Shear strength of adhesively bonded polyolefins with minimal surface preparation

Interest in polyethylene and polypropylene bonding has increased in the last years. However, adhesive joints with adherends which are of low surface energy and which are chemically inert present several difficulties. Generally, their high degree of chemical resistance to solvents and dissimilar solubility parameters limit the usefulness of solvent bonding as a viable assembly technique. One successful approach to adhesive bonding of these materials involves proper selection of surface pre-treatment prior to bonding. With the correct pre-treatment it is possible to glue these materials with one or more of several adhesives required by the applications involved. A second approach is the use of adhesives without surface pre-treatment, such as hot melts, high tack pressure-sensitive adhesives, solvent-based specialty adhesives and, more recently, structural acrylic adhesives as such 3M DP-8005® and Loctite 3030®. In this paper, the shear strengths of two acrylic adhesives were evaluated using the lap shear test method ASTM D3163 and the block shear test method ASTM D4501. Two different industrial polyolefins (polyethylene and polypropylene) were used for adherends. However, the focus of this study was to measure the shear strength of polyethylene joints with acrylic adhesives. The effect of abrasion was also studied. Some test specimens were manually abraded using 180 and 320 grade abrasive paper. An additional goal of this work was to examine the effect of temperature and moisture on mechanical strength of adhesive joints.

Increasing the wear resistance of molds for injection of glass fiber reinforced plastics

Abrasion by glass fibers during injection molding of fiber reinforced plastics raises new challenges to the wear performance of the molds. In the last few decades, a large number of PVD and CVD coatings have been developed with the aim of minimizing abrasion problems. In this work, two different coatings were tested in order to increase the wear resistance of the surface of a mold used for glass fiber reinforced plastics: TiAlSiN and CrN/CrCN/DLC. TiAlSiN was deposited as a graded monolayer coating while CrN/CrCN/DLC was a nanostructured coating consisting of three distinct layers. Both coatings were produced by PVD unbalanced magnetron sputtering and were characterized using scanning electron microscopy (SEM) provided with energy dispersive spectroscopy (EDS), atomic force microscopy (AFM), micro hardness (MH) and scratch test analysis. Coating morphology, thickness, roughness, chemical composition and structure, hardness and adhesion to the substrate were investigated. Wear resistance was characterized through industrial tests with coated samples and an uncoated reference sample inserted in a feed channel of a plastic injection mold working with 30 wt.% glass fiber reinforced polypropylene. Results after 45,000 injection cycles indicate that the wear resistance of the mold was increased by a factor of 25 and 58, by the TiAlSiN and CrN/CrCN/DLC coatings, respectively, over the uncoated mold steel.

Caracterização mecânica e análise da resistência à corrosão em diferentes solos, de aços inoxidáveis duplex

O aço inoxidável é um material de alta durabilidade e resistência, utilizado nos mais diversos setores comerciais. O conhecimento das suas características e propriedades é essencial para uma escolha mais seletiva e vantajosa. Pretende‐se com este trabalho, estudar as propriedades mecânicas, a resistência ao desgaste e o comportamento, em ambientes mais agressivos de três tipos de aços inoxidáveis duplex, produzidos pela OUTOKUMPU e comercialmente conhecidos pelas designações LDX 2101, SAF 2507 e o SAF 2205. Para tal efeito foram realizados ensaios de Dureza Vickers, antes e após dobragem; ensaios de tracção em duas diferentes situações: seguindo a norma NP EN 10002‐ 1:2006 e após a realização de alguns ciclos de carga e descarga; ensaio de Impacto à temperatura ambiente e após arrefecimento criogénico; ensaio de resistência à corrosão. Também foi feito o estudo de resistência ao desgaste com base na técnica de micro‐abrasão por esfera rotativa e o estudo metalográfico. Foi também objetivo deste trabalho, relacionar o uso dos referidos aços duplex e as consequências que esse uso tem para o meio ambiente, bem como o seu comportamento quando exposto a condições extremas. Para tal, foram colocadas amostras dos referidos aços, em dois tipos de solos com condições de humidade e acidez diferentes analisando o seu estado após imersão em solo com condições controladas durante 272 dias.

