<p>This thesis summarizes the outcome of work performed withthe objective to contribute to the knowledge and development ofthe kraft cooking process using spectrophotometricinterfaces.</p><p>In kraft cooking, it is desirable to maximize the removal oflignin in the cook without loss of pulp strength. Theselectivity can be improved by exchanging some of the hydrogensulfide ion in the white liquor for polysulfides. Paper Ipresents a spectrophotometric method for in-line monitoring ofthe electrochemical production of polysulfide using anATR-probe for the UV-Vis range. A linear relation existsbetween the ATR-probe response and the concentration ofabsorbing species. Thus the process can be followed by simplemonitoring of a few wavelengths.</p><p>A spectrophotometric monitoring system using a durableNafion ionomer membrane interface for continuous on-linemeasurement of sulfide and dissolved lignin during kraftcooking has previously been developed by our group. In paperII, the permeation of low molecular weight anions from liquorshaving high ionic strengths through a membrane in Na+ form hasbeen studied. A general relation between penetration and ionsize approximated by molecular weight has been established. Thepenetration of different anions can be explained as a diffusionthrough the winding membrane channels. Further the differentanions transport independently without being interfered by thesample matrix.</p><p>In light of this validation, we applied the membraneinterface to the determination of anthraquinone-2-sulfonate(AQ-S) in alkaline pulping liquor. In paper III, a simple andrapid spectrophotometric method was developed and implementedon real samples. Interferences from other compounds penetratingthe membrane were minimized by reduction of the penetrated AQ-Sand measurement at 520 nm. This method is quick and can be usedon-line. Further, we extended the method to determination ofanthraquinone (AQ) in pulping liquor (paper IV). Although AQ isregarded as insoluble, it was found that the apparentsolubility of AQ in alkaline solutions increases considerablyin the presence of lignin, reaching 0.14 g/L at 90 oC. Thismakes the calibration of AQ possible. Time-resolvedmeasurements of dissolved AQ in 3 kraft-AQ pulping processeswere performed.</p><p>The results show that the membrane has great potential aspart of a selective interface in applications where theconcentrations of small anions are to be monitored in mediawith high ionic strength.</p><p>Keywords: Kraft cooking, On-line, Sulfide, Lignin,Polysulfide excess sulfur, Anthraquinone-2-Sulfonate (AQ-S),Anthraquinone (AQ), Nafion Membrane, UV-Vis, ATR-probe,Spectrophotometric.</p>

<p>In this thesis, size-exclusion chromatography (SEC) of woodpolymers dissolved in lithium chloride/N,N-dimethylacetamide(LiCl/DMAc) has been used to characterize the molar massdistributions (MMD) of wood polymers in pulp fibers afterchemical degradation.</p><p>Characterization of birch kraft pulps subjected to ozonedegradation and acid hydrolysis, respectively, rendereddifferent changes in the MMD. Ozone degradation resulted inlarge redistributions of the original MMD, observed as thedevelopment of a distinct fraction of cellulose withintermediate molar mass. Acid hydrolysis resulted in minorchanges of the original MMD compared to ozonation. Fiberssubjected to acid hydrolysis were considerably weaker thanozonated fibers. These results indicated that there aredifferences in how the two chemicals degrade the fiber.</p><p>The solubility of softwood kraft pulp fibers was enhanced byderivatization of the fiber polymers with ethyl-isocyanateduring simultaneous dissolution in LiCl/DMAc. Thederivatization made it possible to achieve reliable estimationsof the MMD, and hence molar masses, of softwood kraft pulps.The derivatization procedure made it possible to dissolve 90 %of softwood kraft pulps with kappa numbers over 50.</p><p>Severe alkaline degradation of birch and Norway spruce woodchips was studied both by varying the pulping time and byvarying the initial alkali concentration. Differences werefound in the MMD of the two fiber types, and the alkalinedegradation was found to affect polymers in the entire MMD.</p><p>Multi-angular laser light scattering (MALLS) was used as adetection technique with SEC on cellulosic samples. The MMD andaverage molar masses obtained through directstandardcalibration with commercial standards were compared with MMDand molar masses as obtained by MALLS-detection. Largediscrepancies were found, and two methods of correcting forthese discrepancies were developed.</p><p>Theoretical simulations of polymer degradation wereperformed. Random, or homogeneous degradation was used as amodel for alkaline cellulose chain scission, and a resemblancewith experimental data was observed. End-wise depolymerizationof cellulose was also simulated and the results are discussedin the light of experimentally observed MMD.</p><p><b>Keywords:</b>cellulose, kraft pulp, birch, spruce,ozonation, acid hydrolysis, degradation, MMD, sizeexclusionchromatography, light scattering, molar mass, chainscission</p>

Die konventionelle Kälteerzeugung mit Kompressionskältemaschinen ist mit vielen Nachteilen verbunden: hohe elektrische Lastspitzen, Energieverbräuche, Umweltbelastungen, signifikante Kosten sowie ein umfangreicher Einsatz von ozonabbauenden Kältemitteln in den letzten Jahren. Eine wesentliche Verbesserung kann durch die Kraft-Wärme-Kälte-Kopplung erreicht werden. Durch die thermisch angetriebenen Kältemaschinen ist eine rationelle Nutzung der im Kühllastfall ausreichend vorhandenen Wärme möglich. Um die Kälteerzeugung weiter energetisch, wirtschaftlich und ökologisch zu verbessern, stellt der Einsatz von Kältespeichern eine aussichtsreiche Alternative dar. In diesem Projekt wird deshalb der Kältespeicher-Einsatz speziell für die Randbedingungen in Deutschland untersucht.

