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Effects of mixing and pumping energy on technological and microstructural properties of cement-based mortarsTakahashi, Keisuke 09 December 2014 (has links) (PDF)
Numerous recurrent situations following mixing and pumping of mortars and concretes cause degradation of fluidity and hardening characteristics. Which, in turn, lead to adverse effects on the quality of workmanship and structural defects.
Nonetheless, relatively little research on the mixing and pumping energies used for the onsite transport and preparation of mortar or concrete has been directed at the core reasons or mechanisms for changes in technological properties.
This dissertation describes and explains the effects of various mixing and pumping parameters on the mortar characteristics in a field trial and on a laboratory scale.
Observations using a rheograph revealed that shearing action does exhibit the most pronounced influence on the characteristics of mortars during the pumping. The performed investigations indicate that higher shearing actions, for example, excessive mixing duration and long-distance pumping lead to reduced flowability, accelerated and increased hydration rate, increased early compressive strength and early-age shrinkage.
From these findings, the underlying mechanism responsible for acceleration and increase of hydration rate is pinpointed as: the increased dissolution from the active surface area due to the destruction of the protective superficial layers of cement
grains, as well as a transition from flocculation to dispersion. The creation of new surfaces leads to further consumption of active super plasticizer in solution phase and to subsequent degrading changes in fluidity (decreasing flowability). The degradation of fluidity and densification of microstructure provoked by the hydration changes do increase the early age shrinkage of mortar.
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Efetividade da antissepsia bucal prévia com clorexidina na prevenção da contaminação da moldagem com alginato e sua influência na distorção do material / Efectivity of a preprocedural mouthrinse with chlorhexidine in the microbial contamination of dental impressions and its influence on the material s distortionCubas, Gloria Beatriz de Azevedo 07 December 2012 (has links)
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Previous issue date: 2012-12-07 / The aims of this randomised controlled trial were to evaluate the influence of a preprocedural 0.12% chlorhexidine mouthrinse on the microbial contamination of dental impressions, subsequently disinfected with sodium hypoclorite or water (control). The second objective was to evaluate if aqueous solution of 0.12% chlorhexidine mixed with irreversible hydrocolloid powder would decrease microbial contamination of dental impressions. Forty subjects underwent maxillary dental impressions with irreversible hydrocolloid and were randomly divided into two groups (n=20) according to the preprocedural mouthrinse (0.12% chlorhexidine or placebo).The dental impressions were then divided into two subgroups and disinfected with sodium hypochlorite or water (control). In the second part, 20 subjects underwent maxillary dental impressions with irreversible hydrocolloid and randomly assigned into two groups according to the mixed agent used (0.12% chlorhexidine or water). Saliva and alginate samples were assessed for microbiological counts of total micro-organisms, total streptococci and Candida species. Surface roughness of the impressions and dimensional stability of the casts were also evaluated. Chlorhexidine preprocedural mouthrinse significantly reduced (p<0.05) microbial contamination. Small but significant alterations were produced on dimensional stability and surface quality when sodium hypochlorite was used as disinfectant after the impression (p=0.005). The results also showed that the use of aqueous 0.12% chlorhexidine mixed with the powder of irreversible hydrocolloid decreased the percentage of total micro-organisms and total Streptococci counts (p<0.001), without producing alterations in surface quality and dimensional stability. It can be concluded that 0.12% chlorhexidine used as preprocedural mouthrinse, or mixed with irreversible hydrocolloid powder, are effective methods in reducing microbial contamination of alginate impressions, without causing damage to the physical and mechanical properties of the material / Os objetivos deste ensaio clínico randomizado foram (I) avaliar a influência de um bochecho, com solução de clorexidina 0,12% e placebo, previamente a realização de moldagens bucais, posteriormente desinfetadas com hipoclorito de sódio ou água (controle) na contaminação de moldagens de alginato; e (II) avaliar se solução aquosa de clorexidina 0,12% misturada com o pó de hidrocolóide irreversível reduziria a contaminação microbiana de moldagens bucais.Quarenta voluntários foram submetidos a moldagens bucais com hidrocolóide irreversível e foram divididos de forma randomizada em 2 grupos (n=20) de acordo com a solução bucal (0,12% clorexidina ou placebo). As moldagens bucais foram divididas em 2 grupos e desinfetadas com hipoclorito de sódio ou água (controle). Na segunda parte do ensaio clinico, 20 voluntários foram submetidos a moldagens bucais com hidrocolóide irreversível e foram divididos em 2 grupos de acordo com a solução usada no preparo do alginato (0,12% clorexidina ou água).Amostras de saliva e alginato foram avaliados quanto a contagem microbiana de microrganismos totais, estreptococos totais e espécies de Candida. Rugosidade de superfície e estabilidade dimensional de modelos de gesso também foram avaliados. Bochecho com solução bucal de clorexidina reduziu de forma significativamente (p<0,005) a contaminação microbiana. Pequenas mais significativas alterações dimensionais e de rugosidade de superfície foram produzidas quando hipoclorito de sódio foi utilizado como agente desinfetante pós-moldagem (p=0,005). Os resultados também demonstraram que o uso de solução de clorexidina 0,12% misturada ao pó de hidrocolóide irreversível reduziu a percentagem de microrganismos totais e estreptococos (p<0.001), sem causar alterações de rugosidade de superfície e estabilidade dimensional. Pode ser concluído que o uso de solução de clorexidina 0,12% usada como bochecho bucal ou misturada ao pó de hidrocolóide irreversível são métodos eficientes na redução microbiana de moldagens de alginato, sem causarem danos as propriedades físicas e mecânicas do material
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DEVELOPMENT OF A METHOD TO EVALUATE WRINKLING TENDENCY OF INK-JET PAPERSMulaka, Brahmananda Reddy 20 September 2005 (has links)
No description available.
