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Master of Science

no abstract provided by author / Master of Science

M.S.

In nearly all chemical industries the problem of wastes is one of importance, and in any scientific study of waste disposal, the concept of the B.O.D. of the waste is vital. The B.O.D. is usually measured by an arbitrary standard test procedure, but may be determined by manometric measurement of the free oxygen utilized. In either case, the B.O.D. determination requires at least 24 hours. Since the free oxygen involved in the B.O.D. of a waste is utilized in metabolic processes of various microorganisms present, an increase in the number of microorganisms lowers the time required for oxidation of the wastes. In this investigation, the B.O.D. of several wastes was determined by measuring the change in the oxygen uptake of high concentrations of microorganisms because of the presence of the waste. These determinations involved a modification of the resting cell technic used in conjunction with direct Warburg technics. High concentrations of washed cells were prepared and small amounts of the waste added. A control was prepared with distilled water. The effects of waste concentration, bacterial concentration, and temperature were studied. The wastes studied included raw sewage, blowdown liquor and total mill wastes from a semichemical pulp mill, and effluent from an anaerobic, sewage-blowdown liquor digester. The concentrations of microorganisms used ranged from 3.4 to 17.0 milligrams of dry bacterial cells in a total volume of 2.5 milliliters of a 0.05 molar phosphate buffer at a pH of 6.8. The manometric B.O.D. was determined at 30°C. The manometric B.O.D. remained constant at 1,785 parts per million for 1:50 and 1:125 volumetric dilutions of the effluent. The manometric B.O.D. remained constant at 10,200 parts per million for volumetric dilutions ranging from 1:125 to 1:1000 for a sample of the blowdown liquor. The manometric B.O.D. of sewage, blowdown liquor, and mixtures of the two wastes was determined. The values obtained were compared with the standard five-day B.O.D. The manometric B.O.D. of the sewage and the blowdown liquor was 413 parts per million and 13,760 parts per million, respectively. The standard five-day B.O.D. of the sewage and the blowdown liquor was 495 parts per million and 37,800 parts per million, respectively. The manometric B.O.D. of 1:1 by volume mixture of the two wastes was 9,900 parts per million, while the standard five-day B.O.D. was 31,200 parts per million. / Master of Science