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Thesis (D.M.A.)--Ohio State University, 2005. / Title from first page of PDF file. Document formatted into pages; contains xiv, 107 p.; also includes graphics, music. Includes bibliographical references (p. 103-107). Available online via OhioLINK's ETD Center.

Techn. Univ., Diss., 2004--Darmstadt

Bakgrund: Ett stort ansvar vilar på sjuksköterskan, inte minst ansvaret att ta hand om sig själv för att kunna utföra en god och säker omvårdnad med den individuella patienten i fokus, speciellt när det gäller vård i livets slutskede. Tidigare forskning visar att det är emotionellt krävande att arbeta med människor som snart ska dö och att sjuksköterskan behöver emotionell kraft för att klara av detta svåra arbete. Syfte: Syftet var att belysa faktorer som sjuksköterskan upplever ger kraft för att emotionellt klara av att vårda patienter i livets slutskede. Metod: Analys av redan färdigställda kvalitativa originalartiklars resultatdata till en syntetiserande sammanställning över det området som valts att belysas vilket resulterade i tre teman med underteman. Resultat: Själva arbetet i sig, att få kraft av att vårda patienter i livets slutskede, gav sjuksköterskorna kraft vilket framkom som att trivas med sitt jobb, att känna tacksamhet och starkt engagemang samt att få möjlighet till lärande, utveckling och känslomässig kompetens. Vidare återfanns att hämta kraft i sociala relationer samt att få kraft av att ha balans som viktigt för att sjuksköterskorna skulle klara av att vårda patienter i livets slutskede. Sjuksköterskorna fick balans genom att ta hand om sig själv och genom att sätta gränser. Diskussion: Både positiva och negativa upplevelser kan ge sjuksköterskan kraft och det finns flera kraftkällor som sjuksköterskan använder sig av men dessa kan inte användas var och en för sig utan måste ses i ett sammanhang. / Background: A major responsibility rests on the nurse, not least the responsibility to take care of herself in order to perform a good and secure health care with the individual patient in focus, especially when it comes to end-of-life care. Previous research shows that it is emotionally challenging to work with people who are about to die and that the nurse needs emotional strength to manage this difficult task. Aim: The aim was to elucidate factors that the nurse experience gives strength emotionally while managing to care for patients in the end of life. Methods: The authors analyzed the results of already completed articles and made a synthesizing summary of the selected area that was to be elucidated, which resulted in several themes. Results: The work itself, having strength from caring for patients at the end of life, gave the nurses strength which was revealed as being satisfied with her/his ​​job, feeling gratitude and strong commitment and having opportunity for learning, development and emotional competence. Gaining strength in social relationships and getting strength from having balance was also revealed as important for the nurses when managing to care for patients in the end of life was. The nurses could get in balance by taking care of her/himself and by setting limits. Discussions: Both positive and negative experiences can give the nurse strength and there are several sources of power that the nurse uses but these cannot be used each one in isolation but must be viewed in context.

