Novel materials based on chitosan, its derivatives and cellulose fibres

O presente trabalho tem como principal objectivo o desenvolvimento de novos materiais baseados em quitosano, seus derivados e celulose, na forma de nanofibras ou de papel. Em primeiro lugar procedeu-se à purificação das amostras comerciais de quitosano e à sua caracterização exaustiva em termos morfológicos e físicoquímicos. Devido a valores contraditórios encontrados na literatura relativamente à energia de superfície do quitosano, e tendo em conta a sua utilização como precursor de modificações químicas e a sua aplicação em misturas com outros materiais, realizou-se também um estudo sistemático da determinação da energia de superfície do quitosano, da quitina e seus respectivos homólogos monoméricos, por medição de ângulos de contacto Em todas as amostras comerciais destes polímeros identificaram-se impurezas não polares que estão associadas a erros na determinação da componente polar da energia de superfície. Após a remoção destas impurezas, o valor da energia total de superfície (gs), e em particular da sua componente polar, aumentou consideravelmente. Depois de purificadas e caracterizadas, algumas das amostras de quitosano foram então usadas na preparação de filmes nanocompósitos, nomeadamente dois quitosanos com diferentes graus de polimerização, correspondentes derivados solúveis em água (cloreto de N-(3-(N,N,N-trimetilamónio)-2- hidroxipropilo) de quitosano) e nanofibras de celulose como reforço (celulose nanofibrilada (NFC) e celulose bacteriana (BC). Estes filmes transparentes foram preparados através de um processo simples e com conotação ‘verde’ pela dispersão homogénea de diferentes teores de NFC (até 60%) e BC (até 40%) nas soluções de quitosano (1.5% w/v) seguida da evaporação do solvente. Os filmes obtidos foram depois caracterizados por diversas técnicas, tais como SEM, AFM, difracção de raio-X, TGA, DMA, ensaios de tracção e espectroscopia no visível. Estes filmes são altamente transparentes e apresentam melhores propriedades mecânicas e maior estabilidade térmica do que os correspondentes filmes sem reforço. Outra abordagem deste trabalho envolveu o revestimento de folhas de papel de E. globulus com quitosano e dois derivados, um derivado fluorescente e um derivado solúvel em água, numa máquina de revestimentos (‘máquina de colagem’) à escala piloto. Este estudo envolveu inicialmente a deposição de 1 a 5 camadas do derivado de quitosano fluorescente sobre as folhas de papel de forma a estudar a sua distribuição nas folhas em termos de espalhamento e penetração, através de medições de reflectância e luminescência. Os resultados mostraram que, por um lado, a distribuição do quitosano na superfície era homogénea e que, por outro lado, a sua penetração através dos poros do papel cessou após três deposições. Depois da terceira camada verificou-se a formação de um filme contínuo de quitosano sobre a superfície do papel. Estes resultados mostram que este derivado de quitosano fluorescente pode ser utilizado como marcador na optimização e compreensão de mecanismos de deposição de quitosano em papel e outros substratos. Depois de conhecida a distribuição do quitosano nas folhas de papel, estudou-se o efeito do revestimento de quitosano e do seu derivado solúvel em água nas propriedades finais do papel. As propriedades morfológicas, mecânicas, superficiais, ópticas, assim como a permeabilidade ao ar e ao vapor de água, a aptidão à impressão e o envelhecimento do papel, foram exaustivamente avaliadas. De uma forma geral, os revestimentos com quitosano e com o seu derivado solúvel em água tiveram um impacto positivo nas propriedades finais do papel, que se mostrou ser dependente do número de camadas depositadas. Os resultados também mostraram que os papéis revestidos com o derivado solúvel em água apresentaram melhores propriedades ópticas, aptidão à impressão e melhores resultados em relação ao envelhecimento do que os papéis revestidos com quitosano. Assim, o uso de derivados de quitosano solúveis em água em processos de revestimento de papel representa uma estratégia bastante interessante e sustentável para o desenvolvimento de novos materiais funcionais ou na melhoria das propriedades finais dos papéis. Por fim, tendo como objectivo valorizar os resíduos e fracções menos nobres da quitina e do quitosano provenientes da indústria transformadora, estes polímeros foram convertidos em polióis viscosos através de uma reacção simples de oxipropilação. Este processo tem também conotação "verde" uma vez que não requer solvente, não origina subprodutos e não exige nenhuma operação específica (separação, purificação, etc) para isolar o produto da reacção. As amostras de quitina e quitosano foram pré-activadas com KOH e depois modificadas com um excesso de óxido de propileno (PO) num reactor apropriado. Em todos os casos, o produto da reacção foi um líquido viscoso composto por quitina ou quitosano oxipropilados e homopolímero de PO. Estas duas fracções foram separadas e caracterizadas.

