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The influence of inorganic particles on debonding efficiency of fluff pulp / Effekten av oorganiska partiklar på defibreringsenergi hos fluffmassaLindbäck, Vera January 2024 (has links)
Fluffmassa är, i ordets rätta bemärkelse, ett fluffigt material som i de allra flesta fall tillverkas av fibrer ifrån trä, den utgör en viktig del i blöjor, hygienprodukter, näsdukar och ett flertal andra produkter. Syftet med fluffmassa i absorptionsprodukter är framförallt att sprida vätskan, öka absorbtionshastigheten och behålla superabsorberande polymerer på plats i nätverket. Två viktiga kvalitetsparametrar hos fluffmassan är defibreringsenergi och knuthalt. Dessa är korrelerade till hur enkelt fibrerna kan separeras ifrån varandra i torr eller fuktad luft. Denna separation av fibrer är ett högst avgörande steg för att skapa den fluffiga massan ifrån torkade massaark. Målet med arbetet har varit att reducera defibreringsenergin och knuthalten genom att behandla massa med oorganiska partiklar genom att använda den sk. lager-på-lager (LbL) – metoden där en konsekutiv behandling av fibrerna med motsatt laddade polyelektrolyter och nanopartilkar. Genom att belägga fiberytan med tunna skikt av ett oorganiskt material var avsikten att reducera fiber-fiber-interaktionerna för att slutligen minska defiberingsenergin och knuthalten. Studien visade att en viss effekt kunde uppnås med LbL-skikt av pDADMAC (diallyldimetylammonium klorid) och MMT (montmorillonit) vilket noterades som en minskning av knuthalten från 35% till ungefär 20%, medan defibreringsenergin däremot var oförändrad jämfört med ett obehandlat referensprov. De bildade lagren visade sig vara tunnare och jämnare än förväntat vilket sannolikt ledde till en relativt liten minskning av kontaktyta och molekylär adhesion mellan fibrerna vilket kan förklara den relativt sett låga effekten av tillsatserna. De tunna lagren kan också vara en förklaring till varför ingen nämnvärd skillnad detekteras för olika antal av bildade bilager. Eftersom enbart maximalt 3 bilager studerades kan det vara rimligt att anta att en ytterligare adsorption av bilager kan leda till en ytterligare minskning av knuthalten och defibreringsenergin. Eftersom MMT-partiklarna inte var direkt synliga i SEM-analyserna är det svårt att säga exakt hur de är fördelade på fiberytan. Antingen är de jämnt fördelade eller så har vissa områden på fiberytan inte blivit täckta av MMT. Resultaten indikerar också att det finns många intressanta sätt att förbättra lagren för att nå lägre defibrerinsergier och knuthalter. Genom att tex. adsorbera större partiklar istället för tunna MMT-partiklar skulle det vara möjligt att skapa en högre ytråhet och därmed en minskad kontaktyta mellan fibrerna vilket i sin tur skulle kunna minska knuthalten och defibreringsenergin. / Fluff pulp is indeed a fluffy material, it is most commonly composed of pulp fibers from wood and it serves as a vital constituent in diapers, feminine hygiene products, napkins and a variety of other products. The purpose of fluff pulp in absorbent products is mainly to distribute fluids, increase absorption speed and hold superabsorbent polymers within the network. Two important quality parameters of fluff pulp are the defibration energy and the knot content, which are related to the ease at which the fibers can be separated from each other under dry to moist conditions. This separation of fibers is an essential step in generating the fluffy material from sheets. This project aims to reduce the defibration energy and the knot content by treating fibers with inorganic particles according to the Layer-by-Layer (LBL) technique. The main assumption was that by applying coatings to the fibers, the inter-fiber interactions can be reduced leading to a lowered defibration energy and knot content. The study showed that some effect was accomplished using layers of pDADMAC (diallydimethylammoinium chloride) and MMT (montmorillonite clay), the knot content was reduced from 35% to around 20%, but the defibration energy was unchanged compared to the untreated reference sample. The formed LBL layers appeared to be thinner and smoother than anticipated which likely lead to only a slight decrease in contact area between the fibers, hence, the reduction of knot content was detectable but not very large. Since the formed LBL layers were so thin it was difficult to find any distinguishable difference for the different numbers of bilayers, however, the maximum number of bilayers produced was only three and additional layers could lead to an amplified effect. Since the MMT particles could not be clearly visualized from the SEM instruments, it is difficult to conclude exactly how the clay platelets were distributed on the fibers. Either the MMT was distributed rather evenly across the surface of the fibers, or some areas of the fibers were left free from LbLs. The results from the present investigation show that there are many interesting ways to further improve the layers to reach lower defibration energies and knot contents. As an example the adsorption of larger particles instead of thin MMT platelets could be used allowing for a minimization of the contact area between the fibers due to an increased surface roughness of to the fiber surfaces.