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Effects of mixing and pumping energy on technological and microstructural properties of cement-based mortarsTakahashi, Keisuke 28 November 2014 (has links)
Numerous recurrent situations following mixing and pumping of mortars and concretes cause degradation of fluidity and hardening characteristics. Which, in turn, lead to adverse effects on the quality of workmanship and structural defects.
Nonetheless, relatively little research on the mixing and pumping energies used for the onsite transport and preparation of mortar or concrete has been directed at the core reasons or mechanisms for changes in technological properties.
This dissertation describes and explains the effects of various mixing and pumping parameters on the mortar characteristics in a field trial and on a laboratory scale.
Observations using a rheograph revealed that shearing action does exhibit the most pronounced influence on the characteristics of mortars during the pumping. The performed investigations indicate that higher shearing actions, for example, excessive mixing duration and long-distance pumping lead to reduced flowability, accelerated and increased hydration rate, increased early compressive strength and early-age shrinkage.
From these findings, the underlying mechanism responsible for acceleration and increase of hydration rate is pinpointed as: the increased dissolution from the active surface area due to the destruction of the protective superficial layers of cement
grains, as well as a transition from flocculation to dispersion. The creation of new surfaces leads to further consumption of active super plasticizer in solution phase and to subsequent degrading changes in fluidity (decreasing flowability). The degradation of fluidity and densification of microstructure provoked by the hydration changes do increase the early age shrinkage of mortar.
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Modelización de la variación dimensional de los tejidos de punto por recogida durante todo el proceso productivoLlinares Berenguer, Jorge Óscar 24 October 2022 (has links)
Tesis por compendio / [ES] El objetivo de esta tesis se considera de gran relevancia para los técnicos de las industrias textiles de género de punto, ya que contribuye a simplificar enormemente los cálculos productivos en las empresas de género de punto por trama. Ofrece un método eficaz para predecir el encogimiento longitudinal, transversal y al ancho de los tejidos de punto después de los procesos de tejeduría, tintura y acabados a partir de la forma dimensional que adopte la malla. Esta investigación se ha realizado con el análisis de más de 700 muestras de tejido extraídas de sus respectivas partidas de tejido. Con este análisis se han obtenido modelos de regresión lineal. Después de la verificación de los resultados obtenidos se validan los modelos, apreciando mínimos errores que verifican su aplicabilidad.
Esta Tesis Doctoral comienza con el análisis de la variación dimensional de las tres estructuras fundamentales: interlock, 1x1 rib y single jersey. Durante los procesos de tejeduría, tintura y acabado de los tejidos de punto, se pueden dar una serie de circunstancias que pueden alterar la calidad del producto final del tejido y por consiguiente su transmisión directa al artículo al que va a ser destinado. Uno de estos factores que ha creado mucha incertidumbre en su trabajo a los técnicos de las industrias textiles ha sido la estabilidad dimensional de los tejidos de punto.
La aplicación de los resultados de la Tesis puede proporcionar un importante ahorro de tiempo a las empresas de género de punto y, en consecuencia, un ahorro de inversión en stock de productos intermedios. Con la aplicación de los modelos desarrollados, las empresas no necesitan utilizar los métodos de cálculo comunes consistentes en la aplicación de la norma UNE EN ISO 6330-2012, que requiere un día de parada en la producción hasta la obtención de los resultados.
También en esta tesis doctoral se han propuesto modelos que expliquen la variabilidad de la longitud del hilo absorbido por una malla, en cada una de las tres estructuras fundamentales, a partir de modelos que utilizan otras variables mucho más sencillas de analizar. De esta forma se deja de un lado el cálculo tradicional utilizado basado en la norma UNE-EN 14970, ya que este procedimiento es algo engorroso, requiriendo mucho tiempo y un aparato de medición del hilo. Con la utilización de los modelos propuestos se agiliza la estimación de la longitud de malla entre los estados de relajación propuestos, dos en tejeduría (Tejeduría y relajación en seco y Tejeduría y relajación en húmedo) y dos en tintura (Tintura y relajación en seco y tintura y relajación en húmedo). / [CA] L'objectiu d'aquesta tesi es considera de gran rellevància per als tècnics de les indústries tèxtils de gènere de punt, ja que contribueix a simplificar enormement els càlculs productius a les empreses de gènere de punt per trama.
