QC 20120315

This dissertation examines the relation between occupational exposure to the solvent methylene chloride and mortality in a cohort of cellulose fiber production workers. The first paper, entitled The Mortality of Cellulose Fiber Production Workers, presents the main results of the mortality follow-up of the cellulose fiber workers cohort through September 1, 1986. Mortality from neoplastic and non-neoplastic disease among cellulose fiber production workers is compared to that of the U.S. and local (county level) populations, while controlling for the effects of gender, race, calendar period, and age. Mortality from cancers of the lung, breast, and pancreas, and ischemic heart disease was less than expected. Excess mortality was observed for melanoma of the skin, cancer of the buccal cavity and pharynx, tumors of the liver and biliary tract, and accidental deaths. Three deaths from cancer of the bile ducts were observed (3 observed, 0.15 expected, SMR=20). This is the first known report of an association between exposure to methylene chloride and cancer of the bile ducts. [TRUNCATED]

Hornification is the term used to describe the irreversible changes that occur in cellulose fibers due to recycling. While the effects of hornification have been documented, there are several conflicting hypotheses that attempt to explain the causes. In this research, AFM surface adhesion measurements made on virgin and recycled bleached kraft pulp show that recycling increases the apparent hydrophilicity of the fiber surface. Yet, the water retention values and tensile strength decrease as expected, which is consistent with internal cross-linking of the bonding sites and a reduction in hydrophilicity. Recycling does not affect the amount of monolayer water bound to the fiber surface indicating that the pore water is reduced but not the water bound to fiber surfaces. It is proposed that the contact area between the AFM tip and the fiber is greater for recycled material than for virgin. Image analysis of the fiber surface supports this conclusion, revealing a decrease in the surface roughness. The irregularity of fiber surfaces is apparent in AFM images at all but the smallest scales, with macroscopic fiber features dominating the roughness analyses of images larger than 2500 square nanometers. Hence, in this instance, the surface adhesion values are more a measure of the topography of the surface than of its chemistry. An application to newsprint is illustrated, revealing the limitations of AFM analysis of samples with a high degree of variability.

Steam exploded fibers from Yellow Poplar (Liriodendron tulipifera) wood were assessed in terms of (a) their impact on torque during melt processing of a thermoplastic cellulose ester (plasticized CAB); (b) their fiber incorporation and dispersion characteristics in a CAB-based composite by SEM and image analysis, respectively; and (c) their impact on the mechanical properties (under tension) of CAB-based composites having fiber contents of between 10 and 40% by weight. The fibers included water-washed steam exploded fibers (WEF), alkali-extracted fibers (AEF), acetylated fibers (AAEF), all from Yellow poplar (log Ro = 4.23), and oat fillers (COF) as control. The stepwise increase in cellulose content by extraction, and especially the (surface) modification by acetylation, contributed to increased torque during melt processing, and to improved interfacial adhesion as well as fiber dispersion. As compared to pure CAB, AAEF generated the highest increase in torque (+ 421%) followed by AEF (+ 260%) and WEF (+ 190%) at 40% fiber content by weight. AAEF was also found to enhance the tensile properties of the resulting composites. SEM studies of the tensile fracture surfaces indicated significant interfacial delamination and also pull - out of fibers when WEF, AEF, and COF were used to reinforce the CAB matrix. Composites with AAEF, by contrast, revealed fracture surfaces with reduced interfacial delamination and with significant fiber fracturing during failure. Image analysis was used to determine fiber dispersion within the resulting composites quantitatively. Significant improvement in fiber dispersion was achieved when the matrix was reinforced with acetylated fibers (AAEF). Fiber addition to the matrix resulted in loss of strain at break (- 80 to - 93%) and slight or significant increases in modulus (+ 47 to + 103%) depending on fiber type at 40% fiber content. Maximum stress declined for all fibers except AAEF at all fiber contents. AAEF-based composites revealed a decline in maximum stress when fiber content rose to 10%, and this reversed when fiber content increased beyond 10%. This increase in strength is consistent with the rule of mixtures that stipulates reinforcement of the matrix by fibers that are capable of transferring stresses across the fiber-matrix interface. All fibers suffered length decreases during melt processing. / Master of Science