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2016-03-02T22:55:04Z No. of bitstreams: 1 GiselleKallineGomesCarvalho_DISSERT.pdf: 2257540 bytes, checksum: e731412b34e93ab422b0df96d21ad8b7 (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2016-03-04T00:24:44Z (GMT) No. of bitstreams: 1 GiselleKallineGomesCarvalho_DISSERT.pdf: 2257540 bytes, checksum: e731412b34e93ab422b0df96d21ad8b7 (MD5) / Made available in DSpace on 2016-03-04T00:24:44Z (GMT). No. of bitstreams: 1 GiselleKallineGomesCarvalho_DISSERT.pdf: 2257540 bytes, checksum: e731412b34e93ab422b0df96d21ad8b7 (MD5) Previous issue date: 2014-11-28 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico - CNPq / Atividades industriais de minera??o, galvanoplastia e o processo de extra??o do petr?leo, vem aumentando os n?veis de metais pesados, tais como Cu, Fe, Mg e Cd, nos ecossistemas aqu?ticos. Este aumento est? relacionado ao descarte de efluentes contendo teores desses elementos acima do valor m?ximo permitido por lei. M?todos como troca i?nica, filtra??o por membranas e precipita??o qu?mica vem sendo estudados como meios de tratamentos de efluentes contaminados por esses metais. A precipita??o de metais utilizando tensoativos ani?nicos obtidos a partir de ?cidos carbox?licos surgiu como uma alternativa para a remo??o de metais de efluentes industriais. A rea??o entre ?ons bivalentes dos metais e esses tipos de tensoativos em solu??o aquosa leva a forma??o de carboxilatos de metais, que podem precipitar na forma de flocos e serem removidos, posteriormente, por um processo de decanta??o dos flocos formados ou por uma filtra??o simples. Neste trabalho, a extra??o de metais ? realizada por meio da utiliza??o do tensoativo hexadecanoato de s?dio como agente extrator. O objetivo principal ? estudar o efeito da varia??o da temperatura do meio, pH da solu??o de metal e concentra??o do tensoativo no processo de remo??o do metal. A modelagem estat?stica do estudo mostrou que o processo ? diretamente dependente das varia??es de pH e concentra??o do tensoativo, por?m inversamente proporcional e pouco dependente da varia??o de temperatura, sendo esse ?ltimo efeito considerado desprez?vel na maioria dos casos. O estudo individual do efeito da temperatura apresenta uma forte depend?ncia do processo ? temperatura de Kraft, tanto do tensoativo utilizado como agente extrator como do tensoativo obtido ap?s a rea??o desse tensoativo com o metal. A partir dos dados de temperaturas e concentra??es do tensoativo foi poss?vel o c?lculo da constante de equil?brio para a rea??o entre o hexadecanoato de s?dio e ?ons cobre. Posteriormente, foram determinados par?metros termodin?micos, comprovando que o processo ? exot?rmico e espont?neo. / Industrial activities like mining, electroplating and the oil extraction process, are increasing the levels of heavy metals such as Cu, Fe, Mg and Cd in aquatic ecosystems. This increase is related to the discharge of effluents containing trace of this elements above the maximum allowed by law. Methods such as ion exchange, membrane filtration and chemical precipitation have been studied as a means of treatment of these metals contamination. The precipitation of metals using anionic surfactants derived from carboxylic acids emerged as an alternative for the removal of metals from industrial effluents. The reaction between bivalent ions and these types of surfactants in aqueous solution leads to the formation of metal carboxylates, which can precipitate in the form of flakes and are subsequently removed by a process of decantation or simple filtration. In this work the metals extraction is performed by using the surfactant sodium hexadecanoate as extracting agent. The main purpose was to study the effect of temperature, solution pH, and concentration of surfactant in the metal removal process. The statistical design of the process showed that the process is directly dependent to changes in pH and concentration of surfactant, but inversely proportional and somewhat dependent to temperature variation, with the latter effect being considered negligible in most cases. The individual study of the effect of temperature showed a strong dependence of the process with the Kraft point, both for the surfactant used as extracting agent, as for the surfactant obtained after the reaction of this surfactant with the metal. From data of temperatures and concentrations of the surfactant was possible to calculate the equilibrium constant for the reaction between sodium hexadecanoate and copper ions. Later, thermodynamic parameters were determined, showing that the process is exothermic and spontaneous.

