Cellulose swelling by protic solvents: which properties of the biopolymer and the solvent matter?

The question posed in the title has been addressed by studying the swelling of celluloses at 20 C by twenty protic solvents, including water; linear- and branched-chain aliphatic alcohols; unsaturated aliphatic alcohols, and alkoxyalcohols. The biopolymers investigated included microcrystalline cellulose, MC, native and never-dried mercerized cotton cellulose, cotton and M-cotton, and native and never-dried mercerized eucalyptus cellulose, eucalyptus and M-eucalyptus, respectively. In most cases, better correlations with the physico-chemical properties of the solvents were obtained when the swelling was expressed as number of moles of solvent/anhydroglucose unit, nSw, rather than as % increase in sample weight. The descriptors employed in these correlations included, where available, Hildebrand`s solubility parameters, Gutmann`s acceptor and donor numbers, solvent molar volume, V(S), as well as solvatochromic parameters. The latter, employed for the first time for correlating the swelling of biopolymers, included empirical solvent polarity, E(T)(30), solvent ""acidity"", alpha(S), ""basicity"", beta(S), and dipolarity/polarizability, pi(S)*, respectively. Small regression coefficients and large sums of the squares of the residues were obtained when values of nSw were correlated with two solvent parameters. Much better correlations were obtained with three solvent parameters. The most statistically significant descriptor in the correlation equation depends on the cellulose, being pi(S)* for MC, cotton, and eucalyptus, and V(S) for M-cotton and M-eucalyptus. The best correlations were obtained with the same set of four parameters for all celluloses, namely, solvent pKa (or alpha(S)) beta(S), pi(S)*, and V(S), respectively. These results indicate that the supra-molecular structure of the biopolymer, in particular the average sizes of crystallites and micro-pores, and the presence of its chains in parallel (cellulose I) or anti-parallel (cellulose II) arrangements control its swelling. At least for the present biopolymer/solvent systems, use of solvatochromic parameters is a superior alternative to Hildebrand`s solubility parameters and/or Gutmann`s acceptor and donor numbers. The relevance of these results to the accessibility of the hydroxyl groups of cellulose, hence to its reactivity, is briefly discussed.

Ionized-air-treated curaua fibers as reinforcement for phenolic matrices

Curaua fibers were treated with ionized air to improve the fiber/phenolic matrix adhesion.The treatment with ionized air did not change the thermal stability of the fibers. The impact strength increased with increase in the fiber treatment time. SEM micrographs of the fibers showed that the ionized air treatment led to separation of the fiber bundles. Treatment for 12 h also caused a partial degradation of the fibers, which prompted the matrix to transfer the load to a poorer reinforcing agent during impact, thereby decreasing the impact strength of the related composite. The composites reinforced with fibers treated with ionized air absorbed less water than those reinforced with untreated fibers.

Soda-Treated Sisal/Polypropylene Composites

Treated sisal fibers were used as reinforcement of polypropylene (PP) composites, with maleic anhydride-grafted PP (MAPP) as coupling agent. The composites were made by melting processing of PP with the fiber in a heated roller followed by multiple extrusions in a single-screw extruder. Injection molded specimens were produced for the characterization of the material. In order to improve the adhesion between fiber and matrix and to eliminate odorous substances, sisal fibers were treated with boiling water and with NaOH solutions at 3 and 10 wt.%. The mechanical properties of the composites were assessed by tensile, bend and impact tests. Additionally, the morphology of the composites and the adhesion at he fiber-matrix interface were analyzed by SEM. The fiber treatment led to very light and odorless materials, with yields of 95, 74 and 62 wt.% for treatments with hot water, 3 and 10 wt.% soda solution respectively. Fiber treatment caused an appreciable change in fiber characteristics, yet the mechanical properties under tensile and flexural tests were not influenced by that treatment. Only the impact strength increased in the composites with alkali-treated sisal fibers.

