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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
301

Poeira de estrelas : o cinema hollywoodiano na midia brasileira das decadas de 40 e 50

Meneguello, Cristina, 1967- 15 December 1992 (has links)
Orientador: Alcir Lenharo / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Filosofia e Ciencias Humanas / Made available in DSpace on 2018-07-17T09:35:31Z (GMT). No. of bitstreams: 1 Meneguello_Cristina_M.pdf: 6846616 bytes, checksum: 0d4e7f6360e1aba5c8a459b4de03311e (MD5) Previous issue date: 1992 / Resumo: Não informado. / Abstract: Not informed. / Mestrado / Mestre em História Social
302

Convecção natural por difusão dupla em cavidades

Trevisan, Osvair Vidal, 1952- 07 May 1986 (has links)
Orientador: Adrian Bejan / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Campinas / Made available in DSpace on 2018-07-17T20:40:51Z (GMT). No. of bitstreams: 1 Trevisan_OsvairVidal_D.pdf: 4369077 bytes, checksum: f79049e355dac6ec6de2231614684c22 (MD5) Previous issue date: 1986 / Resumo: Apresenta-se nesta dissertação um conjunto de estudos analíticos e extensa cobertura de simulação numérica sobre a convecção natural em cavidades. A atenção é voltada para a convecção promovida pela combinação dos efeitos de empuxo devidos às variações de temperatura e concentração.O fenômeno é examinado para as configurações verticais: o transporte de calor e massa se dá na direção horizontal, com os gradientes aplicados nas paredes verticais da geometria retangular. Ambas as configurações porosas e não porosas são contempladas. A análise de escala e a linearização de Oseen são as técnicas analíticas utilizadas. O problema é investigado para diferentes condições de contorno e os resultados numéricos se estendem pelos domínios não abrangidos pela parte analítica do estudo. / Abstract: The present dissertation reports a set of analytical studies and extensive coverage by numerical simulation on natural convection ocurring in enclosures. The focus is on convection promoted by the combination of buoyancy effects due to both temperature an concentration variations. The phenomenon is examined the vertical configurations: the heat and mass transfer occur in the horizontal direction while the gradients are applied at end vertical wal1s of a rectangular geometry. Both porous and non-porous configurations are considered. Scale analysis and a Oseen linearized solution are the analytical techniques used. The problem is investigated for different boundary conditions and the numerical experiments are extended to the domains not covered by the analytical branch. / Doutorado / Doutor em Engenharia Mecânica
303

Area interfacial em colunas de recheio : influencia da viscosidade do liquido e da velocidade superficial do gas