The aim of the study was to find out the relationship between the DP and the tensile properties of different regenerated cellulose fibers. During the process to make regenerated cellulose fibers from wood, the reduction in DP of cellulose is a necessary process to enable fiber extrusion. The reduction of the DP is usually from 1000 to 350 (Coley 1953). The reduction in DP is necessary, first to make the cellulose soluble, and then further decrease in DP is required to control the viscosity of the solution to minimize the mechanical difficulties during processing faced. It is a fact that the reduction in DP is a compromise which is necessary, as reduction in DP means reduction in tensile properties of the fiber produced. The reduction in DP is optimized to make the process both processing and the final product more feasible. The relation in DP and the strength of the fibers is rather obvious i.e. higher the DP higher the tensile strength, but researchers have different views regarding the relationship. By the experiments performed by us we tried to come to a conclusion regarding the difference in opinions. Different types of regenerated cellulose fibers were collected from various sources. Both wet and dry tenacities of 19 different viscose, bamboo viscose, kupro viscose, modal and Tencel fibers were determined. The fiber linear density was also measured, but for some samples we had to take the fiber density value as provided by the manufacturer, due to the limitation of the instrument regarding the fiber length and low fiber linear density. Then out of all the samples 10 were selected (based on our and company’s interest). SEC analysis was used to determine the DP of the samples. These tests were not carried out by us but by MoRe Research. The results of both the analysis were gathered, analyzed and commented upon. / Program: Master Programme in Textile Technology

The objectives of the research are to establish the process of obtaining regenerated fibers and films from wood pulp and bagasse pulp with the ionic liquid 1-Butyl-3-methylimidazolium Chloride (BMIMCl) as a solvent; to study the impacts on tensile strength of different spinning parameters; to find the optimal spinning condition, and to obtain regenerated cellulose products with flame retardant properties. Solutions were obtained by dissolving cellulose (wood/bagasse) pulp into the BMIMCl. The solutions were extruded in a dry-jet and wet-spinning method using water as a coagulation bath. The obtained fibers were tested to evaluate the properties such as tensile strength, thermal property, thermal mechanical property, crystal order, and ionic liquid residue in obtained fiber. The orthogonal experiments were designed to find out the strongest affective variable and the optimal condition of the spinning process. The regenerated cellulose films with melamine resin or zinc oxide were obtained. Their flame retardant properties were tested. Cellulose fiber with melamine resin was also obtained. Thermo-gravimetric analyzer (TGA) was used to measure the thermal properties of obtained products, and to calculate their activation energies. Dynamic mechanical analysis (DMA) was used to determine the thermal mechanical properties of obtained fibers. Wide angle X-ray diffraction (WAXD) was used to measure the degree of crystallinity and degree of crystal orientation. The tensile strength was tested by a tensile machine. To evaluate the quantity of ionic liquid residue in the regenerated fibers, the instrumental methods of FT-IR and Mass Spectrometry were applied. Research results indicated increases in the degree of crystallinity and storage modulus under a higher fiber drawing speed. Both regenerated bagasse fibers and regenerated wood fibers had similar thermal properties. However, the regenerated bagasse fibers showed a higher degree of crystallinity and a higher tenacity than the regenerated wood fibers obtained under the same condition. The study also revealed water treatment would be helpful for eliminating the ionic residue in regenerated fibers. It was also found the concentration of cellulose in the BMIMCl solution affected the tensile strength of regenerated fiber mostly. Certain amount of melamine or zinc oxide nanoparticles contained in the cellulose matrix could improve the flame retardant property effectively. / text