Den vanligaste biopolymeren på jorden är cellulosa och det är ett viktigt material i utvecklingen mot ett hållbart samhälle. Cellulosan och dess egenskaper kan modifieras genom kemiska reaktioner. Reaktiviteten hos cellulosans OH-grupper är låg på grund av en tät kristallstruktur, men kan förbättras genom t.ex. svällning eller upplösning följt av utfällning. I det här projeket kommer cellulosa från tre källor, microkristallin cellulose (Avicel), lövedsmassa (björk och asp) och barrvedsmassa (tall och gran) att lösas upp i natriumhydroxid och sedan fällas ut med två olika syror och ett organiskt lösningsmedel. Syrorna som användes var ättiksyra och svavelsyra och det organiska lösningsmedlet var etanol. Därefter jämfördes utbytet av den utfällda cellulosan.  Upplösning av Avicel 2.5 viktprocent gjordes i natriumhydroxid-lösning (10%) vid 5 oC och fälldes ut med de tre fällningsmedlen för att bestämma vilket som gav högst utbyte. Ättiksyra gav de bästa resultaten och användes i följande experiment på massa. Massornas löslighet var låg och den olösta massan var tvungen att separeras genom centrifugering innan utfällning av lösningen kunde göras. Hydrolys av massorna utfördes för att öka lösligheten och utfällningsutbytet. Upplösning av Avicel i kall natriumhydroxid och utfällning var framgångsrik. Utbytet vid utfällning med syror var högt. Det fanns ingen topp för maximalt utbyte när syrorna användes som antilösningsmedel, men etanol hade ett maximalt utbyte men lägre än för syrorna. Resultaten med massa var inte lika bra som för Avicel. De separerade olösta delarna var stora för båda massorna, men HW hade större del olöst material. Utbytet av fällning var lågt eftersom det fanns mindre cellulosa upplöst som kunde fällas ut. Hydrolysen av HW och SW var framgångsrik. Detta gjorde det möjligt att lösa upp och fälla ut mer cellulosa från massan. / Cellulose is the most abundant biopolymer on earth and is an important material in developing a sustainable society. The properties of cellulose can be modified by chemical treatment or reactions. The reactivity is fairly low in crystalline cellulose but can be increased if the dense crystal structure is disrupted by e.g. swelling or dissolution followed by precipitation. Dissolution of cellulose is difficult and this project aims to dissolve cellulose from three sources (Avicel and two sulfate pulps). One of the pulps had a tiny fraction of softwood and mostly birch and aspen, hardwood pulp (HW). The other of the pulps was made of pine and spruce, softwood pulp (SW). The raw materials were dissolved in sodium hydroxide (NaOH) and then precipitated with two acids and an anti-solvent (acetic acid (HOAc), sulfuric acid (H2SO4), or ethanol (EtOH)). The yields of the precipitated products were compared. Avicel 2.5 wt% was dissolved in NaOH solution (10%) at 5 oC and precipitated with the two acids and EtOH to determine the highest yield. HOAc gave the best results and was used in the following experiments on pulp. The solubility of pulps was low and the undissolved pulp had to be separated by centrifugation before precipitation of the solution. Hydrolyzation of the pulps was performed to increase the solubility and the precipitation yield. Dissolution of Avicel in cold NaOH and precipitation was successful. The yield at precipitation with acids was high. There was no peak of maximal yield when the acids were used to precipitate, but EtOH had a maximal yield but lower than for the acids. The results with pulp were not as good as for Avicel. The separated undissolved parts were big for both pulps, but HW was the worst. The yield of precipitation was low as there was less cellulose dissolved that could be precipitated. The hydrolysis of HW and SW was successful. This made it possible to dissolve and precipitate more cellulose from the pulp.