Compósitos de polímeros naturais e nanopartículas metálicas

Esta tese descreve diversas estratégias de preparação assim como a caracterização de nanocompósitos com base em distintos biopolímeros. Em particular foi estudada a incorporação de nanopartículas (NPs) metálicas, nomeadamente de Ag, Cu e Au. Estes nanomateriais apresentam um potencial prático enorme em diversas áreas, no entanto foi investigada especificamente a sua aplicação como materiais antimicrobianos. No primeiro capítulo apresenta-se uma revisão bibliográfica, onde são realçados os principais tópicos discutidos ao longo da tese. Inicialmente apresenta-se uma contextualização deste trabalho sendo seguidamente apresentadas algumas considerações sobre nanocompósitos e o seu impacto tecnológico atual. Em seguida, descrevem-se as vantagens do uso de NPs como cargas nos materiais compósitos especificamente no caso de bionanocompósitos. Foi focado o uso da celulose como matriz uma vez que foi o composto “base” usado neste trabalho. Fez-se a descrição exaustiva das metodologias existentes na literatura para a preparação dos nanocompósitos celulósicos com diferentes NPs metálicas assim como das respetivas aplicações. Dentro das aplicações, foi dado especial destaque às propriedades antimicrobianas dos materiais preparados seja a nível da sua atividade antibacteriana ou antifúngica. Esta introdução privilegia o trabalho relacionado diretamente com os sistemas descritos nos capítulos subsequentes. No segundo capítulo apresentam-se os resultados obtidos para nanocompósitos de prata em matriz celulósica. Através do uso de metodologias, tais como a síntese in situ e a pós-deposição, foram preparados diversos materiais usando dois substratos celulósicos distintos nomeadamente a celulose vegetal e bacteriana. Estes nanocompósitos foram caracterizados em termos da sua morfologia e composição química, verificando-se a importância destas características na sua atividade antibacteriana. Foi verificado que nanocompósitos com teores de Ag de 5 x 10-4 (% m/m) são suficientes para obter atividade antibacteriana. A libertação de Ag(I) foi estudada em alguns destes materiais de modo a tentar perceber o mecanismo subjacente a este tipo de nanocompósitos. No terceiro capítulo é apresentado o estudo de NPs coloidais de Ag e Au como cargas para a preparação de nanocompósitos à base de quitosano nãomodificado e modificado quimicamente (derivado solúvel em água e derivado anfifílico). Foram preparados filmes finos de espessura de 9-14 μm, caracterizando-se as suas propriedades óticas e antibacterianas. As propriedades óticas foram ajustadas, quer pela variação do teor de NPs de Ag (0,3-3,9% m/m) ou pela utilização de amostras de NPs com distribuição de tamanho de partícula distinta. Foi investigada a atividade antibacteriana tanto para bactérias Gram-negativas (Klebsiella pneumoniae e Escherichia coli) como para Gram-positivas (Staphylococcus aureus). Para nanocompósitos preparados com o quitosano não modificado verificou-se uma dependência em função do teor de Ag. No caso do uso de derivados modificados, os materiais preparados mostraram uma eficiência superior, mesmo sem NPs de Ag. No quarto capítulo é apresentada a síntese e caracterização de nanocompósitos de pululano e NPs de Ag. Neste estudo é avaliada a atividade antifúngica dos filmes compósitos preparados contra o Aspergillus niger usando protocolos padrão. Estes materiais foram preparados na forma de filmes (66-74 μm de espessura) por evaporação de solvente da mistura de pululano e coloides de Ag. Foi observado o aumento da inibição do fungo na presença dos nanocompósitos, tendo sido pela primeira vez mostrado o efeito disruptivo destes materiais sobre os esporos do A. niger através da análise das imagens de SEM. Este efeito ocorre na presença dos filmes devido à presença das cargas de NPs de Ag dispersas no pululano. O desenvolvimento de materiais de papel com NPs de Cu é um desafio devido à propensão destas espécies em oxidar sob condições ambiente. No quinto capítulo é descrita pela primeira vez o estudo comparativo do crescimento e estabilidade de NPs de Cu em celulose vegetal e bacteriana. Para além disso foi avaliado o uso de nanoestruturas com diferentes dimensionalidades como cargas, nomeadamente nanoesferas e nanofios. Foi observado que o uso de nanofios aumenta a resistência à oxidação destes nanocompósitos para tempos de exposição ao ar mais prolongados. As matrizes celulósicas apresentam comportamento distinto no crescimento e/ou adsorção das NPs de Cu. A celulose bacteriana foi o substrato mais eficiente para retardar a oxidação das NPs. A atividade antibacteriana destes nanocompósitos foi avaliada. Ao longo desta dissertação são apresentados métodos distintos para a obtenção de nanocompósitos com base em biopolímeros e NPs metálicas. Estes estudos permitiram não só a preparação de novos nanocompósitos mas também compreender e otimizar os mecanismos subjacentes à sua preparação. Ao mesmo tempo, este trabalho contribuiu para a transferência de tecnologia e conhecimento entre a área da Nanotecnologia e a área dos materiais derivados de fontes renováveis. As propriedades apresentadas por estes nanomateriais mostraram a sua possível aplicação como novos materiais antimicrobianos, no entanto é possível antecipar futuras aplicações em outras áreas tecnológicas.