Cellulose fiber was used to reinforce higher melting temperature engineering thermoplastics, such as nylon 6 and nylon 66. The continuous extrusion - direct compression molding processing and extrusion-injection molding were chosen to make cellulose fiber/nylon 6 or 66 composites. Tensile, flexural and Izod impact tests were used to demonstrate the mechanical properties of the composites. The continuous extrusion-compression molding processing can decrease the thermal degradation of cellulose fiber, but fiber doesn't disperse well with this procedure. Injection molding gave samples with better fiber dispersion and less void content, and thus gave better mechanical properties than compression molding. Low temperature compounding was used to extrude cellulose fiber/nylon composites. Plasticizer and a ceramic powder were used to decrease the processing temperature. Low temperature extrusion gave better mechanical properties than high temperature extrusion. The tensile modulus of nylon 6 composite with 30 % fiber can reach 5GPa; with a tensile strength of 68MPa; a flexural modulus of 4GPa, and a flexural strength of 100MPa. The tensile modulus of nylon 66 composites with 30 %fiber can reach 5GPa;with a flexural modulus of 5GPa; a tensile strength of 70MPa; and a flexural strength of 147MPa. The effect of thermal degradation on fiber properties was estimated. The Halpin-Tsai model and the Cox model were used to estimate the composite modulus. The Kelly-Tyson model was used to estimate the composite strength. The result indicates that the change of fiber properties determines the final properties of composites. Fiber length has a minor affect on both modulus and strength as long as the fiber length is above the critical length.

Au cours de ce travail, le taux d’extractibles de cinq essences camerounaises a été évalué par la technique d’extraction accélérée ASE 200 et au Soxhlet. Le taux d’extractibles varie de 4,4 à 17,7%. Le screening des extraits a révélé la présence de polyphénols, de saponines, de flavonoïdes, de stérols et de terpènes. Les phénols totaux contenus dans les extraits ont été évalués par la méthode de Folin–Ciocalteu en utilisant l’acide gallique comme standard. La teneur varie de 16,5 à 165,83 mg éq acide gallique / g d’extrait. Le dosage des tannins condensés par la méthode colorimétrique a permis de montrer que ces derniers varient de 0,15 à 23,61 g cyanidin équivalents / 100 g de matière sèche. L’identification des composés contenus dans les extraits par GC-MS a permis d’identifier de l’homopterocarpine et de la pterocarpine dans les extraits de padouk. Les extraits de tali contiennent de la catéchine, l’acide gallique et du pyrogallole. L’acide gallique, le squalène et les triterpènes sont les composés majoritairement identifiés dans les extraits de movingui. La durabilité naturelle des bois a été évaluée par la norme européenne EN 350-1, 1994. Il ressort que les pertes de masse deviennent plus importantes lorsque les éprouvettes de bois ont été extraites. La perte de masse des éprouvettes non extraites varie de 0,1 à 59% (le hêtre a été pris comme référence). Les essais d’inhibition de croissances sur les champignons de pourriture ont montré qu’à des concentrations de 250 ppm, nos extraits étaient fongistatiques et qu’à des concentrations de 500 ppm certains extrait étaient fongicides (extrait de tali). L’évaluation des propriétés antioxydante