Ofereix un mètode eficaç per predir l'encongiment longitudinal i transversal dels teixits de punt després dels processos de teixidura, tintura i acabats a partir de la forma dimensional que adopte la malla. Aquesta investigació s'ha fet amb l'anàlisi de més de 700 mostres de teixit extretes de les respectives partides de teixit. Amb aquesta anàlisi s'han obtingut models de regressió lineal. Després de la verificació dels resultats obtinguts es validen els models, apreciant mínims errors que verifiquen la seua aplicabilitat.
Aquesta Tesi Doctoral comença amb l'anàlisi de la variació dimensional de les tres estructures fonamentals: interlock, 1x1 rib i single jersei. Durant els processos de teixidura, tintura i acabat dels teixits de punt, es poden donar una sèrie de circumstàncies que poden alterar la qualitat del producte final del teixit i per tant la seva transmissió directa a l'article a què serà destinat. Un d'aquests factors que ha creat molta incertesa a la feina als tècnics de les indústries tèxtils ha estat l'estabilitat dimensional dels teixits de punt.
L'aplicació dels resultats de la Tesi pot proporcionar un important estalvi de temps a les empreses de gènere de punt i, en conseqüència, un estalvi d'inversió en estoc de productes intermedis. Amb l'aplicació dels models desenvolupats, les empreses no necessiten utilitzar els mètodes de càlcul comuns consistents en l'aplicació de la norma UNE EN ISO 6330-2012, que requereix un dia de parada a la producció fins a l'obtenció dels resultats.
També en aquesta tesi doctoral s'han proposat models que expliquen la variabilitat de la longitud del fil absorbit per una malla, en cadascuna de les tres estructures fonamentals, a partir de models que utilitzen altres variables molt més senzilles d'analitzar. D'aquesta manera es deixa d'una banda el càlcul tradicional utilitzat basat en la norma UNE-EN 14970, ja que aquest procediment és una mica molest, requerint molt de temps i un aparell de mesura del fil. Amb la utilització dels models proposats s'agilitza l'estimació de la longitud de malla entre els estats de relaxació proposats, dos en teixidura (Teixidura i relaxació en sec i Teixidura i relaxació en humit) i dos en tintura (Tintura i relaxació en sec i tintura i relaxació en humit). / [EN] The objective of this thesis is considered of great relevance for the technical of the knitwear textile industries, since it greatly simplifies the productive calculations in weft knitting companies.
It offers an effective method for predicting the longitudinal and transverse shrinkage of knitted fabrics after the knitting, dyeing and finishing processes, based on the dimensional shape adopted by the loop. This research has been carried out with the analysis of more than 700 knitting samples extracted from their respective fabrics items. With this analysis we have obtained linear regression models. After verification of the results obtained, the models are validated, appreciating minimum errors that verify their applicability.
This Doctoral Thesis begins with the analysis of the dimensional variation of the three fundamental structures: interlock, 1x1 rib and single jersey. During the
knitting, dyeing and finishing processes of knitted fabrics, can be given a series of circumstances that can alter the quality of the final product of the fabric and therefore its direct transmission to the article to which it is going to be intended. One of these factors that has created a lot of uncertainty in your work technical of the textile industries has been the dimensional stability of knitted fabrics.
The application of the results of the Thesis can provide a significant save time for knitting companies and, consequently, an investment savings in stock of intermediate products. With the application of developed models, companies do not need to use the calculation methods consisting of the application of the UNE EN ISO 6330-2012 standard, which It requires a day of stoppage in production until the results are obtained.