Uma abordagem à incorporação de lenhinosulfonatos e materiais reciclados em misturas de SBR para produção sustentável de solas

Mestrado em Engenharia Química - Ramo Otimização Energética na Indústria Química

Otimização do Funcionamento da ETAR das Termas de S. Vicente, Penafiel

A água é um recurso natural único, escasso e essencial a todos os seres vivos, o que a torna um bem de extrema importância. Nos dias de hoje, o desperdício deste bem, aliado ao aumento da sua procura, tornou-se um problema devido à decrescente disponibilidade de água doce no nosso planeta. Todas as águas que rejeitamos depois da sua utilização para diversos fins, designadas de águas residuais, necessitam de tratamento antes de serem devolvidas ao meio ambiente. O seu tratamento é realizado numa Estação de Tratamento de Águas Residuais (ETAR) e o processo de tratamento depende das suas características. A ETAR das Termas de S. Vicente, em Penafiel, trabalha no seu limite de capacidade, apresenta uma sobrecarga hidráulica gerada por uma afluência de águas pluviais e o processamento das lamas geradas não permite uma secagem tão completa como seria desejável. Assim, este trabalho teve como objetivo o estudo do funcionamento desta ETAR com a finalidade de propor soluções que o possam otimizar. As soluções propostas para otimizar o funcionamento da ETAR em estudo são: i) a substituição de grades de limpeza manual por grades de limpeza automática de forma a reduzir a necessidade da intervenção do operador ao nível da remoção e condicionamento dos gradados; ii) a construção de um desarenador arejado que além de remover areias de diâmetro superior a 0,2 mm promove também a remoção de gorduras, protegendo desta forma os equipamentos a jusante da abrasão/desgaste prematuros e reduzindo a formação de depósitos nas tubagens; iii) a construção de um tanque de equalização de forma a garantir uma distribuição mais uniforme dos caudais e da carga poluente; iv) a substituição do enchimento do leito percolador por um meio de suporte plástico que permite atingir melhores eficiências de remoção neste tratamento biológico; v) a alteração do agente de desinfeção para radiação ultravioleta, evitando a adição de produtos químicos na água residual e possível formação de subprodutos prejudiciais ao ambiente, como ocorreria no caso da cloragem; e vi) a substituição da desidratação de lamas em leitos de secagem por filtros de banda, que é um processo mais rápido, que ocupa menos espaço e permite atingir elevadas eficiências de remoção de humidade. Para cada uma das sugestões são apresentadas as correspondentes especificações técnicas e dimensionamento. As sugestões de melhoria apresentadas neste trabalho constituem uma alternativa mais económica do que a ampliação da ETAR, que genericamente corresponde à duplicação da linha de tratamento atual. Devido à menor complexidade em termos de construção, estas sugestões podem vir a ser implementadas num futuro próximo, prolongando assim um pouco mais a vida útil da ETAR atual.

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.

La paleolaguna de Otuma como potencial para la reconstrucción de las condiciones paleoceanográficas de Pisco.

Se describe la geomorfología del relieve de la paleolaguna de Otuma y se evalúa la preservación de sus registros calcáreos y su potencialidad para la reconstrucción paleoceanográfica y paleoecológica. Un pequeño acantilado marino y una plataforma de abrasión de suave pendiente con predominancia de arena y grava, sugieren un fondo submareal somero de 3,5 m de profundidad a 80 m de distancia de la orilla. La distribución de los registros calcáreos in situ, sobre el fondo de la paleolaguna sugiere un patrón de zonación ecológica. La abundancia de Argopecten purpuratus en los conchales demuestra su dominancia y la presencia de un antiguo y muy productivo banco natural de concha de abanico con una estructura de tallas 40 -140 mm. La preservación de las conchas permitió el análisis de sus anillos o líneas de crecimiento y la reconstruccion de sus ritmos y patrones de crecimiento que son valiosos para la reconstrucción de la variabilidad ambiental.

The Catharanthus roseus 16-hydroxytabersonine O-methyltransferase involved in vindoline biosynthesis /