This thesis deals with processing of nanocellulose originating from pulps, with focus on mechanical pulp fibres and fines fractions. The nanocellulose materials produced within this research project were tested for different purposes ranging from strength additives in paper and paperboard products, via composite films to foam materials. TAPPI (Technical Association of Pulp &amp; Paper Industry) has recently suggested a standard terminology and nomenclature for nanocellulose materials (see paper I). In spite of that we have decided to use the terms nano-ligno-cellulose (NLC), microfibrillated cellulose (MFC), nanofibrillated cellulose (NFC) and nanocellulose (NC) in this thesis . It is well-known that mainly chemical pulps are used as starting material in nanocellulose production. However, chemical pulps as bleached sulphite and bleached kraft are quite expensive. One more cost-effective alternative can be to use fibres or fines fractions from thermo-mechanical pulp (TMP) and chemi-thermomechanical pulp (CTMP).   In paper II-IV, fractionation has been used to obtain fines fractions that can easily be mechanically treated using homogenisation. The idea with this study was to investigate the possibility to use fractions of low quality materials from fines fractions for the production of nanocellulose. The integration of a nanocellulose unit process in a high-yield pulping production line has a potential to become a future way to improve the quality level of traditional products such as paper and paperboard grades.   Paper III describes how to utilise the crill measurement technique as a tool for qualitative estimation of the amount of micro- and nano-material produced in a certain process. The crill values of TMP- and CTMP-based nanocelluloses were measured as a function of the homogenisation time. Results showed that the crill values of both TMP-NLC and CTMP-NLC correlated with the homogenisation time. In Paper V pretreating methods, hydrogen peroxide and TEMPO are evaluated. Crill measurement showed that hydrogen peroxide pretreatment (1% and 4%) and mechanical treatment time did not improve fibrillation efficiency as much as expected. However, for TEMPO-oxidised nanocelluloses, the crill value significantly increased with both the TEMPO chemical treatment and mechanical treatment time. In paper V-VII TEMPO-mediated oxidation systems (TEMPO/NaBr/NaClO) are applied to these fibres (CTMP and Sulphite pulp) in order to swell them so that it becomes easy to disrupt the fibres into nanofibres with mechanical treatment.   The demand for paperboard and other packaging materials are steadily increasing. Paper strength properties are crucial when the paperboard is to withstand high load. A solution that are investigated in papers IV and VI, is to use MFC as an alternative paper strength additive in papermaking. However, if one wish to target extremely higher strength improvement results, particularly for packaging paperboards, then it would be fair to use MFC or cationic starch (CS). In paper VI CS or TEMPO-based MFC was used to improve the strength properties of CTMP-based paperboard products. Results here indicate significant strength improvement with the use of different levels of CS (i.e., 20 and 10 kg t–1) and 5% MFC. The strengthening impact of 5% MFC was approximately equal to that of 10 kg t–1 of CS.   In paper VII, NFC and nanographite (NG) was used when producing composite films with enhanced sheet-resistance and mechanical properties. The films produced being quite stable, flexible, and bendable. Realising this concept of NFC-NG composite film would create new possibilities for technological advancement in the area of high-yield pulp technology.  Finally, in paper VIII, a new processing method for nanocellulose is introduced  where an organic acid (i.e., formic acid) is used. This eco-friendly approach has shown to be successful, a nanocellulose with a uniform size distribution has been produced. / <p>Vid tidpunkten för disputationen var följande delarbeten opublicerade: delarbete 5 och 7 inskickade, delarbete 6 och 8 manuskript.</p><p>At the time of the doctoral defence the following papers were unpublished: paper 5 and 7 submitted, paper 6 and 8 manuscripts.</p>

Cavalcanti, BN. Resposta de fibroblastos de polpa humanos frente a substâncias liberadas por capeadores pulpares diretos [Tese de Doutorado]. São Paulo: Faculdade de Odontologia da USP; 2003. RESUMO O objetivo do presente estudo foi o de avaliar os efeitos citotóxicos de substâncias liberadas durante a aplicação de materiais utilizados em capeamento pulpar direto, sobre fibroblastos de polpa dentária humana. Utilizou-se para o experimento meios condicionados pelas substâncias a serem testadas, divididas nos grupos a seguir: grupo I: controle (meio de cultivo sem condicionamento); grupo II: cimento de hidróxido de cálcio; grupo III: adesivo dentinário; grupo IV: ácido ortofosfórico a 37%. O condicionamento foi realizado, colocando-se meio de cultivo fresco sobre os materiais de modo que a presa (grupo II), polimerização (grupo III) ou o contato direto (grupo IV) liberassem substâncias para esse meio de cultivo. Esse meio era colocado sobre as células durante todo o experimento, excetuando-se o grupo IV, onde o contato foi feito por um período de 15 segundos, conforme recomendações clínicas. Posteriormente foram realizadas contagens em hemocitômetro pelo método de exclusão por azul de Trypan, que cora somente as células mortas. As contagens foram realizadas em períodos de 0, 6, 12 e 24 horas para o experimento de viabilidade celular (curto prazo), onde se avaliou o percentual de células vivas sobre o total de células, e em períodos de 1, 3, 5 e 7 dias para o experimento de sobrevivência celular, no qual se avaliou o número absoluto de células vivas. Observou-se que as substâncias liberadas pelo adesivo dentinário são citotóxicas em qualquer período, diminuindo consideravelmente a viabilidade celular e afetando suas curvas de crescimento. Aquelas liberadas pelo ácido ortofosfórico a 37% provocam diminuição da viabilidade somente nos primeiros momentos do contato com as células, enquanto as substâncias liberadas durante a presa do hidróxido de cálcio não são citotóxicas em nenhum momento. / The purpose of the present study was to evaluate the cytotoxic effects of substances leached during the use of direct pulp capping materials, on human pulp fibroblasts. There were used cell culture mediums conditioned by the test materials, as follows: group I: control (fresh medium without conditioning); group II: calcium hydroxide cement; group III: bonding system; group IV: 37% orthophosphoric acid. The medium conditioning was made, pouring the fresh conditioning medium on the materials, in order that its setting (group II), polymerization (group III) or the direct contact (group IV) would be able to leach substances to this culture medium. These conditioned mediums were put on the cells for the entire experiment, excepting the group IV, in which the mediums were put in contact with the cells for 15 seconds, following clinical recommendations. Cell counting was performed in hemocytometer, using the Trypan blue exclusion method, which mark only the dead cells. These counting was made at experimental times of 0, 6, 12 and 24 hours for the cell viability assay (short term), where it is evaluated the percentage of live cells on the total number of cells, and at experimental times of 1, 3, 5 and 7 days for the survival assay, in which is evaluated the absolute number of live cells. It was observed that the substances leached by the bonding system are cytotoxic at all experimental times, decreasing significantly the cell viability and affecting its growing rate. Those leached by the 37% orthophosphoric acid decreased the cell viability only at the first contact with the cells, and the substances leached during the setting of the calcium hydroxide cement are not cytotoxic.