Sampaio Neto, Oscar Zalla 03 February 1994 (has links)
Orientador: Antonio Jose Meirelles / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-07-18T22:23:04Z (GMT). No. of bitstreams: 1 SampaioNeto_OscarZalla_M.pdf: 4148089 bytes, checksum: b907deea2d888235bce5980f8d8ec35b (MD5) Previous issue date: 1994 / Resumo: Foram realizados experimentos em uma coluna de vidro com 78 mm de diâmetro interno empacotada com anéis de Raschig de 7 mm, em um leito de 1,15 m objetivando-se estudar a influência da viscosidade da fase líquida e das condições hidrodinâmicas da fase gasosa na formação da área interfacial efetiva de transferência de massa. Este fundamental parâmetro nos projetos de torres recheadas, foi determinado em experimentos de absorção acompanhada de reação de pseudo-primeira ordem. A reação se deu entre o dióxido de carbono e a dietanolamina em solução aquosa de etilenoglicol no primeiro conjunto de experimentos e entre o dióxido de carbono e o hidróxido de sódio em solução de água e açúcar. A concentração de dióxido de carbono na fase gasosa foi de 2,5%. A escolha desses sistemas possibilitou variar a viscosidade do líquido em uma faixa de 1x10-3 até 2x10-2 Kg/m.s e a velocidade superficial da fase gasosa de 8x10-3 até 2x10-1m/s. A viscosidade do líquido apresentou uma influência em geral negativa sobre a formação da área interfacial efetiva'. Sob condições de baixa velocidade superficial da fase gasosa, a viscosidade do líquido influenciou positivamente em uma faixa de 1xl0-3até 3x10-3Kgjm.s, em função possivelmente da melhoria da molhabilidade do recheio. Na faixa estudada a velocidade superficial do gás tem um efeito positivo, no entanto, sua influência diminui com o aumento da viscosidade do líquido. Todos os dados puderam ser satisfatoriamente correlacionados por uma equação onde a área interfacial efetiva é apresentada como uma função dos números de Reynolds das fases . líquida e gasosa, sendo que para este último o expoente traz o numero de Kaptisa / Abstract: Experiments were carried out in a 78 mm glass column packed with 7 mm glass Raschig rings to a depth of 1,15 m. The subject of this work was to study the influence of the liquid phase viscosity and hydrodynamic conditions on mass transfer effective interfacial area. Effective interfacial area was determined by chemical absorption experiments with .pseudo-first order reaction. Two gas-liquid systems have been used: (1) carbon dioxide - diethanolamine in aqueous ethyleneglycol solutions and (2) carbon dioxide - sodium hydroxide in aqueous sugar solutions. The gas phase dioxide carbon concentration was 2,5%. These systems covered a viscosity range from 1x10-3 to 2x10-2 Kg/m. s and superficial gas velocity from 8x10-3 to 2x10-1 m/s. The liquid viscosity presented negative influence upon effective interfacial area formation. Under low superficial gas velocity conditions the liquid viscosity could influence positively with range of 1xl0-3 to 3x10-3 Kg/m.s, caused possibly by the improvement packed wetabillity. The superficial gas velocity in the studied range had a positive effect, but its influence decreases as liquid viscosity increases. All the data could be satisfactorily represented by an equation which relates the effective interfacial area as a function of vapor and liquid phase Reynolds numbers. The expoente for the vapor phase Reynolds number is the Kaptisa number / Mestrado / Mestre em Engenharia de Alimentos
304

Analise do comportamento de reservatorios heterogeneos submetidos a injeção de agua

Ferreira, Deise Massulo 21 December 1994 (has links)
Orientadores: Antonio Claudio de Franca Correa, Maria Cristina Cunha / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Geociências / Made available in DSpace on 2018-07-19T17:08:12Z (GMT). No. of bitstreams: 1 Ferreira_DeiseMassulo_M.pdf: 2477176 bytes, checksum: 1df830690c242eb5d718985938f764e6 (MD5) Previous issue date: 1994 / Resumo: A presente dissertação estuda o deslocamento unidimensional ele dois fluidos incompressíveis, com o fluido molhante deslocando o não-molhante, em reservatórios heterogêneos compostos de uma fração contínua de maio transmissibilidade englobando uma fração descontínua de menor transmissibilidade.A formulação matemática adotada para representar o escoamento incompressível no meio heterogêneo admite fluxo convectivo na fração mais permoporosa e transferência de massa entre a fração mais permo-porosa e a fração menos permo-porosa, proporcional à diferença de saturação entre as duas frações. O sistema hiperlico de equações é resolvido pelo método das características para uma curva de fluxo fracionário genérica. A soluçãO obtida mostra a formação de uma frente de avanço na fração mais permo-porosa, cuja velocidade e saturação diminuem com o tempo, devido à troca de massa entre as duas frações do meio poroso. A redução da velocidade da frente de avanço da fração mais permo-porosa depende da intensidade da recuperação do óleo da fração menos permo-porosa. Os modelos de transferência de massa reportados na literatura são usados para calcular o coeficiente de transferência de massa do modelo proposto. A validação do modelo é feita através do ajuste a um experimento de laboratório reportado na literatura. Uma outra formulação para a transferência de massa, baseada na equação da difusão, é apresentada. A solução numérica para esta formulação exigiu um excessivo tempo computacional, o que conduziu ao desenvolvimento de uma solução aproximada, baseada no teorema de valor médio para integrais. É apresentado um exemplo prático com dados de campo / Abstract: The present work studies the incompressible flow of two immiscible fluids (a wetting fluid displacing a non_wetting one) in heterogeneous reservoirs composed of a continuous fraction of high transmissibility surrounding a discontiÍmous fraction of low transmissibility. The mathematical formulation used to represent the incompressible flow in the heterogeneous medium admits flow due to convective forces in the more permeable fraction, and mass transfer between the more permeable fraction and the less permeable fraction, which is proportional to the difference in: saturation between them. The resultant hyperbolic system of equations is solved by the method of characteristics for a generic fractional flow curve. The solution leads to a shock front of saturation of the wetting fluid in the more permeable fraction, whose velocity and saturation decrease in time, due to the mass transfer between the two fractions. The rate of reduction in the velocity of the shock front depends on the intensity of oi! recovery from the less permeable fraction of the reservoir. The mass transfer models reported in the petroleum literature are used to calculate the mass transfer coefficient of the proposed model. The model validation is obtained through a laboratory experiment reported in the literature. Another mathematical formulation that considers a diffusion-type equation for the less permeable fraction is presented. The numerical solution for this formulation is time consuming. So an approximate solution, based on the mean value theorem for integrais, was developped. A practical example with field data is presented. / Mestrado / Geoengenharia de Reservatorios / Mestre em Ciências
305