Madagascar periwinkle (Catharanthus roseus) produces the well known and remarkably complex dimeric anticancer alkaloids vinblastine and vincristine that are derived by coupling vindoline and catharanthine monomers. This thesis describes the novel application of carborundum abrasion (CA) technique as a tool for large scale isolation of leaf epidermis enriched proteins. This technique was used to facilitate the purification to apparent homogeneity of 16-hydroxytabersonine-16-0-methyltransferse (l60MT) that catalyses the second step in the 6 step pathway that converts tabersonine into vindoline. This versatile tool was also used to harvest leaf epidermis enriched mRNAs that facilitated the molecular cloning of the 160MT. Functional expression and biochemical characterization of recombinant 160MT enzyme showed that it had a very narrow substrate specificity and high affinity for 16-hydroxytabersonine, since other closely related monoterpene indole alkaloids (MIAs) did not act as substrates. In addition to allowing the cloning of this gene, CA technique clearly showed that 160MT is predominantly expressed in Catharanthus leaf epidermis, in contrast to several other OMTs that appear to be expressed in other Catharanthus tissues. The results provide compelling evidence that most of the pathway for vindoline biosynthesis including the 0- methylation of 16-hydroxytabersonine occurs exclusively in leaf epidermis, with subsequent steps occurring in other leaf cell types. Small molecule O-methyltransferases (OMTs) (E.C. 2.1.1.6.x) catalyze the transfer of the reactive methyl group of S-adenosyl-L-methionine (SAM) to free hydroxyl groups of acceptor molecules. Plant OMTs, unlike their monomeric mammalian homologues, exist as functional homodimers. While the biological advantages for dimer fonnation with plant OMTs remain to be established, studies with OMTs from the benzylisoquinoline producing plant, Thalictrum tuberosum, showed that co-expression of 2 recombinant OMTs produced novel substrate specificities not found when each rOMT was expressed individually (Frick, Kutchan, 1999) . These results suggest that OMTs can fonn heterodimers that confer novel substrate specificities not possible with the homodimer alone. The present study describes a 160MT model based strategy attempting to modify the substrate specificity by site-specific mutagenesis. Our failure to generate altered substrate acceptance profiles in our 160MT mutants has lead us to study the biochemical properties ofhomodimers and heterodimers. Experimental evidence is provided to show that active sites found on OMT dimers function independently and that bifunctional heterodimeric OMTs may be fonned in vivo to produce a broader and more diverse range of natural products in plants.

Localization and functional characterization of iridoid biosynthetic genes in Catharanthus roseus /

Catharanthus roseus is the sole biological source of the medicinal compounds vinblastine and vincristine. These chemotherapeutic compounds are produced in the aerial organs of the plant, however they accumulate in small amounts constituting only about 0.0002% of the fresh weight of the leaf. Their limited biological supply and high economical value makes its biosynthesis important to study. Vinblastine and vincristine are dimeric monoterpene indole alkaloids, which consists of two monomers vindoline and catharanthine. The monoterpene indole alkaloids (MIA's) contain a monoterpene moiety which is derived from the iridoid secologanin and an indole moiety tryptamine derived from the amino acid tryptophan. The biosynthesis of the monoterpene indole alkaloids has been localized to at least three cell types namely, the epidermis, the laticifer and the internal phloem assisted parenchyma. Carborundum abrasion (CA) technique was developed to selectively harvest epidermis enriched plant material. This technique can be used to harvest metabolites, protein or RNA. Sequencing of an expressed sequence tagged (EST) library from epidermis enriched mRNA demonstrated that this cell type is active in synthesizing a variety of secondary metabolites namely, flavonoids, lipids, triterpenes and monoterpene indole alkaloids. Virtually all of the known genes involved in monterpene indole alkaloid biosynthesis were sequenced from this library.This EST library is a source for many candidate genes involved in MIA biosynthesis. A contig derived from 12 EST's had high similarity (E'^') to a salicylic acid methyltransferase. Cloning and functional characterization of this gene revealed that it was the carboxyl methyltransferase imethyltransferase (LAMT). In planta characterization of LAMT revealed that it has a 10- fold enrichment in the leaf epidermis as compared to the whole leaf specific activity. Characterization of the recombinant enzyme revealed that vLAMT has a narrow substate specificity as it only accepts loganic acid (100%) and secologanic acid (10%) as substrates. rLAMT has a high Km value for its substrate loganic acid (14.76 mM) and shows strong product inhibition for loganin (Kj 215 |iM). The strong product inhibition and low affinity for its substrate may suggest why the iridoid moiety is the limiting factor in monoterpene indole alkaloid biosynthesis. Metabolite profiling of C. roseus organs shows that secologanin accumulates within these organs and constitutues 0.07- 0.45% of the fresh weight; however loganin does not accumulate within these organs suggesting that the product inhibition of loganin with LAMT is not physiologically relevant. The limiting factor to iridoid and MIA biosynthesis seems to be related to the spatial separation of secologanin and the MIA pathway, although secologanin is synthesized in the epidermis, only 2-5% of the total secologanin is found in the epidermis while the remaining secologanin is found within the leaf body inaccessable to alkaloid biosynthesis. These studies emphasize the biochemical specialization of the epidermis for the production of secondary metabolites. The epidermal cells synthesize metabolites that are sequestered within the plant and metabolites that are secreted to the leaf surface. The secreted metabolites comprise the epidermome, a layer separating the plant from its environment.