Orientador: Rubens Maciel Filho / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-13T23:08:44Z (GMT). No. of bitstreams: 1 Polowski_NataschaVigdis_D.pdf: 3937033 bytes, checksum: 67463e72c2fe6b2c2bf718ee1aefe5cd (MD5) Previous issue date: 2009 / Resumo: Neste trabalho foram desenvolvidos três modelos para predição de Número Kappa (Modelo Determinístico, Modelo Neural e Modelo Híbrido). O Modelo determinístico inclui transferência de massa e reações cinéticas intrínsecas baseadas em reações paralelas de lignina, celulose e hemicelulose. Este divide o processo de deslignificação em 3 estágios ou fases, sendo que as 3 fases correspondem a 3 diferentes tipos de lignina (inicial, principal e residual). O modelo é específico para polpa de eucalipto (fibra curta) e digestor batelada. Umas das contribuições para este modelo proposto foram às inclusões de reações para lignina, hemicelulose e celulose total, carboidratos, além do Número Kappa. Para Modelo Determinístico foram utilizados dados experimentais coletados no RAIZ - Instituto de Investigação da Floresta e Papel e dados gerados pelas simulações. As variáveis operacionais utilizadas como dados de entrada foram: espessura, temperatura inicial, álcali efetivo, relação licor madeira, tempo de cozimento, densidade e porosidade. O Modelo Determinístico também foi desenvolvido para digestor contínuo e foi validado com dados industriais para fibra curta de eucalipto. A modelagem feita para um digestor batelada é a mesma que para um digestor contínuo, sendo que no contínuo existem de 3 a 4 etapas dentro do equipamento. Por conseguinte, o digestor contínuo é modelado como se fosse um batelada só que fracionadamente (temperaturas e tempos para cada estágio do equipamento e de forma seqüencial). Neste trabalho foi empregado um método de otimização (Programação Quadrática Sucessiva) para definir o procedimento de operação no digestor contínuo permitisse a obtenção do produto (polpa) com teores inferiores a 1,5 % de lignina residual. Industrialmente este valor está em torno de 3 % de lignina residual. O Modelo Neural proposto é do tipo "feedforward" e com treinamento por retropropagação. Para este modelo as variáveis de entrada (inputs) foram temperatura, álcali efetivo e Fator H. A variável de saída (output) é o Número Kappa. A quantidade de neurônios ocultos foi definida pelo modelo neural que apresentou o menor erro para o conjunto de validação e treinamento. O número de interações também foi definido a partir do menor erro gerado pelas simulações. Este modelo foi validado com dados industriais e experimentais. O Modelo Híbrido utilizou como variáveis de entrada Kappa Neural e Teórico, temperatura e Fator H e a variável de saída é o Número Kappa Híbrido. Este foi validado com dados industriais. Os modelos apresentados (Determinístico, Neural e Híbrido) são ferramentas úteis para as fábricas de celulose e papel, uma vez que existe a possibilidade de serem aplicados para simulação de processos, otimização e controle. Os modelos podem ser testados para diferentes condições operacionais sem alterar a produção. Além de possibilitarem melhor controle de algumas variáveis no processo fabril, isto, sem perda de qualidade do produto. Neste estudo a rede neural e os modelos cinéticos apresentaram resultados equivalentes. Palavras-chaves: Número Kappa, Modelo Determinístico, Modelo Neural e Modelo Híbrido / Abstract: In this work three models were developed for prediction of Kappa number (Deterministic Model, Neural and Hybrid Model). The Deterministic Model includes mass transfer and reaction kinetics based on intrinsic parallel reactions of lignin, cellulose and hemicellulose. This divides the process of Delignification in 3 stages or phases, with the 3 phases correspond to 3 different types of lignin (initial, bulk and residual). The model is specific to the eucalyptus pulp (short fiber) and batch digester. One of the contributions to this proposed model were the inclusion of reactions for lignin, cellulose and hemicellulose total, carbohydrates, than the Kappa number. Deterministic model was used for experimental data collected in the RAIZ - Instituto de Investigação da Floresta e Papel and data generated by simulations. The operating variables used as input data were: thickness, initial temperature, effective alkali, liquor ratio wood, the cooking time, density and porosity. The Deterministic Model was developed for continuous digester, and was validated with industrial data for short fiber eucalyptus. The modeling done for a batch digester is the same as for a continuous digester, which are continuous in 3 to 4 steps inside the equipment. Wherefore the continuous digester is modeled as a single batch that fractionation (temperatures and times for each stage of the equipment and sequential manner). This study employed a method of optimization (Successive Quadratic Programming) to define the procedure for operation in continuous digester allowed to obtain the product (pulp) with levels below 1.5% of residual lignin. Industrially this value is around 3% of residual lignin. The Neural Model is proposed as "feedforward" and training by backpropagation. For this