Production and application of fine fractions made of chemical pulp for enhanced paperboard strength

Björk, Elisabeth January 2020 (has links)
For all kinds of paperboard packages, the bending stiffness of the paperboard is a crucial property. In multi-ply folding boxboard (FBB) grades, this is obtained by placing different stocks in the outer and centre plies of the board. In the outer plies, a stock with a high tensile stiffness is used, typically made from refined kraft pulp fibres. In the middle ply/plies a stock with more bulky properties is placed, typically comprising of a high proportion of CTMP (chemi-thermomechanical pulp). CTMP fibres are stiffer and more inflexible with poor bonding abilities resulting in low strength properties. To increase the bonding strength in the middle ply, broke, containing chemical pulp is added, and sometimes refined chemical kraft pulp as well. Both fibres and fines, i.e. smaller fibre fragments, in a pulp have a significant contribution to the properties of the product. Fines produced during refining of chemical pulp are especially beneficial for increasing the strength. To achieve pulp fraction with higher fines content the pulp can be fractionated with a micro-perforated screen basket; a fine fraction produced from a screen with very small holes will contain a large proportion of fines. By adding such a fine fraction to a middle ply stock, the bulk properties of the main pulp, for example a CTMP, can be conserved as less refining of this pulp is required to achieve the targeted strength properties. However, a drawback is that the fine fraction usually has a very low mass concentration after the screening process as a lot of water pass through the screen together with the fines and fibre fragments. The excess water must be removed to maintain the water balance of the papermaking process. Further, the larger volumes require extra pumping capacity. A resource-efficient production of a fine fraction must target a high fine fraction mass concentration and a high content of fines and short fibre fragments in order to be implemented industrially. The focus of the present work was on separation efficiency (i.e. the difference in fibre length distribution caused by screening) and process efficiency (i.e. the concentration of the fine fraction) for production of a fine fraction of chemical pulp by screening, and the utilisation of the fine fraction as strength agent. Pilot-scale fractionation trials with a pressure screen with different microperforated screen baskets were performed in order to evaluate how the separation efficiency and process efficiency were affected by parameters such as feed concentration, pulp type (hardwood or softwood kraft pulp), hole size of the screen, and refining treatment prior to screening. The trials were evaluated using fibre length distributions, flow rates and concentrations of viii the feed flow and the fractions. Here, two complementary quantitative measures, Proportion in fine fraction (for process efficiency) and Fine fraction enrichment (for separation efficiency), were developed. To evaluate the strength enhancing effect of the obtained fine fraction, a lab scale study was performed where the fine fraction of a highly refined pulp was compared with the highly refined pulp as strength agent for a CTMP. The results of this study were verified in a pilot paper machine trial. In a second pilot paper machine trial, sheets with different CTMP proportions in the middle ply were studied in order to find out if the bulk could be increased while maintaining strength, by using a fine fraction made from refined chemical pulp. Regarding process efficiency, it was found that the most important parameter to obtain a high fine fraction concentration was a high feed concentration. Further, a higher fine fraction concentration for a given screening process was also obtained when using hardwood pulp and refining the pulp prior to the screening process. A higher feed concentration also had a positive effect on the separation efficiency. Small holes and a smooth surface of the screen basket were also important to improve the separation efficiency. It was shown that, when used as a strength agent in a CTMP pulp, the fine fraction of highly refined kraft pulp was twice as efficient as the highly refined kraft pulp, when added at equal mass proportion. However, both in the lab and pilot trial the strength increase was accompanied by a decreased bulk. This was expected, and to avoid this the proportion of the bulky CTMP had to be