An investigation of geological and geochemical characteristics of late-Quaternay sediments in the Georgian Bay Region, Southern Ontario

Core samples of postglacial sediments and sediment surface samples from Shepherd Lake on the Bruce Peninsula, Harts Lake on the Canadian Shield, and two cores from Georgian Bay (core P-l in the western deep part and core P-7 in the eastern shallow part) have been analyzed for pH, grain size distribution, water content, bulk density, loss on ignition at 4500C and 11000 C, major oxides (Si02 ,A1203,!FeO,MgO,CaO, Na20,K20,Ti02 ,MnO and P205) and trace elements (Ba,Zr,Sr,y,S, Zn,Cu,Ni,Ce and Rb). The sediment in Georgian Bay are generally fine grained (fine silt to very fine silty clay) and the grain size decreases from the Canadian Shield (core p-7) towards the Bruce Peninsula (core P-l) along the assumed direction of sediment transport. This trend coincides with a decrease in sorting coefficient and an increase in roundness. Other physical characteristics, such as water content, bulk density and loss on ignition are positively correlated with the composition of sediments and their compaction, as well as with the energy of the depositional environment. Analyses of sediment surface samples from Shepherd Lake and Harts Lake indicate the influence of bedrock and surficial deposits in the watershed on pH condition that is also influenced by the organic matter content and probably I ! I man's activities. Organic matter content increases significantly in the surface sediment in these small lakes as a result of either natural eutrophication or anthropogenic organic loading. The extremely high organic matter content in Shepherd Lake sediment indicates rapid natural eutrophication in this closed basin and high biological productivity during postglacial time, probably due to high nutrient levels and shallow depth. The chemical composition of the Canadian Shield bedrock is positively correlated with the chemical characteristics of predominantly inorganic lake sediments that were derived from the Shield rocks by glacial abrasion and by postglacial weathering and erosion of both bedrock and surficial deposits. High correlation coefficients were found between organic matter in lake sediments and major oxides (Si02,AI203,.~FeO, MgO,CaO,K20 and MnO) , as well as some trace elements (Ba,Y, S,Zn,Cu,Ni and Rb). The chemical composition of sediments in Harts Lake and core P-7 in Georgian Bay on the Canadian Shield differs from the chemistry of sediments in Shepherd Lake and core P-l in Georgian Bay on the Bruce Peninsula. The difference between cores P-l and P-7 is indicated by values of Si02 , AI203 ,:LFeo,Mgo,CaO,Ba,Zr,Sr,y and S, and also by the organic matter content. This study indicates that the processes of sediment transport, depositional environment, weathering of the rocks and surficial deposits in the watershed, as well as chemical composition of source rocks all affect the chemical characteristics of lake sediments. The stratigraphic changes and variations in lake sediment chemistry with regard to major oxides, trace elements, and organic matter content are probably related to the history of glacial and postglacial lake stages of the Georgian Bay Region and, therefore, the geochemical data can make a useful contribution to a better understanding of the Late-Quaternary history of the Great Lakes.

Étude taphonomique des assemblages fauniques de la formation géologique Mursi et du membre A de la Formation Shungura, Éthiopie

La formation géologique Mursi est datée à plus de 4 millions d’années, ce qui correspond à la période de l’émergence présumée des australopithèques, premiers hominines présentant une bipédie incontestable. La collection faunique Mursi (N=201) est comparée à celle du membre A de la Formation Shungura (N=300) sur une base taphonomique. La taphonomie est la science dédiée aux modes de formation des fossiles ainsi qu’aux traces laissées par ceux-ci. L’objectif principal de ce mémoire est de vérifier quelles sont les différences et ressemblances entre ces deux assemblages fossiles et d’en tirer des interprétations paléoenvironnementales. Pour chacun des agents taphonomiques (météorisation, piétinement, etc.), les fossiles sont gradés en fonction de stades prédéfinis tirés des écrits scientifiques. Finalement, malgré quelques différences (action des carnivores, intempérisation) on constate que les assemblages sont assez semblables et que, comme prédit par les reconstructions paléoenvironnementales préexistantes, leur lien à l’eau est assez bien démontré (groupes de Voorhies, abrasion).