Physical Vapor Deposited Thin Films of Lignins Extracted from Sugar Cane Bagasse: Morphology, Electrical Properties, and Sensing Applications

The concern related to the environmental degradation and to the exhaustion of natural resources has induced the research on biodegradable materials obtained from renewable sources, which involves fundamental properties and general application. In this context, we have fabricated thin films of lignins, which were extracted from sugar cane bagasse via modified organosolv process using ethanol as organic solvent. The films were made using the vacuum thermal evaporation technique (PVD, physical vapor deposition) grown up to 120 nm. The main objective was to explore basic properties such as electrical and surface morphology and the sensing performance of these lignins as transducers. The PVD film growth was monitored via ultraviolet-visible (UV-vis) absorption spectroscopy and quartz crystal microbalance, revealing a linear relationship between absorbance and film thickness. The 120 nm lignin PVD film morphology presented small aggregates spread all over the film surface on the nanometer scale (atomic force microscopy, AFM) and homogeneous on the micrometer scale (optical microscopy). The PVD films were deposited onto Au interdigitated electrode (IDE) for both electrical characterization and sensing experiments. In the case of electrical characterization, current versus voltage (I vs V) dc measurements were carried out for the Au IDE coated with 120 nm lignin PVD film, leading to a conductivity of 3.6 x 10(-10) S/m. Using impedance spectroscopy, also for the Au IDE coated with the 120 nm lignin PVD film, dielectric constant of 8.0, tan delta of 3.9 x 10(-3)) and conductivity of 1.75 x 10(-9) S/m were calculated at 1 kHz. As a proof-of-principle, the application of these lignins as transducers in sensing devices was monitored by both impedance spectroscopy (capacitance vs frequency) and I versus time dc measurements toward aniline vapor (saturated atmosphere). The electrical responses showed that the sensing units are sensible to aniline vapor with the process being reversible. AFM images conducted directly onto the sensing units (Au IDE coated with 120 nm lignin PVD film) before and after the sensing experiments showed a decrease in the PVD film roughness from 5.8 to 3.2 nm after exposing to aniline.

Valorization of an Industrial Organosolv-Sugarcane Bagasse Lignin: Characterization and Use as a Matrix in Biobased Composites Reinforced With Sisal Fibers

In the present study, the main focus was the characterization and application of the by-product lignin isolated through an industrial organosolv acid hydrolysis process from sugarcane bagasse, aiming at the production of bioethanol. The sugarcane lignin was characterized and used to prepare phenolic-type resins. The analysis confirmed that the industrial sugarcane lignin is of HGS type, with a high proportion of the less substituted aromatic ring p-hydroxyphenyl units, which favors further reaction with formaldehyde. The lignin-formaldehyde resins were used to produce biobased composites reinforced with different proportions of randomly distributed sisal fibers. The presence of lignin moieties in both the fiber and matrix increases their mutual affinity, as confirmed by SEM images, which showed good adhesion at the biocomposite fiber/matrix interface. This in turn allowed good load transference from the matrix to the fiber, leading to biobased composites with good impact strength (near 500 J m(-1) for a 40 wt% sisal fiber-reinforced composite). The study demonstrates that sugarcane bagasse lignin obtained from a bioethanol plant can be used without excessive purification in the preparation of lignocellulosic fiber-reinforced biobased composites displaying high mechanical properties. Biotechnol. Bioeng. 2010;107: 612-621. (C) 2010 Wiley Periodicals, Inc.

Biobased composites from glyoxal-phenolic resins and sisal fibers

Lignocellulosic materials can significantly contribute to the development of biobased composites. In this work, glyoxal-phenolic resins for composites were prepared using glyoxal, which is a dialdehyde obtained from several natural resources. The resins were characterized by (1)H, (13)C, (2)D, and (31)P NMR spectroscopies. Resorcinol (10%) was used as an accelerator for curing the glyoxal-phenol resins in order to obtain the thermosets. The impact-strength measurement showed that regardless of the cure cycle used, the reinforcement of thermosets by 30% (w/w) sisal fibers improved the impact strength by one order of magnitude. Curing with cycle 1 (150 degrees C) induced a high diffusion coefficient for water absorption in composites, due to less interaction between the sisal fibers and water. The composites cured with cycle 2 (180 degrees C) had less glyoxal resin coverage of the cellulosic fibers, as observed by images of the fractured interface observed by SEM. This study shows that biobased composites with good properties can be prepared using a high proportion of materials obtained from natural resources. (C) 2009 Elsevier Ltd. All rights reserved.