Kimberly-Clark (Canada) records, 1960-1987

Kimberly, Clark & Company was founded in Wisconsin in 1872. The founding partners were John A. Kimberly, Havilah Babcock, Charles B. Clark, and Frank C. Stattuck. That same year, the company built the Globe Mill, which made newsprint from linen and cotton rags. The company soon established a reputation for developing new and innovative paper products and processes. In the 1920s, Kimberly-Clark opened a Canadian Pulp Mill and Power plant known as the Spruce Falls Power and Paper Company, in Kapuskasing, Ontario. Other branches of Kimberly-Clark were established in Ontario at Huntsville and Terrace Bay.

Do electricity supply constraints matter for comparative advantage? : a neoclassical approach

This paper examines the extent to which electricity supply constraints could affect sectoral specialization. For this purpose, an empirical trade model is estimated from 1990-2008 panel data on 15 OECD countries and 12 manufacturing sectors. We find that along with Ricardian technological differences and Heckscher-Ohlin factor-endowment differences, productivity-adjusted electricity capacity drives sectoral specialization in several sectors. Among them, electrical equipment, transport equipment, machinery, chemicals, and paper products will see lower output shares as a result of decreases in productivity-adjusted electricity capacity. Furthermore, our dynamic panel estimation reveals that the effects of Ricardian technological differences dominate in the short-run, and factor endowment differences and productivity-adjusted electricity capacity tend to have a significant effect in only the long-run.

Waste material series,

Reproduced from type-written copy.

The data base : the potential for energy conservation in nine selected industries /

v.1. Selected plastics.--v.2. Petroleum refining.--v.3. Cement.--v.4. Copper.--v.5. Aluminum.--v.6. Steel.--v.7. Glass.--v.8. Selected paper products.--v.9.Styrene butadiene rubber.

Annual report.

Report year ends December 31.