increased. The pilot paper machine trial with an increased CTMP proportion in the middle ply and a fine fraction of refined kraft pulp as strength agent demonstrated that it was possible to produce sheets with an increased bulk and maintained z-strength. / Böjstyvheten är en viktig egenskap för alla sorters hårda förpackningar. I flerskiktskartong får man böjstyvhet genom att ha ytterskikt med hög dragstyvhet tillverkade av fibrer från kemisk massa och ett mittskikt med hög bulk från styva fibrer, ofta med en stor andel CTMP (kemitermomekanisk massa). CTMP-fibrer är styva men ger lägre styrka i arket. För att öka styrkan i mittskiktet tillsätter man utskott (kasserad kartong) som delvis innehåller kemisk massa, och ibland även ren högmald kemisk massa. Både fibrer och finmaterial (fines) har stor betydelse för slutproduktens egenskaper. Fines som skapas vid malning av kemisk massa är särskilt effektiva för att öka styrkan. Genom att fraktionera massa med en mikroperforerad sil kan man få en finfraktion med högt finesinnehåll. Mikroperforerade silar är effektiva för längdfraktionering av massa; fines anrikas i den fraktionen som passerar silen medan långa fibrer stannar i den andra fraktionen. Genom att använda en sådan finfraktion i mittskiktet kan man få tillräcklig styrka och samtidigt behålla mer av bulken från CTMP:n genom att man inte behöver mala den för att få styrka. En nackdel är att finfraktionen vanligtvis har väldigt låg masskoncentration eftersom mycket vatten passerar silen tillsammans med fines och fiberfragment. Detta extra vatten måste tas bort för att vattenbalansen i papperstillverkningsprocessen ska bibehållas. Dessutom kräver den större volymen ökad pumpkapacitet. För att kunna använda en finfraktion industriellt behövs en effektiv produktion med hög koncentration och högt finesinnehåll. Fokus i det här arbetet lades på separationseffektivitet (skillnaden i fiberlängdsfördelning som resultat av silningen) och processeffektivitet (koncentrationen i finfraktionen) för tillverkning av en finfraktion av kemisk massa genom silning samt dess utnyttjande som styrkehöjande tillsats i ett mittskikt av kartong. För att utvärdera hur separationseffektiviteten och processeffektiviteten påverkas av parametrar som koncentrationen i flödet in till silen, typ av kemisk massa (gjord av lövved eller barrved), hålstorlek i silen samt malningen av massan, gjordes fraktioneringsförsök i pilotskala med en trycksil med olika mikroperforerade silkorgar. Resultatet av fraktioneringen utvärderades med hjälp av fiberlängdsfördelningar, flöden och koncentrationer i flödet till silen och de två fraktionerna efter silen. För utvärderingen togs två olika utvärderingsmetoder fram: Proportion i finfraktionen (för processeffektivitet) och Finfraktionsanrikning (för x separationseffektivitet). För att utvärdera hur effektiv en finfraktion av kemisk massa var som styrkeadditiv i ett CTMP-ark gjordes labbförsök där tillsats av högmald kemisk massa jämfördes med tillsats av enbart en finfraktion av den högmalda kemiska massan. Resultaten verifierades med ett försök på en pilotpappersmaskin. I ett följande försök på pilotpappersmaskinen tillverkades ark med ökat CTMP-innehåll för att öka bulken, och med en tillsats av en finfraktion av kemisk massa som styrkeadditiv. När det gäller processeffektivitet var hög koncentration i flödet till silen den viktigaste parametern för att få hög koncentration på finfraktionen. Detta var också positivt för separationseffektiviteten, färre av de längre partiklarna hamnade i finfraktionen. Vidare blev finfraktionens koncentration högre för lövvedsmassa. En finfraktion som ska användas som styrkeadditiv ska vara tillverkad av mald massa, malning av massan var också fördelaktigt för finfraktionens koncentration. Små hål och en slät yta på silkorgen var också positivt för separationseffektiviteten. Som styrkeadditiv i CTMP var finfraktionen av högmald kemisk massa dubbelt så effektiv som den högmalda kemiska massan vid lika stor tillsats. Men i både labbförsök och pilotförsök minskade bulken när styrkan ökade. Det var väntat eftersom att ersätta en del av originalmassan som har hög bulk, med en finfraktion eller högmald massa, som båda har mycket lägre bulk, alltid minskar bulken på arket. För att undvika en bulkförlust måste massasammansättningen i arket ändras. Försöket på pilotpappersmaskinen med ökat CTMP innehåll och en finfraktion av mald kemisk massa som styrkeadditiv visade att det är möjligt att tillverka ett ark med högre bulk och bibehållen styrka.
306