Also in this doctoral thesis models have been proposed that explain the variability of the length of the thread absorbed by a loop, in each of the three fundamental structures, from models that use other variables much easier to analyze. In this way, it leaves aside the traditional calculation used based on the UNE-EN 14970 standard, since this procedure is somewhat cumbersome, requiring a lot of time and a thread measurement. With the use of the proposed models, the estimation of the loop length between the proposed relaxation states, two in knitting (knitting and dry relaxation and knitting and wet relaxation) and two in dyeing (dyeing and dry relaxation and dyeing and wet relaxation). / Llinares Berenguer, JÓ. (2022). Modelización de la variación dimensional de los tejidos de punto por recogida durante todo el proceso productivo [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/188844 / Compendio
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Extended impregnation kraft cooking of softwood : Effects on reject, yield, pulping uniformity, and physical propertiesKarlström, Katarina January 2009 (has links)
<p>Converting wood into paper is a complex process involving many different stages, one of which is pulping. Pulping involves liberating the wood fibres from each other, which can be done either chemically or mechanically. This thesis focuses on the most common chemical pulping method, the kraft cooking process, and especially on a recently developed improvement of the impregnation phase, which is the first part of a kraft cook.</p><p>Extended impregnation kraft cooking (EIC) technique is demonstrated to be an improvement of the kraft pulping process and provides a way to utilize softwood to a higher degree, at higher pulp yield. We demonstrate that it is possible to produce softwood (<em>Picea abies</em>) kraft pulp using a new cooking technique, resulting in a pulp that can be defibrated without inline refining at as high lignin content as 8% on wood, measured as kappa numbers above 90. Lignin is the wood constituent that holds the wood fibres together in the wood matrix. The new cooking technique uses the differences in reaction rate between the diffusion and consumption of hydroxide ions; it is used to ensure a homogenous impregnation of wood chips at lower impregnation temperatures and longer impregnation times than are generally used in the industry. The applied cooking temperatures are also substantially lower than those used in conventional kraft pulping systems, promoting uniform delignification. This results in a narrower kappa number distribution than in lab-cooked conventional kraft pulp.</p><p>High-kappa-number pulps were investigated for pulp sheet properties such as tensile strength, tensile stiffness, and compression strength. It was demonstrated that an EIC pulp of kappa number 95 has strength properties comparable to those of a conventional pulp of kappa number 82. Comparing the effects of starch multilayers on conventional and EIC pulps reveals similar effects. The use of the starch multilayer treatment increased the tensile index and decreased the tensile stiffness and short-span compression test (SCT) indices.</p><p>The EIC technique has also been used to produce a series of bleachable-grade pulps. The results indicate the possibility of increasing the lignin content of the pulp entering the oxygen delignification stage, since the reject content of gently defibered pulp is lower than 0.1% at kappa number 49.</p><p>In this thesis, we recommend that wood chips be impregnated for 2 h at 110 °C to neutralize acidic compounds in the wood and impregnate the chips with cooking chemicals, and that the ensuing cook be performed at 135–140 °C, depending on the target kappa number. We also recommend increasing the available amounts of cooking chemicals in the impregnation stage by using a higher liquor-to-wood ratio and keeping the alkali profile fairly high in the ensuing cook. This concept will reduce the amount of reject material, increase the pulping uniformity, and increase the selectivity towards lignin degradation in the kraft cook.</p> / <p>Omvandling av ved till papper är en komplicerad process som består av många olika steg där ett är massaframställningen (eng. <em>pulping</em>). Massaframställning medför att vedfibrerna frigörs från varandra på kemisk eller mekanisk väg. Denna avhandling fokuserar på den vanligaste kemiska metoden, sulfatkokning och speciellt den nyligen utvecklade förbättringen av impregnerings fasen, som är den första delen av ett sulfatkok. <em></em></p><p>Här visas att<em> Extended Impregnation kraft Cooking </em>(EIC) innebär en förbättring av sulfatkokningen och ett sätt att uppnå högre vedutnyttjande vid högre utbyte för barrved. Vi visar att det är möjligt att producera barrvedsmassa med en ny kokningsprincip som resulterar i en massa som är defibrerbar utan inline-raffinering vid så högt lignin innehåll som 8% (på ved), mätt som kappatal över 90. Lignin är den vedkomponent som håller ihop vedfibrerna i vedmatrisen. Kokningsprincipen utnyttjar skillnaderna i reaktionshastighet mellan diffusion och konsumtion av hydroxidjoner och nyttjas till att skapa en homogen impregnering av vedflisen vid lägre impregneringstemperatur och under längre tid än vad som vanligen används i industrin. De använda koktemperaturerna är också betydligt lägre än vid konventionell sulfatkokning vilket gynnar jämn delignifiering. Detta resulterar i en smalare kappatalsfördelning jämfört med laboratoriekokade konventionella massor.