Essays on Energy Economics and Industrial Organization

The dissertation consists of three chapters related to the low-price guarantee marketing strategy and energy efficiency analysis. The low-price guarantee is a marketing strategy in which firms promise to charge consumers the lowest price among their competitors. Chapter 1 addresses the research question "Does a Low-Price Guarantee Induce Lower Prices'' by looking into the retail gasoline industry in Quebec where there was a major branded firm which started a low-price guarantee back in 1996. Chapter 2 does a consumer welfare analysis of low-price guarantees to drive police indications and offers a new explanation of the firms' incentives to adopt a low-price guarantee. Chapter 3 develops the energy performance indicators (EPIs) to measure energy efficiency of the manufacturing plants in pulp, paper and paperboard industry.

Chapter 1 revisits the traditional view that a low-price guarantee results in higher prices by facilitating collusion. Using accurate market definitions and station-level data from the retail gasoline industry in Quebec, I conducted a descriptive analysis based on stations and price zones to compare the price and sales movement before and after the guarantee was adopted. I find that, contrary to the traditional view, the stores that offered the guarantee significantly decreased their prices and increased their sales. I also build a difference-in-difference model to quantify the decrease in posted price of the stores that offered the guarantee to be 0.7 cents per liter. While this change is significant, I do not find the response in comeptitors' prices to be significant. The sales of the stores that offered the guarantee increased significantly while the competitors' sales decreased significantly. However, the significance vanishes if I use the station clustered standard errors. Comparing my observations and the predictions of different theories of modeling low-price guarantees, I conclude the empirical evidence here supports that the low-price guarantee is a simple commitment device and induces lower prices.

Chapter 2 conducts a consumer welfare analysis of low-price guarantees to address the antitrust concerns and potential regulations from the government; explains the firms' potential incentives to adopt a low-price guarantee. Using station-level data from the retail gasoline industry in Quebec, I estimated consumers' demand of gasoline by a structural model with spatial competition incorporating the low-price guarantee as a commitment device, which allows firms to pre-commit to charge the lowest price among their competitors. The counterfactual analysis under the Bertrand competition setting shows that the stores that offered the guarantee attracted a lot more consumers and decreased their posted price by 0.6 cents per liter. Although the matching stores suffered a decrease in profits from gasoline sales, they are incentivized to adopt the low-price guarantee to attract more consumers to visit the store likely increasing profits at attached convenience stores. Firms have strong incentives to adopt a low-price guarantee on the product that their consumers are most price-sensitive about, while earning a profit from the products that are not covered in the guarantee. I estimate that consumers earn about 0.3% more surplus when the low-price guarantee is in place, which suggests that the authorities should not be concerned and regulate low-price guarantees. In Appendix B, I also propose an empirical model to look into how low-price guarantees would change consumer search behavior and whether consumer search plays an important role in estimating consumer surplus accurately.

Chapter 3, joint with Gale Boyd, describes work with the pulp, paper, and paperboard (PP&PB) industry to provide a plant-level indicator of energy efficiency for facilities that produce various types of paper products in the United States. Organizations that implement strategic energy management programs undertake a set of activities that, if carried out properly, have the potential to deliver sustained energy savings. Energy performance benchmarking is a key activity of strategic energy management and one way to enable companies to set energy efficiency targets for manufacturing facilities. The opportunity to assess plant energy performance through a comparison with similar plants in its industry is a highly desirable and strategic method of benchmarking for industrial energy managers. However, access to energy performance data for conducting industry benchmarking is usually unavailable to most industrial energy managers. The U.S. Environmental Protection Agency (EPA), through its ENERGY STAR program, seeks to overcome this barrier through the development of manufacturing sector-based plant energy performance indicators (EPIs) that encourage U.S. industries to use energy more efficiently. In the development of the energy performance indicator tools, consideration is given to the role that performance-based indicators play in motivating change; the steps necessary for indicator development, from interacting with an industry in securing adequate data for the indicator; and actual application and use of an indicator when complete. How indicators are employed in EPA’s efforts to encourage industries to voluntarily improve their use of energy is discussed as well. The chapter describes the data and statistical methods used to construct the EPI for plants within selected segments of the pulp, paper, and paperboard industry: specifically pulp mills and integrated paper & paperboard mills. The individual equations are presented, as are the instructions for using those equations as implemented in an associated Microsoft Excel-based spreadsheet tool.