Pulp compositions and their influence on the production of dialcohol cellulose / Olika sammansättningar av pappersmassa och deras påverkan på produktionen av dialkoholcellulosa

Carlsson, Viktoria January 2020 (has links)
The characteristics of products made from pulp can be modified through different methods. If the pulp is refined either laboratory or industrially, the fibres in the pulp become more flexible and therefore creates stronger bonds to each other, which results in a final product with a higher strength. The refining process also causes the formation of small fibre pieces that are called fines, which also contribute to the increased strength. The major component in pulp is cellulose, which can be chemically modified to materials with changed properties. Periodate oxidation of cellulose results in dialdehyde cellulose that can be further reduced with sodium borohydride to obtain dialcohol cellulose, which is a material with a higher ductility compared to regular cellulose. In this thesis, different pulp compositions and their influence on the production of dialcohol cellulose (DALC) were investigated. The aim of the study was to find out how the ductility of paper sheets made from DALC were affected by the presence of fines in the pulp. Nine different pulp compositions were prepared for the modification: unrefined pulp, unrefined pulp with added fines, industrially refined pulp, dewatered industrially refined pulp, and pulp refined 1000, 3000, 5000, 10 000 and 15 000 revolutions with a PFI Mill. Paper sheets were made with a Rapid Köthen sheet former and the mechanical properties of the sheets were tested with a Zwick Roell tensile tester. The surface of the sheets were analyzed using a scanning electron microscope (SEM). The results obtained from the tensile tests showed that DALC made from unrefined pulp and DALC made from pulp highly refined with a PFI Mill, resulted in sheets with a high strain-at-break. For each increased degree of refining with the PFI Mill, the resulting DALC sheets showed an improved elongation and tensile strength. When DALC was produced from industrially refined pulp and from unrefined pulp with added fines, the resulting sheets had a lower strain-at-break. These findings indicate that the presence of fines in the pulp do have a negative effect on the ductility of the resulting DALC sheets.
307

A glândula salivar cefálica e os compostos da secreção e de superfície cuticular em algumas espécies de abelhas eussociais (Hymenoptera, Apinae) /