</p><p>Massor med höga kappatal undersöktes med avseende på egenskaper hos handark, såsom dragstyrka, dragstyvhet och kompressionsstyrka Det visades att handark från EIC massa vid kappatal 95 hade jämförbara styrkeegenskaper med konventionell massa vid kappatal 82. Vid jämförelse av effekten av stärkelse multilager på konventionella och EIC massor avslöjar liknande effekter. Användningen av stärkelsemultilager ökade dragindex och minskade dragstyvhets- och kompressions index (SCT, short-compression test).</p><p>Kokprincipen har även använts för att ta fram en serie blekbara massor. Resultaten visar på möjligheten att öka lignininnehållet i massan in till i syrgasdelignifierings-steget eftersom spetinnehållet för milt defibrerad massa var lägre än 0,1% vid kappatal 49.</p><p>I den här avhandlingen rekommenderar vi att vedflis impregneras i 2 timmar vid 110 °C för att neutralisera sura komponenter i veden och impregnera flisen med kokkemikalier, samt att utföra det efterföljande koket vid 135–140 °C beroende på önskat kappatal. Vi rekommenderar även att öka den tillgängliga mängden kokkemikalier i impregneringssteget genom att använda högre vätske-ved förhållande och att hålla alkali profilen relativt hög i det efterföljande koket. Detta koncept reducerar spetmängden, ger jämnare kokning och ökar selektiviteten för nedbrytning av lignin i sulfatkoket.</p>
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Stabilité bidimensionnelle de modèles de sillage d’aéronefs / Two-dimensional stability of aircraft wake vorticesJugier, Rémi 28 September 2016 (has links)
Le contrôle des tourbillons de sillages d'aéronefs permet de réduire leur dangerosité et d'augmenter par conséquent le débit de décollages et d'atterrissages dans les aéroports. Ce contrôle permettrait également d'agir sur la formation des rainées de condensation et des cirrus artificiels en haute atmosphère dans le but de réduire le forçage radiatif terrestre causé par l'aviation. Brion (2014) ont montré par analyse de stabilité modale que le dipôle de Lamb-Chaplygin, souvent utilisé comme un modèle représentatif des tourbillons de sillage en champ lointain, est bidimensionnellement instable à des nombres de Reynolds faibles. Nous étendons premièrement cette analyse de stabilité modale bidimensionnelle à des modèles de dipôles plus réalistes, pour une large gamme de rapport d'aspect, et obtenons, à faibles nombre de Reynolds, des instabilités de même nature (modes de déplacement) que pour le dipôle de Lamb-Chaplygin. Nous montrons cependant que la croissance des instabilités observées dépend fortement du rapport d'aspect du dipôle, et que cette croissance est fortement diminuée lorsque la diffusion du dipôle est prise en compte. Nous étudions ensuite la stabilité bidimensionnelle transitoire en champ lointain (dipôles) et en champ proche (nappes de vorticité), en atmosphères homogène et stratifiée. Dans tous les cas, les perturbations optimales sont des spirales de vorticité orientées à contre-cisaillement et situées en périphérie des tourbillons, qui conduisent in fine aux instabilités écrites par l'analyse modale grâce à un mécanisme de contamination du cœur des tourbillons, initialement identifié par Antkowiak & Brancher 2004 sur un tourbillon isolé. / Aircraft wake vortex control allows for reducing of their dangerousness and consequently improve airport take-off / landing requencies. Contrails and artificial cirrus clouds formation could also be influenced through this control of wake vortices and allow for reducing of terrestrial radiative forcing generated by aviation. Brion (2014) have shown by a modal stability analysis that the Lamb-Chaplygin dipole, often used as a far-field model for aircraft wake vortices, is unstable to two-dimensional perturbations at Iow Reynolds numbers. We first extend this twodimensional modal stability analysis to more realistic dipole models, for a Wide range of aspect ratios, and obtain, for Iow Reynolds numbers, instabilities of the same nature (displacement modes) as for the Lamb-Chaplygin dipole. However, we show that the growth of those modes depends greatly on the dipole aspect ratio, and that this growth is greatly diminished hen the dipole diffusion is taken into account. We then study two-dimensional transient growth for far-field models (dipoles) and near-field models (vorticity sheets), in homogeneous and stratified atmospheres. ln all cases, optimal perturbations are vorticity spirals oriented against shear and located at the periphery of the vortices, which eventually lead to development of the instabilities described in the modal analysis through a contamination mechanism of the vortex cores, initially identified by Antkowiak & Brancher (2004) for an isolated vortex.