Briefing paper on eTextbooks and third party eLearning products and their implications for Australian university libraries

The briefing paper was commissioned by the Council of Australian University Librarians (CAUL) to examine the current picture and evolving role of electronic textbooks (eTextbooks) and third party eLearning products in the academic arena. The study reviews industry trends, identifies the major players and considers the different stakeholder perspectives of eTextbook adoption. Within the context of learning and teaching in the digital age, specific areas of research, policy and practice are highlighted to consider the implications that eTextbooks might have for universities in general and for university libraries in particular. An environmental scan focused on the analysis of current developments and the anticipated future directions of digital learning resources in Australia, as well as in other major English speaking countries such as the United Kingdom and the United States. This research guided the development of key interview questions aimed at examining, at a deeper level, diverse stakeholder perspectives about the roles university libraries can play in the adoption of digital learning content.

Determination of nitrite in meat products and water using dapsone with combined spot test/diffuse reflectance on filter paper

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Developed country imports of manufactured products from LDCs : a research paper /

"ER 80-10476."

The effect of consumer risk perceptions and information search on willingness to buy GM food products: A cross cultural analysis

This paper seeks to address the widespread call in the literature for the cross-cultural examination ( and validation) of accepted concepts within consumer behaviour, such as consumer risk perceptions and information search. The findings of the study provide support for a number of accepted relationships, whilst identifying distinct cross cultural differences in external information search and willingness to buy genetically modified (GM) food products by consumers.

Drivers of technology substitution : successive generations of high tech products