Quand le désespoir cache l’innommable : une étude des critères de suspicion pour distinguer les suicides par pendaison des homicides déguisés

L’objectif de la présente étude est d’étudier les différences entre les homicides par strangulation et les suicides par pendaison ainsi que l’importance du rôle que jouent les lésions dans la détermination du mode de décès dans les cas apparents de pendaison, et ce dans l’optique d’établir un outil permettant de renseigner le coroner ou médecin légiste sur le mode de décès probable dans les cas apparents de pendaison. Deux cent quatorze cas de suicide par pendaison ont été révisés rétrospectivement et comparés à 51 cas d’homicide par strangulation. La fréquence d’ecchymoses (6,1 %), d’abrasions (4,7 %) et de lacérations (0,5 %) était significativement plus faible chez les victimes de suicide par pendaison que chez les victimes d’homicides par strangulation (58,8 %, 51,0 % et 5,9 % respectivement). Les ecchymoses, chez les victimes de suicide par pendaison, se trouvent habituellement sur les membres supérieurs antérieurs et postérieurs ou sur les membres inférieurs antérieurs. Elles se situent généralement soit sur les membres supérieurs, soit sur les membres inférieurs, et non aux deux endroits à la fois. Les abrasions sont davantage susceptibles de se trouver sur la face postérieure des membres supérieurs et sur la face antérieure des membres inférieurs. Cette concentration préférentielle n’est pas observée chez les victimes d’homicide par strangulation. De possibles critères de suspicion et des modèles de prédiction du mode de décès sont évalués.

A Novel Accelerator Combination for the Low Temperature Curing of Silica-Filled NBR Compounds

Zinc salts of ethyl, isopropyl, and butyl xanthates were prepared in the laboratory. The effect of these xanthates in combination with zinc diethyldithiocarbamate (ZDC) on the vulcanization of silica-filled NBR compounds has been studied at different temperatures. The cure times of these compounds were compared with that of NBR compounds containing tetramethylthiuram disulphide/dibenzthiazyl disulphide. The rubber compounds with the xanthates and ZDC were cured at various temperatures from 60 to 150°C. The sheets were molded and properties such as tensile strength, tear strength, crosslink density, elongation at break, compression set, abrasion resistance, flex resistance, heat buildup, etc. were evaluated. The properties showed that zinc salt of xanthate/ZDC combination has a positive synergistic effect on the cure rate and mechanical properties of NBR compounds.

Low Temperature Curing of NBR for Property Improvement

Zinc salts of ethyl, isopropyl, and butyl xanthates are prepared in the laboratory, and the effect of these xanthates with zinc diethyl dithiocarbamate (ZDC) on the vulcanization of HAF-filled nitrile butadiene rubber (NBR) compounds has been studied at different temperatures. The cure times of these compounds have been compared with that of NBR compounds containing TMTD/MBTS. The rubber compounds with the three xanthate accelerators and ZDC are cured at various temperatures from 60 to 150°C. The sheets are molded and properties such as tensile strength, tear strength, cross-link density, elongation at break, compression set, abrasion resistance, flex resistance, etc. have been evaluated. The properties show that zinc salt of the xanthate/ZDC accelerator system has a positive synergistic effect on the cure rate and mechanical properties of NBR compounds.

Studies on Xanthate/Dithiocarbamate Accelerator Combination in NR/BR Blends

Zinc butyl xanthate [Zn(bxt)2] was prepared in the laboratory . The effect of this xanthate with zinc diethyl dithiocarbamate (ZDC) on the vulcanization of natural rubber ( NR), polybutadiene rubber (BR), and NR/BR blend has been studied at different temperatures. The amounts of Zn (bxt)2 and ZDC in the compounds were optimized by varying the amount of ZDC from 0 . 75 to 1.5 phr and Zn (bxt)2 from 0 . 75 to 1 .5 phr. The cure characteristics were also studied . HAF filled NR, BR, and NR / BR blend compounds were cured at different temperatures from 60 to 150 C. The sheets were molded and properties such as tensile strength, tear strength, crosslink density and elongation at break, compression set, abrasion resistance, etc. were evaluated. The results show that the mechanical properties of 80NR/20BR blends are closer to that of NR vulcanizates, properties of 60NR/40BR blends are closer to BR vulcanizates, while the 70NR/30BR blends show an intermediate property.