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Extended impregnation kraft cooking of softwood : Effects on reject, yield, pulping uniformity, and physical propertiesKarlström, Katarina January 2009 (has links)
Converting wood into paper is a complex process involving many different stages, one of which is pulping. Pulping involves liberating the wood fibres from each other, which can be done either chemically or mechanically. This thesis focuses on the most common chemical pulping method, the kraft cooking process, and especially on a recently developed improvement of the impregnation phase, which is the first part of a kraft cook. Extended impregnation kraft cooking (EIC) technique is demonstrated to be an improvement of the kraft pulping process and provides a way to utilize softwood to a higher degree, at higher pulp yield. We demonstrate that it is possible to produce softwood (Picea abies) kraft pulp using a new cooking technique, resulting in a pulp that can be defibrated without inline refining at as high lignin content as 8% on wood, measured as kappa numbers above 90. Lignin is the wood constituent that holds the wood fibres together in the wood matrix. The new cooking technique uses the differences in reaction rate between the diffusion and consumption of hydroxide ions; it is used to ensure a homogenous impregnation of wood chips at lower impregnation temperatures and longer impregnation times than are generally used in the industry. The applied cooking temperatures are also substantially lower than those used in conventional kraft pulping systems, promoting uniform delignification. This results in a narrower kappa number distribution than in lab-cooked conventional kraft pulp. High-kappa-number pulps were investigated for pulp sheet properties such as tensile strength, tensile stiffness, and compression strength. It was demonstrated that an EIC pulp of kappa number 95 has strength properties comparable to those of a conventional pulp of kappa number 82. Comparing the effects of starch multilayers on conventional and EIC pulps reveals similar effects. The use of the starch multilayer treatment increased the tensile index and decreased the tensile stiffness and short-span compression test (SCT) indices. The EIC technique has also been used to produce a series of bleachable-grade pulps. The results indicate the possibility of increasing the lignin content of the pulp entering the oxygen delignification stage, since the reject content of gently defibered pulp is lower than 0.1% at kappa number 49. In this thesis, we recommend that wood chips be impregnated for 2 h at 110 °C to neutralize acidic compounds in the wood and impregnate the chips with cooking chemicals, and that the ensuing cook be performed at 135–140 °C, depending on the target kappa number. We also recommend increasing the available amounts of cooking chemicals in the impregnation stage by using a higher liquor-to-wood ratio and keeping the alkali profile fairly high in the ensuing cook. This concept will reduce the amount of reject material, increase the pulping uniformity, and increase the selectivity towards lignin degradation in the kraft cook. / Omvandling av ved till papper är en komplicerad process som består av många olika steg där ett är massaframställningen (eng. pulping). Massaframställning medför att vedfibrerna frigörs från varandra på kemisk eller mekanisk väg. Denna avhandling fokuserar på den vanligaste kemiska metoden, sulfatkokning och speciellt den nyligen utvecklade förbättringen av impregnerings fasen, som är den första delen av ett sulfatkok. Här visas att Extended Impregnation kraft Cooking (EIC) innebär en förbättring av sulfatkokningen och ett sätt att uppnå högre vedutnyttjande vid högre utbyte för barrved. Vi visar att det är möjligt att producera barrvedsmassa med en ny kokningsprincip som resulterar i en massa som är defibrerbar utan inline-raffinering vid så högt lignin innehåll som 8% (på ved), mätt som kappatal över 90. Lignin är den vedkomponent som håller ihop vedfibrerna i vedmatrisen. Kokningsprincipen utnyttjar skillnaderna i reaktionshastighet mellan diffusion och konsumtion av hydroxidjoner och nyttjas till att skapa en homogen impregnering av vedflisen vid lägre impregneringstemperatur och under längre tid än vad som vanligen används i industrin. De använda koktemperaturerna är också betydligt lägre än vid konventionell sulfatkokning vilket gynnar jämn delignifiering. Detta resulterar i en smalare kappatalsfördelning jämfört med laboratoriekokade