Poiani, Silvana Beani. January 2012 (has links)
Orientador: Carminda da Cruz Landim / Banca: Ronaldo Zucchi / Banca: José Eduardo Serrão / Banca: Fabio Santos do Nascimento / Banca: Norberto Peporine Lopes / Resumo: As espécies de abelhas eussociais usam várias estratégias para a comunicação entre os membros da sociedade com a finalidade de coordenar as diferentes tarefas das quais esta sociedade depende. A comunicação através de sinais químicos é uma das mais difundidas e tem papel primordial na manutenção das colônias. As fontes dos compostos químicos usados na comunicação podem ser várias, mas boa parte dos compostos tem origem em glândulas exócrinas distribuídas pelo corpo das abelhas. O presente estudo abrange a análise da composição das glândulas salivares cefálicas (GSC) e da superfície cuticular através de cromatografia em fase gasosa e espectrometria de massas e de testes citoquímicos para detecção de compostos lipídicos e de atividade de fosfatases ácidas nas glândulas de operárias abelhas eussociais das espécies Apis mellifera, Scaptotrigona postica e Melipona quadrifasciata enquanto recém emergidas, trabalhando na área de cria e como forrageiras. As diferenças qualitativas e quantitativas obtidas na análise cromatográfica foram submetidas a análises estatísticas. O objetivo do estudo foi o de testar hipóteses de que há correlação entre a fisiologia das células glandulares e das substâncias presentes na secreção e na superfície cuticular, a fim de verificar: 1. Mudanças na composição celular relacionáveis à função secretora; 2. Relação entre a fase da vida/função das operárias e a composição da secreção glandular e dos compostos cuticulares, ou seja, que a composição da secreção pode funcionar na colônia como sinais, tanto de reconhecimento como de capacitação para determinada tarefa; 3. Se existe a possibilidade da contribuição da glândula para a formação do perfil químico cuticular nestas espécies de... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Eusocial bees use several strategies for communication among the members of the society with the purpose of coordinating the different tasks necessary to colony maintenance. The communication by chemical cues is one of the most frequent. There are several sources for the chemicals used in the communication, but most of them are produced by exocrine glands distributed over all body of the bees The present study includes analysis of the secretion compounds from cephalic salivary glands (CSG) and from cuticular surface by gas chromatography-mass spectrometry and citochemical tests for lipid detection and acid phosphatase activities in CSG of workers' of Apis mellifera, Scaptotrigona postica and Melipona quadrifasciata in different phases of life: newly emerged, working in brood area and foragers. The qualitative and quantitative differences obtained in the chemical analysis were submitted to statistical analyses. The objective of the study was to correlate the glandular cells physiology comparing the substances in their cytoplasm and those found in glandular secretion and on cuticular surface in order to test some hypothesis and verify: 1. Changes in the cellular compounds related to the secretory function; 2. The relationship between the phase/task of the workers' and the compounds in glandular secretion and on cuticular surface; 3. If exist the possibility of gland contribution to forming the cuticular chemical profile in these species of bees. Previous morphological studies of glandular cells showed the lipid nature of the CSG secretion, therefore, glandular citochemical analysis aimed to show the presence of these compounds with the purpose of accompanying their production dynamics, storage, origin and discharge, while the research of acid phosphatase activity aimed to accompany the cellular development... (Complete abstract click electronic access below) / Doutor
308

Xylan reactions in kraft cooking and their influence on paper sheet properties

Danielsson, Sverker January 2006 (has links)
Xylan is the main hemicellulose in birch, eucalyptus, and most other hardwood species. During kraft pulping a series of chemical reactions and physical processes involving xylan take place. The processes studied in this thesis are the following: dissolution, degradation, redeposition onto the fibres, side group conversion, and cleavage of side groups off the xylan back bone. The side group in native xylan consists of methylglucuronic acid, which is mainly converted into hexenuronic acid during kraft cooking. Hexenuronic acid affect the pulp in terms of increased brightness reversion and deteriorated bleachability. The kinetics of the side group cleavage and conversion reactions were analysed using various analytical tools. The study revealed that the most commonly used methods for methylglucuronic acid measurements are not as accurate as has been claimed in the literature. A modification of two of the methods was suggested and evaluated. A common practice used to minimise the hexenuronic acid content involves use of a high cooking temperature. The kinetic study showed that the degree of substitution of pulp xylan is only slightly affected by temperature, and that the observed effects are likely to be more associated with the xylan content of the pulp than with the hexenuronic acid content of the xylan. For the dissolved xylan, however, the degree of substitution showed a high temperature dependency and moreover it was always higher than in the pulp. Xylan itself is known to have the capacity to increase the strength of the manufactured pulp. This knowledge was applied by exchanging cooking liquors between birch kraft cooks, in which a high amount of xylan is dissolved, and spruce cooks, which contain very small amounts of native xylan. This seems like an attractive alternative for softwood kraft cooking, since both the tensile strength and stiffness increased significantly. The magnitude of the strength increase was correlated with the molecular weight of the added xylan and with the increased surface charge of the fibres. / QC 20101111
309

