante incluir também o tratamento de água, atendendo às implicações na transferência de calor das superfícies com incrustações. Na produção de vapor, verifica-se que os maiores problemas de perda de energia têm a ver com a falta de controlo, no excesso de ar e purgas das caldeiras em exagero. Na distribuição de vapor aborda-se o dimensionamento das tubagens, necessidade de purgas a v montante das válvulas de controlo, a redução de pressão com válvulas redutoras tradicionais; será de destacar a experiência americana no uso de micro turbinas para a redução de pressão com produção simultânea de eletricidade. Em Portugal não se conhecem instalações com esta opção. Fabricantes da República Checa e Áustria, têm tido sucesso em algumas dezenas de instalações de redução de pressão em diversos países europeus (UK, Alemanha, R. Checa, França, etc.). Para determinação de consumos de vapor, para projeto ou mesmo para estimativa em máquinas existentes, disponibiliza-se uma série de equações para os casos mais comuns. Dá-se especial relevo ao problema que se verifica numa grande percentagem de permutadores de calor, que é a estagnação de condensado - “stalled conditions”. Tenta-se também evidenciar as vantagens da recuperação de vapor de flash (infelizmente de pouca tradição em Portugal), e a aplicação de termocompressores. Finalmente aborda-se o benchmarking e monitorização, quer dos custos de vapor quer dos consumos específicos dos produtos. Esta abordagem é algo ligeira, por manifesta falta de estudos publicados. Como trabalhos práticos, foram efetuados levantamentos a instalações de vapor em diversos sectores de atividades; 1. ISEP - Laboratório de Química. Porto, 2. Prio Energy - Fábrica de Biocombustíveis. Porto de Aveiro. 3. Inapal Plásticos. Componentes de Automóvel. Leça do Balio, 4. Malhas Sonix. Tinturaria Têxtil. Barcelos, 5. Uma instalação de cartão canelado e uma instalação de alimentos derivados de soja. Também se inclui um estudo comparativo de custos de vapor usado nos hospitais: quando produzido por geradores de vapor com queima de combustível e quando é produzido por pequenos geradores elétricos. Os resultados estão resumidos em tabelas e conclui-se que se o potencial de poupança se aproxima do referido no início deste trabalho.

Correlation of wear in vivo and six laboratory wear methods.

OBJECTIVE: We examined the correlation between clinical wear rates of restorative materials and enamel (TRAC Research Foundation, Provo, USA) and the results of six laboratory test methods (ACTA, Alabama (generalized, localized), Ivoclar (vertical, volumetric), Munich, OHSU (abrasion, attrition), Zurich). METHODS: Individual clinical wear data were available from clinical trials that were conducted by TRAC Research Foundation (formerly CRA) together with general practitioners. For each of the n=28 materials (21 composite resins for intra-coronal restorations [20 direct and 1 indirect], 5 resin materials for crowns, 1 amalgam, enamel) a minimum of 30 restorations had been placed in posterior teeth, mainly molars. The recall intervals were up to 5 years with the majority of materials (n=27) being monitored, however, only for up to 2 years. For the laboratory data, the databases MEDLINE and IADR abstracts were searched for wear data on materials which were also clinically tested by TRAC Research Foundation. Only those data for which the same test parameters (e.g. number of cycles, loading force, type of antagonist) had been published were included in the study. A different quantity of data was available for each laboratory method: Ivoclar (n=22), Zurich (n=20), Alabama (n=17), OHSU and ACTA (n=12), Munich (n=7). The clinical results were summed up in an index and a linear mixed model was fitted to the log wear measurements including the following factors: material, time (0.5, 1, 2 and 3 years), tooth (premolar/molar) and gender (male/female) as fixed effects, and patient as random effect. Relative ranks were created for each material and method; the same was performed with the clinical results. RESULTS: The mean age of the subjects was 40 (±12) years. The materials had been mostly applied in molars (81%) and 95% of the intracoronal restorations were Class II restorations. The mean number of individual wear data per material was 25 (range 14-42). The mean coefficient of variation of clinical wear data was 53%. The only significant correlation was reached by OHSU (abrasion) with a Spearman r of 0.86 (p=0.001). Zurich, ACTA, Alabama generalized wear and Ivoclar (volume) had correlation coefficients between 0.3 and 0.4. For Zurich, Alabama generalized wear and Munich, the correlation coefficient improved if only composites for direct use were taken into consideration. The combination of different laboratory methods did not significantly improve the correlation. SIGNIFICANCE: The clinical wear of composite resins is mainly dependent on differences between patients and less on the differences between materials. Laboratory methods to test conventional resins for wear are therefore less important, especially since most of them do not reflect the clinical wear.