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Dynamic (or 2D) FT-IR spectroscopy in combination withpolarized IR irradiation has been used in this work to studywood polymer orientation and interactions on theultrastructural level in wood fibers in the native state aswell as the effects of different pulping processes. The woodpolymer interactions were studied under both dry and humidconditions. The matrix of lignin and hemicelluloses located between thewell-ordered cellulose fibrils in the wood cell wall of sprucewas here shown to be more highly ordered than has earlier beenrevealed. It was confirmed that glucomannan is orientedparallel to the cellulose fibrils and is highly coupled to it.The lignin was also shown to have a main orientation in thestructure although this is probably not as strong as that ofglucomannan. The orientation of the lignin may derive from thefact that the polysaccharides act as templates during thelignification of the cell wall. This organization implies thatnot only the cellulose but also the lignin and thehemicelluloses have different mechanical properties in thelongitudinal and cross-fiber directions. The ability to gain molecular information on the stresstransfer in polymers with dynamic FT-IR spectroscopy made itpossible to verify experimentally earlier molecularcalculations on the stress transfer within the cellulose chain.It was also possible to show, on the molecular level, thedominant importance of the cellulose fibrils for the stresstransfer in the longitudinal direction of pulp fibers,including lignin-rich mechanical pulp fibers. The glucomannanof softwood fibers was also shown to participate in the stresstransfer in the fiber direction indicating a close associationwith the cellulose, whereas the xylan showed no dynamicresponse. Already under dry conditions, the lignin was shown tohave a more viscoelastic response than the polysaccharidesduring the loading of pulp fibers and it was thus able to moveindependently of the cellulose. The enhanced spectral resolution obtained with dynamic FT-IRspectroscopy made it possible to study the crystalstructure/chain order of cellulose in pulp fibers. Thepossibility of following changes in the relative cellulose Iallomorph composition of pulp fibers was demonstrated for somechemical pulps. Dynamic FT-IR experiments under humid conditions and ofelevated temperatures made it possible to study the softeningof the biopolymers in their native environment. This was alsodemonstrated for some different pulps, and this may be apromising tool for obtaining viscoelastic information on themolecular level in composite systems such as wood fibers. <b>Keywords:</b>cellulose, cooperation, crystallinity, dynamictest, glucomannan, hardwood, holocellulose, humidity, infraredspectroscopy, kraft pulp, lignin, mechanical pulp, orientation,polarised light, softwood, strain, sulphite pulp,viscoelasticity, xylan