Polyelectrolyte multilayers of cationic and anionic starch and their use for improving the strength of papers made from mechanical pulps

Lundström, Lisa January 2009 (has links)
Graphic paper is experiencing severe competition from other materials and, most of all, from other media. This means there is a great need to improve paper quality while reducing raw material and production costs. Polyelectrolyte multilayer (PEM) treatment (i.e., consecutively adding cationic and anionic polyelectrolytes to the charged surface of wood fibres and fines, to form layers of these polyelectrolytes on the fibres/fines) has in recent years been found to offer great potential both to introduce new properties and to improve the mechanical properties of papers made of the treated fibres. The main objective of this thesis was to develop a strategy for the PEM treatment of cationic and anionic starch to improve the mechanical properties of paper made of thermomechanical pulp (TMP), since PEM treatment of fibres has displayed great potential to improve the mechanical properties of sheets made of chemical pulp. Mechanical pulp, however, has a large fine material content. Since the fine material is highly charged, polyelectrolyte consumption would be unacceptably high if the entire pulp were PEM treated, so we applied PEM treatment only to a fibre fraction of the pulps in most trials in the present work. The polyelectrolytes used for PEMs have so far mostly been well-defined, expensive ones unsuitable for use in standard paper grades; to develop a more economically realistic alternative, we used cationic and anionic starches. PEM formation on SiO2 surfaces from three differently charged cationic and anionic starches was first evaluated at three different salt levels using quartz crystal microbalance with dissipation (QCM-D) and stagnation point adsorption reflectometry (SPAR). The starch combinations displaying the highest potential for stable PEM formation at higher salt concentrations were then evaluated on an entire TMP pulp, as well as on a fraction of the pulp to reduce the amount of starch needed for PEM formation. The results indicate that it is possible to form PEMs from cationic and anionic starch on a SiO2 surface. The charge density, salt concentration, and combination of starches all influenced PEM formation. PEM formation on mechanical fibres produced large improvements in the mechanical properties of the sheets made of the treated fibres, and the tensile index, stretch-at-break, Z-strength, and Scott bond values all increased. Fractionating the pulp and PEM treating only a fraction of the pulp, the long fibre and middle fraction, produced large decreases in the amount of starch needed and large improvements in the mechanical properties of the sheets when no fine material was subsequently added. As untreated fine material was subsequently added, the improvement in mechanical properties decreased. PEM formation produced almost no reduction in formation and only a slight increase in sheet density. / Grafiskt papper är under hård konkurrens från andra material och, framför allt, andra media.  På grund av detta finns det ett stort behov av att förbättra papperskvalitén samtidigt som råmaterial- och produktionskostnader sänks. Polyelektrolyt-multiskikt (multiskikt) på massa (dvs. växelvis adsorption av katjoniska och anjoniska polyelektrolyter till träfibrer och finmaterial) har på senare år visat sig ha bra potential både för att ge nya egenskaper och för att förbättra de mekaniska egenskaperna hos papper gjorda av behandlad fiber. Huvudsyftet med denna avhandling var att utveckla en strategi för multiskiktsbehandling med katjonisk och anjonisk stärkelse för att förbättra de mekaniska egenskaperna hos papper gjort av behandlad termomekanisk massa (TMP). Multiskiktsbehandling av fiber har visat stor potential för att ge förbättrade mekaniska egenskaper till ark gjorda av behandlad kemisk massa. Mekanisk massa innehåller dock en stor andel högladdat finmaterial som kan öka mängden polyelektrolyt som krävs för multiskiktsbehandling, därför multiskiktsbehandlas bara en fraktion av massan i de flesta experiment i detta arbete. De polyelektrolyter som använts för multiskikt har hittills mest varit väldefinierade och dyra, och därmed opassande för användning i vanliga papperskvalitéer. För att utveckla ett mer realistiskt alternativ så användes katjonisk och anjonisk stärkelse i detta arbete. Multiskiktsuppbyggnad på SiO2-ytor av tre katjoniska och tre anjoniska stärkelser med olika laddningsdensitet utvärderades först vid tre olika saltnivåer genom att använda kvartskristal‑mikrogravimetri (QCM-D) och reflektometri (SPAR). Stärkelsekombinationerna som uppvisade störst potential för en stabil multiskiktsuppbyggnad på högre saltkoncentrationer blev sedan utvärderade på en hel TMP-massa, men även på en fraktion av massan för att minska mängden stärkelse som krävdes för multiskiktsuppbyggnad. Resultaten visar på att det är möjligt att bygga upp multiskikt av katjonisk och anjonisk stärkelse på en SiO2-yta. Laddningsdensiteten, saltkoncentrationen och kombinationen av stärkelser var faktorer som påverkade multiskiktsuppbyggnaden. Multiskiktsuppbyggnad på mekaniska fibrer gav stora förbättringar av de mekaniska egenskaperna hos ark gjorda av behandlad fiber, och dragindex, töjning, Z-styrka och Scott bond-värde ökade. Fraktionering av massan och multiskiktsbehandling av endast en del av massan, långfiber- och mellanfraktion, innebar att mycket mindre stärkelse behövdes och gav stora förbättringar av de mekaniska egenskaperna hos arken om inget obehandlat finmaterial tillsattes efteråt. Då obehandlat finmaterial tillsattes så blev förbättringarna hos de mekaniska egenskaperna mindre. Multiskitsuppbyggnad gav nästan ingen reduktion av formationen och endast en liten ökning i arkdensitet.
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Suberin based polyesters