Pineapple Leaf Fibers for Composites and Cellulose

Pineapple leaf fiber (PALF) which is rich in cellulose, abundantly available, relatively inexpensive, low density, nonabrasive nature, high filling level possible, low energy consumption, high specific properties, biodegradability and has the potential for polymer reinforcement. The utilization of pineapple leaf fiber (PALF) as reinforcements in thermoplastic and thermosetting resins in micro and nano form for developing low cost and lightweight composites is an emerging field of research in polymer science and technology. In this paper we examines the industrial applicabiliy of PALF, mainly for production of composite materials and special papers, chemical feedstocks (bromelin enzyme) and fabrics.

Phenolic matrices and sisal fibers modified with hydroxy terminated polybutadiene rubber: Impact strength, water absorption, and morphological aspects of thermosets and composites

The aim of the present work was to investigate the toughening of phenolic thermoset and its composites reinforced with sisal fibers, using hydroxyl-terminated polybutadiene rubber (HTPB) as both impact modifier and coupling agent. Substantial increase in the impact strength of the thermoset was achieved by the addition 10% of HTPB. Scanning electron microscopy (SEM) images of the material with 15% HTPB content revealed the formation of some rubber aggregates that reduced the efficiency of the toughening mechanism. In composites, the toughening effect was observed only when 2.5% of HTPB was added. The rubber aggregates were found located mainly at the matrix-fiber interface suggesting that HTPB could be used as coupling agent between the sisal fibers and the phenolic matrix. A composite reinforced with sisal fibers pre-impregnated with HTPB was then prepared; its SEM images showed the formation of a thin coating of HTPB on the surface of the fibers. The ability of HTBP as coupling agent between sisal fibers and phenolic matrix was then investigated by preparing a composite reinforced with sisal fibers pre-treated with HTPB. As revealed by its SEM images, the HTPB pre-treatment of the fibers resulted on the formation of a thin coating of HTPB on the surface of the fibers, which provided better compatibility between the fibers and the matrix at their interface, resulting in a material with low water absorption capacity and no loss of impact strength. (C) 2009 Elsevier B.V. All rights reserved.

Characterization of banana, sugarcane bagasse and sponge gourd fibers of Brazil

In recent times, increasing attention has been paid to the use of renewable resources particularly of plant origin keeping in view the ecological concerns, renewability and many governments passing laws for the use of such materials. On the other hand, despite abundant availability of lignocellulosic materials in Brazil, very few attempts have been made about their utilization, probably due to lack of sufficient structure/property data. Systematic studies to know their properties and morphology may bridge this gap while leading to value addition to these natural materials. Chemical composition, X-ray powder diffraction, and morphological studies and thermal behavior aspects in respect of banana, sugarcane bagasse sponge gourd fibers of Brazilian origin are presented. Chemical compositions of the three fibers are found to be different than those reported earlier. X-ray diffraction patterns of these three fibers exhibit mainly cellulose type I structure with the crystallinity indices of 39%, 48% and 50% respectively for these fibers. Morphological studies of the fibers revealed different sizes and arrangement of cells. Thermal stability of all the fibers is found to be around 200 degrees C. Decomposition of both cellulose and hemicelluloses in the fibers takes place at 300 degrees C and above, while the degradation of fibers takes place above 400 degrees C. These data may help finding new uses for these fibers. (C) 2009 Elsevier B.V. All rights reserved.