et colorante des extraits pour envisager de potentielles applications industrielles a été effectuée. Le pouvoir antioxydant des extraits a été évalué par la méthode d’inhibition du linoléate de méthyle induite par l’azobisisobutyronitrile (AIBN). Les résultats obtenus sont satisfaisants car l’activité antioxydante varie de 10 à 86%. Le pouvoir anti-radicalaire des extraits a été évalué en utilisant le radical 2,2-diphényl-1-picrylhydrazyl (DPPH.). Les concentrations nécessaires pour consommer 50% du radical varie de 2,7 à 60,5 mg/L. La capacité des extraits aqueux et alcalins à teindre les fibres naturelles et artificielles a été évaluée. La mesure de la coloration prise par les fibres s’est faite à l’aide d’un colorimètre Datacolor D65°10. Les résultats montrent que ces extraits donnent une coloration jaune avec les extraits de movingui et une coloration rouge avec les extraits de padouk. L’utilisation des extraits pour inhiber la croissance bactérienne a montré que les extraits étaient bactériostatiques pour les concentrations testées / In this work, the accelerated technical ASE 200 and Soxhelet was used to evaluate the amount of extractives contained in five Cameroonian wood species. The amount of extractives ranged from 4.4 to 17.7% with respect to oven-dry matter. Phytochemical screening of the extractives revealed the presence of polyphenols, saponins, flavonoïds, sterols and terpenes. The total phenolic content of the extracts was measured by the Folin-Ciocalteu method using gallic acid as standard. The phenolic content ranged from 16.5 to 165.83 mg eq gallic acid/g of extract. The condensed tannins, evaluated by colorimetric method, ranged from 0.15 to 23.61 g cyanidin equivalents/100 g of dry matter. GC-MS identified the homopterocarpine and pterocarpin as major compound in extracts of padouk. Catechin, gallic acid and pyrogallole were the major compounds found in the extracts of tali. Extracts of movingui consisted mainly of diterpenes and several compounds not readily identifiable. Gallic acid, squalene and triterpenes were the predominant compounds identified in the extracts of movingui. The natural durability of wood was evaluated using the European Standard EN 350-1. Mass losses increased when the wood samples were extracted. Mass losses of non-extracted samples ranged from 0.1 to 59% (with beech taken as a reference). The effect of extractives on fungal growth showed that at 250 ppm concentrations, the extracts were fungistatic and that at 500 ppm concentrations, the extracts of tali were fungicidal.Valorization of the extractives in the food and the textile industries was attempted. In food, the antioxidant activity of the extracts by inhibition of methyl linoleate induced by AIBN was evaluated. The results obtained were satisfactory because all the extracts showed antioxidant activity which varied from 10 to 86%. Then the anti-radical capacity of our extracts was assessed by the DPPH method. The concentration necessary to consume 50% of DPPH varied from 2.7 to 60.5 mg/L. Aqueous and alkaline extracts were used to dye natural and artificial fibers. The coloration taken by the fibers was measured using a Datacolor D65°10 apparatus. These extracts gave a yellow color with extracts of movingui and a red color with extracts of padouk. The effect of extractives on bacteria growth showed that the extracts were bacteriostatic at the tests concentrations