Principal Topic High technology consumer products such as notebooks, digital cameras and DVD players are not introduced into a vacuum. Consumer experience with related earlier generation technologies, such as PCs, film cameras and VCRs, and the installed base of these products strongly impacts the market diffusion of the new generation products. Yet technology substitution has received only sparse attention in the diffusion of innovation literature. Research for consumer durables has been dominated by studies of (first purchase) adoption (c.f. Bass 1969) which do not explicitly consider the presence of an existing product/technology. More recently, considerable attention has also been given to replacement purchases (c.f. Kamakura and Balasubramanian 1987). Only a handful of papers explicitly deal with the diffusion of technology/product substitutes (e.g. Norton and Bass, 1987: Bass and Bass, 2004). They propose diffusion-type aggregate-level sales models that are used to forecast the overall sales for successive generations. Lacking household data, these aggregate models are unable to give insights into the decisions by individual households - whether to adopt generation II, and if so, when and why. This paper makes two contributions. It is the first large-scale empirical study that collects household data for successive generations of technologies in an effort to understand the drivers of adoption. Second, in comparision to traditional analysis that evaluates technology substitution as an ''adoption of innovation'' type process, we propose that from a consumer's perspective, technology substitution combines elements of both adoption (adopting the new generation technology) and replacement (replacing the generation I product with generation II). Based on this proposition, we develop and test a number of hypotheses. Methodology/Key Propositions In some cases, successive generations are clear ''substitutes'' for the earlier generation, in that they have almost identical functionality. For example, successive generations of PCs Pentium I to II to III or flat screen TV substituting for colour TV. More commonly, however, the new technology (generation II) is a ''partial substitute'' for existing technology (generation I). For example, digital cameras substitute for film-based cameras in the sense that they perform the same core function of taking photographs. They have some additional attributes of easier copying and sharing of images. However, the attribute of image quality is inferior. In cases of partial substitution, some consumers will purchase generation II products as substitutes for their generation I product, while other consumers will purchase generation II products as additional products to be used as well as their generation I product. We propose that substitute generation II purchases combine elements of both adoption and replacement, but additional generation II purchases are solely adoption-driven process. Extensive research on innovation adoption has consistently shown consumer innovativeness is the most important consumer characteristic that drives adoption timing (Goldsmith et al. 1995; Gielens and Steenkamp 2007). Hence, we expect consumer innovativeness also to influence both additional and substitute generation II purchases. Hypothesis 1a) More innovative households will make additional generation II purchases earlier. 1 b) More innovative households will make substitute generation II purchases earlier. 1 c) Consumer innovativeness will have a stronger impact on additional generation II purchases than on substitute generation II purchases. As outlined above, substitute generation II purchases act, in part like a replacement purchase for the generation I product. Prior research (Bayus 1991; Grewal et al 2004) identified product age as the most dominant factor influencing replacements. Hence, we hypothesise that: Hypothesis 2: Households with older generation I products will make substitute generation II purchases earlier. Our survey of 8,077 households investigates their adoption of two new generation products: notebooks as a technology change to PCs, and DVD players as a technology shift from VCRs. We employ Cox hazard modelling to study factors influencing the timing of a household's adoption of generation II products. We determine whether this is an additional or substitute purchase by asking whether the generation I product is still used. A separate hazard model is conducted for additional and substitute purchases. Consumer Innovativeness is measured as domain innovativeness adapted from the scales of Goldsmith and Hofacker (1991) and Flynn et al. (1996). The age of the generation I product is calculated based on the most recent household purchase of that product. Control variables include age, size and income of household, and age and education of primary decision-maker. Results and Implications Our preliminary results confirm both our hypotheses. Consumer innovativeness has a strong influence on both additional purchases (exp = 1.11) and substitute purchases (exp = 1.09). Exp is interpreted as the increased probability of purchase for an increase of 1.0 on a 7-point innovativeness scale. Also consistent with our hypotheses, the age of the generation I product has a dramatic influence for substitute purchases of VCR/DVD (exp = 2.92) and a strong influence for PCs/notebooks (exp = 1.30). Exp is interpreted as the increased probability of purchase for an increase of 10 years in the age of the generation I product. Yet, also as hypothesised, there was no influence on additional purchases. The results lead to two key implications. First, there is a clear distinction between additional and substitute purchases of generation II products, each with different drivers. Treating these as a single process will mask the true drivers of adoption. For substitute purchases, product age is a key driver. Hence, implications for marketers of high technology products can utilise data on generation I product age (e.g. from warranty or loyalty programs) to target customers who are more likely to make a purchase.

A national building products inventory

Australia has no nationally accepted building products life cycle inventory (LCI) database for use in building Ecologically Sustainable Development (ESD) assessment (BEA) tools. More information about the sustainability of the supply chain is limited by industry’s lack of real capacity to deliver objective information on process and product environmental impact. Recognition of these deficits emerged during compilation of a National LCI database to inform LCADesign, a prototype 3 dimensional object oriented computer aided design (3-D CAD) commercial building design tool. Development of this Australian LCI represents 24 staff years of effort here since 1995. Further development of LCADesign extensions is proposed as being essential to support key applications demanded from a more holistic theoretical framework calling for modules of new building and construction industry tools. A proposed tool, conceptually called LCADetails, is to serve the building product industries own needs as well as that of commercial building design amongst other industries’ prospective needs. In this paper, a proposition is examined that the existing national LCI database should be further expanded to serve Australian building product industries’ needs as well as to provide details for its client-base from a web based portal containing a module of practical supply and procurement applications. Along with improved supply chain assessment services, this proposed portal is envisaged to facilitate industry environmental life cycle improvement assessment and support decision-making to provide accredited data for operational reporting capabilities, load-based reasoning as well as BEA applications. This paper provides an overview of developments to date, including a novel 3-D CAD information and communications technology (ICT) platform for more holistic integration of existing tools for true cost assessment. Further conceptualisation of future prospects, based on a new holistic life cycle assessment framework LCADevelop, considering stakeholder relationships and their need for a range of complementary tools leveraging automated function off such ICT platforms to inform dimensionally defined operations for such as automotive, civil, transport and industrial applications are also explored.