konventionella massor. Massor med höga kappatal undersöktes med avseende på egenskaper hos handark, såsom dragstyrka, dragstyvhet och kompressionsstyrka Det visades att handark från EIC massa vid kappatal 95 hade jämförbara styrkeegenskaper med konventionell massa vid kappatal 82. Vid jämförelse av effekten av stärkelse multilager på konventionella och EIC massor avslöjar liknande effekter. Användningen av stärkelsemultilager ökade dragindex och minskade dragstyvhets- och kompressions index (SCT, short-compression test). Kokprincipen har även använts för att ta fram en serie blekbara massor. Resultaten visar på möjligheten att öka lignininnehållet i massan in till i syrgasdelignifierings-steget eftersom spetinnehållet för milt defibrerad massa var lägre än 0,1% vid kappatal 49. I den här avhandlingen rekommenderar vi att vedflis impregneras i 2 timmar vid 110 °C för att neutralisera sura komponenter i veden och impregnera flisen med kokkemikalier, samt att utföra det efterföljande koket vid 135–140 °C beroende på önskat kappatal. Vi rekommenderar även att öka den tillgängliga mängden kokkemikalier i impregneringssteget genom att använda högre vätske-ved förhållande och att hålla alkali profilen relativt hög i det efterföljande koket. Detta koncept reducerar spetmängden, ger jämnare kokning och ökar selektiviteten för nedbrytning av lignin i sulfatkoket. / QC 20120216
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Exploring Biopolymer-Clay Nanocomposite Materials by Molecular ModellingWang, Yan January 2015 (has links)
In this thesis, bio-nanocomposites made from two alternative biopolymers and montmorillonite (Mnt) clay have been investigated by molecular modelling. These biopolymers are xyloglucan (XG) and chitosan (CHS), both of which are abundant, renewable, and cost-effective. After being reinforced by Mnt clay nanoparticles, the polymer nanocomposites gains in multifunctionality and in the possibility to register unique combinations of properties, like mechanical, biodegradable, electrical, thermal and gas barrier properties. I apply molecular dynamics (MD) simulations to study the interfacial mechanisms of the adhesion of these biopolymers to the Mnt nanoplatelets at an atomic level. For the XG-Mnt system, a strong binding affinity of XG to a fully hydrated Mnt interface was demonstrated. It was concluded that the dominant driving force for the interfacing is the enthalpy, i.e. the potential energy of the XG-Mnt interacting system. The adsorbed XG favors a flat conformation with a galactose residue in its side chain that facilitates the adsorption of the polymer to the nanoclay. The XG adsorption was found do depend strongly on the hydration ability of counterions. The binding affinity of XG to Mnt was found to be strongest in the K-Mnt/XG system, followed by, in decreasing order, Na-Mnt/XG, Li-Mnt/XG, and Ca-Mnt/XG. The competing mechanism between ions, water and the XG in the interlayer region was shown to play an important role. The dimensional stability upon moisture exposure, i.e. the ability of a material to resist swelling, is an important parameter for biopolymer-clay nanocomposites. While pure clay swells significantly even at low hydration levels, it is here shown that for the XG-Mnt system, at a hydration level below 50%, the inter-lamellar spacing is well preserved, suggesting a stable material performance. However, at higher hydration levels, the XG-Mnt composite was found to exhibit swelling at the same rate as the pure hydrated Mnt clay. For the CHS-Mnt system, the significant electrostatic interactions from the direct charge-charge attraction between the polymer and the Mnt clay play a key role in the composite formation. Varying the degree of acetylation (DA) and the degree of protonation (DPr) resulted in different effects on the polymer-clay interaction. For the heavily acetylated CHS (DA > 50%, also known as chitin), the strong adhesion of the neutral chitin to the Mnt clay was attributed to strong correlation between the acetyl functional groups and the counterions which act as an electrostatic “glue”. Similarly, the poor adhesion of the fully deprotonated (DPr = 0%) neutral CHS to the clay is attributed to a weak correlation between the amino functional group and the counterions. The stress-strain behavior of the CHS-Mnt composite shows that the mechanical properties are highly affected by the volume fraction of the Mnt clay and the degree of exfoliation of the composite. The material structure has a close relationship to the material properties. Biopolymer-clay nanocomposites hold a bright future to replace petroleum-derived polymer plastics and will become widely used in common life. The theme of the thesis is that further critical improvements of these materials can be accomplished by development of the experimental methods in conjunction with increased understanding of the interactions between polymer, clay, water, ions, solutions in