Intelligent Algorithms for a Hybrid FuelCell/Photovoltaic Standalone System : Simulation Of Hybrid FuelCell/Photovoltaic Standalone System

The Intelligent Algorithm is designed for theusing a Battery source. The main function is to automate the Hybrid System through anintelligent Algorithm so that it takes the decision according to the environmental conditionsfor utilizing the Photovoltaic/Solar Energy and in the absence of this, Fuel Cell energy isused. To enhance the performance of the Fuel Cell and Photovoltaic Cell we used batterybank which acts like a buffer and supply the current continuous to the load. To develop the main System whlogic based controller was used. Fuzzy Logic based controller used to develop this system,because they are chosen to be feasible for both controlling the decision process and predictingthe availability of the available energy on the basis of current Photovoltaic and Battery conditions. The Intelligent Algorithm is designed to optimize the performance of the system and to selectthe best available energy source(s) in regard of the input parameters. The enhance function of these Intelligent Controller is to predict the use of available energy resources and turn on thatparticular source for efficient energy utilization. A fuzzy controller was chosen to take thedecisions for the efficient energy utilization from the given resources. The fuzzy logic basedcontroller is designed in the Matlab-Simulink environment. Initially, the fuzzy based ruleswere built. Then MATLAB based simulation system was designed and implemented. Thenthis whole proposed model is simulated and tested for the accuracy of design and performanceof the system.

Effect Of Different Hydrological Model Structures On The Assimilation Of Distributed Uncertain Observations

The reliable evaluation of the flood forecasting is a crucial problem for assessing flood risk and consequent damages. Different hydrological models (distributed, semi-distributed or lumped) have been proposed in order to deal with this issue. The choice of the proper model structure has been investigated by many authors and it is one of the main sources of uncertainty for a correct evaluation of the outflow hydrograph. In addition, the recent increasing of data availability makes possible to update hydrological models as response of real-time observations. For these reasons, the aim of this work it is to evaluate the effect of different structure of a semi-distributed hydrological model in the assimilation of distributed uncertain discharge observations. The study was applied to the Bacchiglione catchment, located in Italy. The first methodological step was to divide the basin in different sub-basins according to topographic characteristics. Secondly, two different structures of the semi-distributed hydrological model were implemented in order to estimate the outflow hydrograph. Then, synthetic observations of uncertain value of discharge were generated, as a function of the observed and simulated value of flow at the basin outlet, and assimilated in the semi-distributed models using a Kalman Filter. Finally, different spatial patterns of sensors location were assumed to update the model state as response of the uncertain discharge observations. The results of this work pointed out that, overall, the assimilation of uncertain observations can improve the hydrologic model performance. In particular, it was found that the model structure is an important factor, of difficult characterization, since can induce different forecasts in terms of outflow discharge. This study is partly supported by the FP7 EU Project WeSenseIt.

Leakage Detection And Localization Method Based On A Hybrid Inverse/Direct Modelling Approach Suitable For Handling Multiple-Leak Scenarios

When an accurate hydraulic network model is available, direct modeling techniques are very straightforward and reliable for on-line leakage detection and localization applied to large class of water distribution networks. In general, this type of techniques based on analytical models can be seen as an application of the well-known fault detection and isolation theory for complex industrial systems. Nonetheless, the assumption of single leak scenarios is usually made considering a certain leak size pattern which may not hold in real applications. Upgrading a leak detection and localization method based on a direct modeling approach to handle multiple-leak scenarios can be, on one hand, quite straightforward but, on the other hand, highly computational demanding for large class of water distribution networks given the huge number of potential water loss hotspots. This paper presents a leakage detection and localization method suitable for multiple-leak scenarios and large class of water distribution networks. This method can be seen as an upgrade of the above mentioned method based on a direct modeling approach in which a global search method based on genetic algorithms has been integrated in order to estimate those network water loss hotspots and the size of the leaks. This is an inverse / direct modeling method which tries to take benefit from both approaches: on one hand, the exploration capability of genetic algorithms to estimate network water loss hotspots and the size of the leaks and on the other hand, the straightforwardness and reliability offered by the availability of an accurate hydraulic model to assess those close network areas around the estimated hotspots. The application of the resulting method in a DMA of the Barcelona water distribution network is provided and discussed. The obtained results show that leakage detection and localization under multiple-leak scenarios may be performed efficiently following an easy procedure.