Characterizing emission and breathing-zone concentrations following exposure cases to fluororesin-based waterproofing spray mists.

Measurements and simulations were performed to assess workers' exposure to solvent vapors and aerosols during the waterproofing of a tiled surface. This investigation followed two recent incidents in the same company where workers experienced acute respiratory illness after spraying a stain-repellent resin containing fluorinated polymers on stone-tiled walls and floors. Because the waterproofing activity had been done for years at the tile company without encountering any exposure problems prior to these cases, it was strongly suspected that the incidents were linked to a recent change in the composition of the coating mixture. Experimental measurements and simulations indicated that the emission rate of particles smaller than 10 microm may be estimated at 0.66 mg/sec (SD 0.10) for the old resin and at 0.37 mg/sec (SD 0.04) for the new one. The measurement of the solvent emission rate from surfaces coated with the two resins indicated that shortly after spraying, the emission was in the range of 18 to 20 mg/sec x m2 and was similar for both products. Solvent and overspray emission rates were introduced in a two-zone compartment model. The results obtained in the near-field indicate significant exposure to overspray mist (7 and 34 mg/m3 for new resin) and solvent vapors (80 to 350 ppm for the new resin). It was also shown that the introduction of the new resin tended to significantly decrease the levels of solvents and particulates in the workers' breathing zone. These results strongly suggest that cases of acute respiratory illness are related to the specific toxicity of the fluorinated polymer itself. The fact that the same polymer is used in various commercial products raises concern regarding other possible occupational and domestic exposures.

Sediment genotoxicity and its relationship to the frequency of chironomid labial plate deformities

Sediment samples were taken from seven locations in the WeIland River in December 1986 and April 1987. The DMSO extracts of these sediment samples showed a significant (ppipe (station D-l) . It was concluded that genotoxic contaminants were associated with the sediments from this l ocation. Analysis of sediment samples from the nearby station D-2 resulted in a significant (p <0 . 05) positive genotoxic response in December but not in April. Chironomids (midge larvae) taken from each of seven study locations were analyzed for the frequency of chironomid labial plate deformities (over 1000 individual specimens were observed) . The samples from station D-l showed the highest frequency of chironomid labial plate deformities (10 . 9% ± 3.2%), while samples from the upstream control (station A) displayed t,he lowest frequency of deformities (3.8% ± 1.3%). All samples were coded to avoid unconscious biases . The results of the genotoxicity study indicated that station D-l in the WeIland River was contaminated with genotoxic materials. The genotoxic materials may have induced the observed increased frequency in chironomid labial plate deformities . Samples from stations C and D-l, located in a downstream portion of the river bounded by an industrialized area were slightly toxic according to -the alkaline phosphatase inhib_ii~ion component of the 50S chromotest analyses. The toxicity of these samples was only evident once they had been activated by the 59 (liver extract) mixture.

Buried Treasure: The Economics of Leak Detection and Water Loss Prevention in Ontario

On average approximately 13% of the water that is withdrawn by Canadian municipal water suppliers is lost before it reaches final users. This is an important topic for several reasons: water losses cost money, losses force water agencies to draw more water from lakes and streams thereby putting more stress on aquatic ecosystems, leaks reduce system reliability, leaks may contribute to future pipe failures, and leaks may allow contaminants to enter water systems thereby reducing water quality and threatening the health of water users. Some benefits of leak detection fall outside water agencies’ accounting purview (e.g. reduced health risks to households connected to public water supply systems) and, as a result, may not be considered adequately in water agency decision-making. Because of the regulatory environment in which Canadian water agencies operate, some of these benefits-especially those external to the agency or those that may accrue to the agency in future time periods- may not be fully counted when agencies decide on leak detection efforts. Our analysis suggests potential reforms to promote increased efforts for leak detection: adoption of a Canada-wide goal of universal water metering; development of full-cost accounting and, pricing for water supplies; and co-operation amongst the provinces to promulgate standards for leak detection efforts and provide incentives to promote improved efficiency and rational investment decision-making.