Olsson, Ann January 2009 (has links)
In the wish to replace oil-based chemicals and materials with such based on biodegradable and renewable resources, this work has been performed. In a biorefinary concept, waste birch bark from paper pulp mills and timber production has been evaluated as a potential source for polyesters.  In the present thesis investigations are made on synthesis of epoxy-functionalized polyesters from the birch outer bark aliphatic suberin ω-hydroxy fatty acid, cis-9,10-epoxy-18-hydroxyoctadecanoic acid. Studies of accessibility and reactivity of cellulose have been performed as a first step to enable covalent attachment or grafting of the epoxy-functionalized polyesters to cellulose.  Candida antarctica lipase B (Novozym 435) is reported to be an efficient catalyst for condensation polymerization of cis-9,10-epoxy-18-hydroxyoctadecanoic acid to form poly(9,10-epoxy-18-hydroxyoctadecanoic acid) with high molecular weight (Mw). Performed in toluene in the presence of molecular sieves a Mw of 20000 (reaction time 68 h, Mw/Mn 2.2) was obtained. Performed in bulk without any drying agent a Mw of 15000  was obtained at a much shorter reaction time (reaction time 3h, Mw/Mn 2.2). Further the same lipase has been used for succesful co-polymerizations of cis-9,10-epoxy-18-hydroxyoctadecanoic acid with lactones. By combining condensation and ring-opening polymerization, epoxy-functionalized linear polyesters and cyclic oligomers have been synthesized. For example, co-polymerization of cis-9,10-epoxy-18-hydroxy-octadecanoic acid and ε-caprolactone performed in toluene in the presence of molecular sieves gave mainly cyclic oligomers, especially at shorter reaction times. Co-polymerization performed in bulk gave linear polyesters with a Mw of 35000 (reaction time 24 h, Mw/Mn 6), irrespective molecular sieves were added or not.  The epoxy-functionalized polyesters could be used for surface modification of pulp fibres and cellulose fibrils, which further can be used for production of new valuable composite materials with improved features. Knowledge of how different processing conditions affect the structure of cellulose is an important tool in the work to achieve successful grafting of produced polyesters to cellulose fibres/fibrils. CP/MAS 13C-NMR spectroscopy has been used to study structural changes caused by the dissolving pulp process. An irreversible increase in average fibril aggregate width from raw pulp to final pulp during the process is shown. This increase in aggregate width could negatively influence the reactivity of the cellulose.

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