model the input variables were temperature, effective alkali and H-Factor. The variable output is the Kappa number. The number of hidden neurons was defined by the neural model that showed the smallest error for the set of validation and training. The number of interactions was also determined from the smallest error generated by simulations. This model was validated with experimental and industrial data. The hybrid model used as input variables and Kappa Neural theoretical, temperature, and factor H and the output variable is the number Kappa Hybrid. This was validated with industrial data. The models presented (deterministic, Neural and Hybrid) are useful tools for the manufacture of pulp and paper, since there is the possibility to be applied to simulation of processes, optimization and control. The models can be tested for different operating conditions without changing the output. Besides, allowing better control of some variables in the manufacturing process, ie without loss of quality of product. In this study, the neural network and the kinetic models showed similar results. Keywords: Kappa number, Deterministic Model, Neural Model and Hybrid Model / Doutorado / Desenvolvimento de Processos Químicos / Doutor em Engenharia Química

Orientadores: Telma Teixeira Franco, Cristiana Maria Pedroso Yoshida / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-15T15:53:33Z (GMT). No. of bitstreams: 1 Reis_ArleteBarbosados_D.pdf: 13934969 bytes, checksum: 03146877cc84caaa322956f2bed59b17 (MD5) Previous issue date: 2010 / Resumo: O revestimento de folhas de papel Kraft foi estudado visando o desenvolvimento de um novo material com potencial para uso em embalagens. Este sistema de recobrimento utilizou apenas matérias-primas naturais de fontes renováveis: a quitosana, um polímero proveniente do descarte da indústria pesqueira e o ácido palmítico. Foram estudadas formulações de recobrimento contendo somente quitosana ou quitosana emulsionada com acido palmítico. Filmes de quitosana (4,0% m/m) e filmes emulsionado de quitosana com a incorporação do lipídio (4,0% de quitosana e 2,0% de ácido palmítico) foram preparados e caracterizados visando o estudo das propriedades de barreira à umidade. Em seguida, amostras com dimensões padronizadas de papel Kraft comercial foram recobertas utilizando dois tipos de extensores (80um e 40um) conferindo gramaturas que variaram entre 0,71g/m2 e 1,06g/m2. Este material foi denominado sistema de embalagem papel-filme de quitosana e sistema de embalagem papel-filme emulsionado de quitosana, os quais foram avaliados quanto à homogeneidade do revestimento, propriedades mecânicas, superfície, barreira a vapor d'água, capacidade de absorção de água e biodegradabilidade. Foi observado aumento da barreira ao vapor d'água na ordem 28% para o sistema de embalagem papel-filme de quitosana e 70% no sistema de embalagem papel-filme emulsionado de quitosana, ambos comparados ao papel Kraft sem revestimento. A análise das propriedades mecânicas indicou aumento do alongamento do sistema papel-filme de quitosana e do sistema emulsionado, ambos comparados às folhas de papel Kraft sem revestimento. Os testes de biodegradabilidade determinados por análise de respiração do solo indicaram aumento da atividade respiratória de todas as amostras nos primeiros quinze dias de experimento, porém de forma mais acentuada para os filmes emulsionados de quitosana. A análise de gravimétrica das amostras indicou aumento da porcentagem de degradação das mesmas / Abstract: Coating of Kraft paper with chitosan was studied in order to develop a new material potentially useful for packaging. This coating system uses natural raw materials from renewable sources, chitosan and fat acids from the disposal of the fishing industry. We studied different formulations of coating made with chitosan and with chitosan emulsified with palmitic acid. Films of chitosan (4.0% w / w) and films of emulsified chitosan and lipid (4.0% chitosan and 2.0% palmitic acid) were prepared and characterized. Standard samples of Kraft paper were covered by using two types of extenders (80mm and 40 mm) producing samples with different amounts of coating, 0.71 g/m2 and 1.06 g/m2. The coated material was named packaging system-chitosan and packing system- emulsified chitosan. These new materials were evaluated for uniformity of coating, mechanical properties, surface, barrier to water vapor, capacity of water absorption and biodegradability. There was an increase of the barrier to water vapor in the order 28% for the system of paper-packaging-chitosan and 70% in the packaging system emulsified chitosan, when compared to the uncoated Kraft paper. Tests for mechanical properties showed increased elongation of the fibers for both materials when compared to uncoated Kraft paper. The biodegradability tests (determined by soil respiration) showed an increase in respiratory activity of all samples in the first fifteen days of the experiment, but more markedly for films of emulsified chitosan. Gravimetric analysis of samples showed increased degradation of them / Doutorado / Desenvolvimento de Processos Químicos / Doutor em Engenharia Química