the polymer-clay mixtures provided by molecular modelling. / I denna avhandling har molekylär modellering och molekyldynamisk (MD) simulering använts för att studera modellsystem för bio-nanokompositer bestående av montmorillonit-lera samt två olika sorters biopolymerer – xyloglukan (XG) och kitosan (CHS). Båda dessa polymerer är naturligt förekommande och mycket vanliga. De är dessutom förnyelsebara och kostnadseffektiva. Då polymererna förstärkts med nanopartiklar av montmorillonit får det resulterande kompositmaterialet en unik kombination av egenskaper såsom mekaniska, elektriska, termiska och barriär egenskaper etc. Genom att använda molekyldynamiska (MD) simuleringar, studeras här växelverkan mellan dessa biopolymerer och lernanopartiklar (Mnt) på grundläggande atomistisk detaljnivå. Mellan XG och Mnt i ett fullt hydrerat system kunde stark bindningsaffinitet påvisas. Den dominerande drivkraften för affiniteten var entalpi, d.v.s. potentiell växelverkansenergi. Den adsorberade XG-kedjan antar en platt konformation på ytan. Ett förslag utifrån simuleringsresultaten var att galaktosresidyn i xyloglukanets sidokedja underlättar adsorptionen till lerytan. Simuleringarna kunde också visa att adsorption av XG till Mnt beror starkt på motjonernas hydreringsförmåga. Bindningsaffiniteten mellan XG och Mnt var som starkast i K-Mnt/XG- systemet. Därefter följde, i minskande ordning, Na-Mnt/XG, Li-Mnt/XG och Ca-Mnt/XG. Det kunde visas att strukturen vid gränsytan styrs av konkurrerande mekanismer mellan joner, vatten och XG. Dimensionsstabilitet vid fuktexponering, d.v.s. förmågan hos ett material att motverka svällning, är en viktig egenskap för biopolymer-lernanokompositer. Ren lera sväller signifikant även vid låga fukthalter. Dock kunde MD simuleringar visa att ett modellsystem av XG-Mnt behåller sitt ursprungliga interlamellära avstånd vid hydreringsnivåer under 50%, vilket indikerar ett stabilare material. Vid högre hydrering uppmättes dock svällningen vara densamma som för ren lera. I CHS-Mnt-systemet visade det sig att direkt elektrostatisk växelverkan med signifikant styrka mellan laddningar på polymer och Mnt-yta spelar störst roll för kompositformeringen. Olika effekt på polymer-lerväxelverkan uppnåddes genom att variera acetyleringsgraden (DA) respektive protoneringsgraden (DPr). För den tungt acetylerade CHS-polymeren (DA > 50%, även kallad kitin) visade sig den starka vidhäftningen bero på korrelation mellan acetylgrupperna och motjonerna som i sin tur verkade som ett elektrostatiskt “lim”. På liknande sätt kunde den svaga vidhäftningen mellan fullt deprotonerad (DPr = 0%) neutral CHS och lera förklaras med en betydligt svagare korrelation mellan aminogrupperna och motjonerna. Spänning-töjningsbeteendet hos CHS-Mnt modellen visar att dess mekaniska egenskaper beror kraftigt på volymsandelen Mnt och graden av exfoliering i kompositen. Materialets struktur är nära relaterat till materialegenskaperna. Framtiden för nanokompositer av biopolymerer och lera är ljus då de kan komma att ersätta oljebaserade plaster och användas frekvent i våra dagliga liv. Materialen kommer successivt förbättras genom utveckling av experimentella metoder i kombination med molekylmodellering för ökad förståelse för växelverkan mellan polymer, lera, vatten, joner och lösningsmedel. / 本论文利用分子动力学模拟技术研究了两种备选生物大分子与蒙脱土(Montmorillonite, Mnt)(一种粘土)组成的生物纳米复合材料,分别是木葡聚糖(Xyloglucan, XG)/蒙脱土和壳聚糖(Chitosan, CHS)/蒙脱土。木葡聚糖与壳聚糖都是自然界广泛存在的生物大分子,资源丰富且取材面宽,提取及加工成本低廉,加之可以生物降解并可再生,是优秀的生物复合材料备选原料。经过蒙脱土纳米颗粒加固后,这些基于生物大分子的复合材料将获得多功能且有多种独特特性相结合的优点,比如,更好的力学性能,生物可降解,良好的导电性能,传热性能和屏蔽气体与液体侵扰的能力等等。论文中,我们采用分子动力学模拟的方法着重对生物大分子与蒙脱土在界面上的粘附相互作用机理进行了深入探讨。 首先,对于木葡聚糖/蒙脱土纳米复合材料,我们发现糖分子与土分子间有着很强的天然亲和力。研究证明它们之间的这种相互作用,热焓是主要的推动力,也就是糖和土分子间的相互作用势能。含有半乳糖残基的木葡聚糖分子(本文中亦称天然木葡聚糖分子)吸附到粘土表面后,分子构型呈现扁平状,半乳糖残基似有辅助木葡聚糖大分子吸附到粘土颗粒上的作用。 进一步研究发现,木葡聚糖分子在粘土表面上的吸附与溶液中抗衡离子的水和作用密切相关。在钾离子平衡的糖/粘土系统中,糖分子与土分子的相互作用最强,钠离子平衡的糖/粘土系统次之,紧接着是锂离子平衡的糖/粘土系统,最弱的是钙离子平衡的糖/粘土系统。研究发现,离子,水分子,以及糖分子在粘土层间的竞争机制在糖分子的粘附过程中起着重要的作用。 材料暴露于潮湿环境中的尺寸稳定性,也就是材料抗肿胀的能力是生物大分子/蒙脱土所构成的复合材料的重要参数。蒙脱土自身即使在很低的潮湿环境下就会有明显地膨胀现象,然而,对木葡聚糖/蒙脱土复合材料来说,尺寸稳定性可以在水和值低于50%以下有效保存。其夹层尺寸的稳定保持暗示了材料在这个程度的潮湿环境下的稳定性。然而,当水和值高于50%时,木葡聚糖/蒙脱土复合材料将出现明显的肿胀现象,表现在夹层尺寸的明显增大,且其膨胀速率与粘土自身的膨胀速率逐渐趋于相当水平。 其次,对于壳聚糖/蒙脱土复合材料,我们发现由电荷-电荷间直接产生地强烈的静电吸引作用是壳聚糖分子与蒙脱土分子相互粘附并构成复合材料的关键因素。通过改变壳聚糖分子的乙酰化程度(Degree of acetylation, DA)和质子化程度(Degree of protonation, DPr),糖分子与土分子的相互作用有着显著地不同。对于乙酰化程度(DA)高于50%的壳聚糖分子(亦成为甲壳素分子chitin, CHT),电中性的甲壳素分子与土分子间的强吸附作用源于乙酰基功能团与抗衡离子的强相关性。抗衡离子此时扮演着类似于“电子胶”的作用,可以有效地将电中性的甲壳素分子与土分子粘结在一起。类似地,当质子化程度最低时,亦即壳聚糖分子完全非质子化,即呈现电中性时,较差的糖/土吸附作用源于氨基功能团与抗衡离子的较弱的相关性。 进一步对壳聚糖/蒙脱土复合材料的分子系统进行应力应变计算发现,复合材料的力学性能直接受蒙脱土体积分数和其剥离程度的影响,通常,粘土的体积分数越大体系的力学性能越高,且剥离程度对材料的整体性能也有直接影响。因此,材料的结构与其性能的表征有着密切联系。 我们相信生物大分子与蒙脱土构成的生物复合材料有着光明的前景,可以取代石油提取物制成的塑料材料,并将能够广泛应用在日常生活中。通过实验技术的改善和应用分子模拟技术对复合材料体系中生物大分子,蒙脱土分子,水分子,离子,溶液环境等混合物质相互作用的理解增加,这种可再生的新材料将会得到重要改进,这也是整本论文的主旋律。 / <p>QC 20150520</p> / Bio-nanocomposites
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