A celulose é o principal polímero derivado de fonte renovável de uso industrial tanto em termos de volume como em número de aplicações. A celulose é comercializada na forma de polpa, que se trata de uma commodity cuja principal aplicação é a indústria de papel e de derivados de celulose, tais como os seus éteres e ésteres. Com o advento das nanoceluloses, que podem ser obtidas diretamente da polpa química, se observa um expressivo aumento no interesse por esses materiais. A modificação superficial tanto das fibras (polpa) como das microfibrilas é de grande interesse, pois podem permitir a ampliação do uso desses materiais uma vez que suas propriedades poderiam ser modificadas. O desenvolvimento de métodos de modificação em meio aquoso da celulose em suspensão é de grande interesse em especial se realizado com o uso de agentes sustentáveis em contexto de química verde. Este trabalho visou a modificação da polpa de celulose por duas vias: química e física, realizadas inteiramente em meio aquoso e utilizando materiais de caráter renováveis. A modificação física da fibra de celulose \"never-dried\" foi feita pelo método de auto-montagem (Layer-by-Layer) com o par de polieletrólito quitosana / carboximetilcelulose (CH / CMC) em meio aquoso. Fibras modificadas foram submetidas à analise morfológica (MEV e microscopia confocal no método de absorção de dois fótons e EDS), propriedade mecânica (módulo elástico e limite de resistência à tração) e potencial zeta. O complexo CH / CMC depositado sobre as fibras apresentou uma espessura de aproximadamente 50 nm por camada e um aumento de aproximadamente 170% no limite de resistência a tração das folhas produzidos a partir das fibras, demonstrando uma forte interação fibra/polieletrólitos. Através da técnica de absorção de dois fótons foi possível identificar a deposição das camadas fora e dentro das fibras sem o uso de cromóforo. A modificação química da nanofibra de celulose foi feita pela enxertia de grupamentos furânicos na superfície da fibra, oxidada. Em seguida de uma reação com uma bismaleimida através da reação de \"click\" de Diels-Alder em meio aquoso. Os géis foram caracterizados por meio da técnica de calorimetria diferencial de varredura (DSC) e viscosimetria, com os quais pode-se verificar o efeito da termorreversibilidade uma vez que a 65°C ocorre gelificação do sistema e 95°C ocorre reversão do gel como resultado das reações DA e retro Diels-Alder. As modificações das fibras e nanofibras de celulose em meio aquoso foram bem-sucedidas, o que pode impulsionar o uso da polpa de celulose em novas aplicações originais como artefatos de papel fortes e géis biocompatíveis, visando a estratégia green chemistry. / Cellulose is the main polymer derived from renewable sources of industrial use, in terms of volume and number of applications. Cellulose is marketed in the pulp form, which is a commodity whose main application is the paper industry and derived from pulp, such as its ethers and esters. The advent of nanocelluloses, which can be obtained directly from the chemical pulp, there is an expressive increase in these materials. The superficial modification in fibers (pulp) and microfibrils is great interest, since they can allow the amplification of the use of these materials since their properties could be modified. The development of methods for modification of cellulose in aqueous suspension is of particular interest especially if carried out with sustainable agents in the context of green chemistry. This work aimed at the modification of the cellulose pulp by two routes: chemistry and physics, performed entirely in aqueous medium and using renewable character materials. The physical modification of the \"never-dried\" cellulose fiber was done by the self-assembly method (Layer-by-Layer) with the polyelectrolyte pair chitosan / carboxymethylcellulose (CH / CMC) in aqueous medium. Modified fibers were subjected to morphological analysis (SEM and confocal microscopy in two-photon absorption technique and EDS), mechanical properties (elastic modulus and tensile strength) and zeta potential. The CH / CMC complex deposited under the fibers had a thickness of approximately 50 nm per layer and an increase of approximately 170% in the tensile strength of the sheets in compare of unmodified fibers sheets, showing a strong interaction between fiber and polyelectrolyte. Through the technique of two-photon adsorption, it was possible to identify the layers deposition outside and inside the fibers without the use of chromophore. The chemical modification of the cellulose nanofiber was made by the grafting of furanic groups on the surface of the oxidized fiber. Following by reaction with a bismaleimide through the \"click\" reaction of Diels-Alder in aqueous medium. The thermoreversible hydrogels were characterized by differential scanning calorimetry (DSC) and viscosimetry, which the effect of thermoreversibility can be verified at 65 °C when the gelation of the system occurs and 95 °C gel reversion occurs because of DA and retro Diels-Alder reactions. Modifications of cellulose fibers and nanofibers in aqueous media have been successful, which may increase the use of cellulose pulp in novel applications such as strong paper artifacts and biocompatible gels, targeting the green chemistry strategy.

This dissertation desribes the behavior of cellulose fiber reinforced concrete. In the theoretical section one can find basic information on cellulose fiber and its methods of production and usage in concrete structures. One can find the information about the effect of high temperature on the mechanical and physical attributes of cellulose fiber reinforced concrete, and also a comparison with other fibers used in concrete based on the research done using scientific literature. Furthermore the details about particular cellulose fibers are provided. In the experimental section the formulas for CHRYSO and GREENCEL concrete are designed. The influence of the addition of various types of cellulose fibers into both liquid and solid states of concrete was researched. Tests were also done on the effect of high temperatures (600 °C and 800 °C) on the firmness and densitiy of concrete, its deformations and visual changes. Furthermore, the resistance of cellulose fibers was monitored by monitoring the development of the pH environment (from pH 4 to pH 12) with long-term deposition of different types of cellulose fibers in these environments.