Notebook with H.K. Woodruff written on the front cover

Notebook with H.K. Woodruff written on the front cover (soft cover). Inside, there is a list of 48 diverse items which include: sword found at Lundy’s Lane, stuffed frog from Long Point, Indian pipe, 5 curious old revolutionary pistols and Mrs. S. Bull’s slippers. At the back of the book there is a list of 22 items including: proclamation issued by Sir Isaac Brock on Feb. 24, 1812 and Egyptian mummy, 1884-1885.

Niagara Falls Handbill Collection, 1838-1886, n.d. (non-inclusive)

According to legend, the Burning Springs were discovered by early natives in the Niagara Peninsula. Bridgewater Mills was built on the site of the spring. During the excavation of the factory; workmen uncovered the spring. Samuel Street and Thomas Clark recognized the potential of this as a tourist attraction so they built a wooden shelter over the spring. The spring was covered with a barrel with a pipe protruding from it. This became the first tourist attraction at Niagara. The Cave of the Winds was a cavern located behind the Bridal Veil Fall. It was originally named the Aeolus Cave. In 1920, a sudden rock fall from the ceiling killed 3 tourists. The cave was destroyed in 1955 as it was deemed dangerous. The captain of the Maid of the Mist was usually a farmer who owned the land where the ship docked. In 1846, the first steam powered Maid of the Mist was launched. By 1848, the first suspension bridge was built over the gorge and the main purpose of the Maid of the Mist was no longer to carry people who needed to travel, but now the focus was on people who wanted to view the Falls at close range. Source: http://www.niagarafrontier.com/burningsprings.html http://www.niagarafrontier.com/winds.html http://reservationsystems.com/niagara_daredevils/maid_of_the_mist.html

Letter to S.D. Woodruff from A. Jeffrey importer of Hardware, Iron, Steel, and Window Glass of St. Catharines, Ont.

Letter to S.D. Woodruff from A. Jeffrey importer of Hardware, Iron, Steel, and Window Glass of St. Catharines, Ont. A. Jeffrey says that he will be able to supply Mr. Woodruff with glass and iron pipe, June 7, 1875.

Comparaison de la force d'adhésion de deux types de résines de collage appliquées sur des surfaces métalliques traitées de différentes façons : une étude in vitro

L’objectif de cette étude était d’évaluer et de comparer la force d’adhésion de deux résines de collage: le ClearfilTM Esthetic Cement & DC Bond Kit (C) et le RelyXTM Unicem (R), sur trois adhérents différents : une surface d’émail, un alliage de métaux non précieux (Np) et un alliage de métaux semi-précieux (Sp). La surface des échantillons des alliages métalliques a subi différents traitements de surface. Sur l’émail (n=15) ainsi que sur les plaquettes d’alliages Np et Sp (n=15), des cylindres de résine étaient appliqués et polymérisés. Suite au processus de collage, les échantillons ont été incubés à 37°C pendant 24 heures, puis ont subi 500 cycles de thermocyclage. Des tests de cisaillement ont été effectués, suivi par l’analyse de la surface des échantillons au microscope à balayage électronique. Une comparaison de type T-test et des comparaisons multiples post hoc, ont été effectuées pour l’analyse statistique (p 0,05). Sur l’émail, les résultats ont démontré que la résine C présentait une force d'adhésion moyenne statistiquement supérieure (33,97±17,18 MPa) à la résine R (10,48±11,23 MPa) (p 0,05). Le type d’alliage utilisé n’influençait pas la force d’adhésion, et ce, peu importe le type de résine de collage (p>0,05). Pour le groupe Sp, la résine C a démontré une adhésion statistiquement supérieure à la résine R, et ce, pour tous les traitements de surface (p 0,05). En conclusion, la résine C a démontré des résultats d’adhésion significativement supérieurs à la résine R sur l’émail ainsi que sur presque toutes les surfaces traitées des alliages de métaux.