Hybrid Auctions II: Experimental Evidence

In this paper we report the results of an experiment designed to examine the properties of a hybrid auction - a Dutch-Vickrey auction, that combines a sealed bid …rst-price auction with a sealed bid second-price auction. This auction mechanism shares some important features with that used in the sale of the companies constituted through the partial division of the Telebras System - the government-owned Telecom holding in Brazil. We designed an experiment where individuals participate in a sequence of independent …rst-price auctions followed by a sequence of hybrid auctions. Several conclusions emerged from this experimental study. First, ex-post e¢ciency was achieved overwhelmingly by the hybrid auctions. Secondly, although overbidding (with respect to the risk-neutral Bayesian Nash equilibrium) was a regular feature of participants’ bidding behavior in the …rst-price auctions — as it is commonly reported in most experimental studies of …rst-price auctions, it was less frequent in the hybrid auctions. By calibrating the results to allow for risk-averse behavior we were able to account for a signi…cant part of the overbidding. Finally, we compared the revenue generated by the hybrid auction with that generated by a standard …rst-price sealed bid auction and the results were ambiguous.

Hybrid Auctions I: Theory

In this paper we examine the properties of a hybrid auction that combines a sealed bid and an ascending auction. In this auction, each bidder submits a sealed bid. Once the highest bid is known, the bidder who submitted it is declared the winner if her bid is higher than the second highest by more than a predetermined amount or percentage. If at least one more bidder submitted a bid su¢ciently close to the highest bid (that is, if the di¤erence between this bid and the highest bid is smaller than the predetermined amount or percentage) the quali…ed buyers compete in an open ascending auction that has the highest bid of the …rst stage as the reserve price. Quali…ed bidders include not only the highest bidder in the …rst stage but also those who bid close enough to her. We show that this auction generates more revenue than a standard auction. Although this hybrid auction does not generate as much revenue as the optimal auction, it is ex-post e¢cient.

Aligning sustainability and corporate strategies: the case of hybrid-electric vehicles and Fiat-Chrysler Automobiles

Este estudo analisa a integração da sustentabilidade ambiental na estratégia das empresas no contexto da indústria automobilística. A implementação de estratégias de sustentabilidade e o desenvolvimento de veículos híbrido-elétricos são investigados com referência ao caso de um ator principal na indústria. Entre as aplicações de mobilidade eléctrica, que irá aumentar a presença no mercado nos próximos anos devido às regulamentações rigorosas e as preferências dos clientes, a pesquisa está focada em veículos híbrido-elétricos. As estratégias de sustentabilidade das grandes fabricantes de automóveis e as implicações subsequentes em termos de desenvolvimento de produtos, com uma atenção especial aos veículos elétricos híbridos, foram analisados através de dados secundários. Além disso, os dados primários foram coletados sobre a estratégia de sustentabilidade de um ator importante na indústria e usados para realizar um estudo de caso. A análise incidiu sobre os fatores críticos e os aspectos que têm impacto sobre as estratégias de sustentabilidade, que visam reduzir o impacto ambiental da indústria automobilística, e sobre o desenvolvimento de veículos híbridos. A análise dos dados mostrou que a Fiat-Chrysler Automobiles (FCA) teve uma ênfase menor na mobilidade eléctrica em termos de relatórios de sustentabilidade. A conclusão apresenta uma avaliação da estratégia corporativa da FCA, em termos de sustentabilidade ambiental, e apresenta um quadro para o desenvolvimento de veículos híbridos com quatro abordagens diferentes que têm impacto sobre a estratégia de sustentabilidade de uma montadora.