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Joint project: Retention of radionuclides relevant for final disposal in natural clay rock and saline systemsSchmeide, Katja, Fritsch, Katharina, Lippold, Holger, Poetsch, Maria, Kulenkampff, Johannes, Lippmann-Pipke, Johanna, Jordan, Norbert, Joseph, Claudia, Moll, Henry, Cherkouk, Andrea, Bader, Miriam 15 March 2016 (has links) (PDF)
The objective of this project was to study the influence of increased salinities on interaction processes in the system radionuclide – organics – clay – aquifer. For this purpose, complexation, redox, sorption, and diffusion studies were performed under variation of the ionic strength (up to 4 mol/kg) and the background electrolyte.
The U(VI) complexation by propionate was studied in dependence on ionic strength (up to 4 mol/kg NaClO4) by TRLFS, ATR FT-IR spectroscopy, and DFT calculations. An influence of ionic strength on stability constants was detected, depending on the charge of the respective complexes. The conditional stability constants, determined for 1:1, 1:2, and 1:3 complexes at specific ionic strengths, were extrapolated to zero ionic strength.
The interaction of the bacteria Sporomusa sp. MT-2.99 and Paenibacillus sp. MT-2.2 cells, isolated from Opalinus Clay, with Pu was studied. The experiments can be divided into such without an electron donor where biosorption is favored and such with addition of Na-pyruvate as an electron donor stimulating also bioreduction processes. Moreover, experiments were performed to study the interactions of the halophilic archaeon Halobacterium noricense DSM-15987 with U(VI), Eu(III), and Cm(III) in 3 M NaCl solutions.
Research for improving process understanding with respect to the mobility of multivalent metals in systems containing humic matter was focused on the reversibility of elementary processes and on their interaction. Kinetic stabilization processes in the dynamics of humate complexation equilibria were quantified in isotope exchange studies. The influence of high salinity on the mobilizing potential of humic-like clay organics was systematically investigated and was described by modeling.
The sorption of Tc(VII)/Tc(IV) onto the iron(II)-containing minerals magnetite and siderite was studied by means of batch sorption experiments, ATR FT-IR and X-ray absorption spectroscopy. The strong Tc retention at these minerals could be attributed to surface-mediated reduction of Tc(VII) to Tc(IV). An influence of ionic strength was not observed.
The influence of ionic strength (up to 3 mol/kg) and background electrolyte (NaCl, CaCl2, MgCl2) on U(VI) sorption onto montmorillonite was studied. The U(VI) sorption is influenced by the background electrolyte, the influence of ionic strength is small. Surface complexation modeling was performed applying the 2SPNE SC/CE model. Surface complexation constants were determined for the NaCl and CaCl2 system and were extrapolated to zero ionic strength. Surface complexation in mixed electrolytes can be modeled applying surface complexation constants derived for pure electrolytes.
The influence of citrate on U(VI) diffusion in Opalinus Clay was studied using Opalinus Clay pore water as background electrolyte. The diffusion parameter values obtained for the HTO through-diffusion and the U(VI) in-diffusion in the absence of citric acid were in agreement with literature data. In the presence of citric acid, U(VI) diffusion was significantly retarded, which was attributed to a change in speciation, probably U(VI) was reduced to U(IV).
Larger-scale heterogeneous material effects on diffusive transport were investigated with PET. Diffusion parameters were derived by optimum fit of a FEM-model to the measurement. These parameters are in accordance with the results from 1D-through-diffusion experiments. Deviations from the simple transversal-isotropic behavior, which are identified as residuals from the model, are indications for heterogeneous transport on the mm-scale.
PET measurements were also conducted in order to display the improvement of the EDZ with waterglass injections. These experiments enable to draw conclusions on the complex reactive transport process and thus an estimation of the achieved improvement of the barrier function. The image reconstruction procedure was largely improved, mainly with the aid of Monte-Carlo simulations, and now allows quantitative analysis and error estimation.
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Enantioselektive Darstellung bioaktiver FlavanoneWitt, Morris 01 July 2014 (has links) (PDF)
Diese Dissertation beschreibt die Synthese der vier Flavanone Lonchocarpol A, 6-Dimethylallylnaringenin, Glabrol und Euchrenon A7. Des weiteren konnten drei dieser Naturstoffe enantiomerenrein mit Hilfe einer kinetischen Racematspaltung hergestellt werden. Dabei wurden die Carboxylkohlenstoffe selektiv mit einer asymmetrischen Transferhydrierung nach Noyori reduziert.
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Enantioselektive Darstellung bioaktiver FlavanoneWitt, Morris 15 January 2014 (has links)
Diese Dissertation beschreibt die Synthese der vier Flavanone Lonchocarpol A, 6-Dimethylallylnaringenin, Glabrol und Euchrenon A7. Des weiteren konnten drei dieser Naturstoffe enantiomerenrein mit Hilfe einer kinetischen Racematspaltung hergestellt werden. Dabei wurden die Carboxylkohlenstoffe selektiv mit einer asymmetrischen Transferhydrierung nach Noyori reduziert.
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Joint project: Retention of radionuclides relevant for final disposal in natural clay rock and saline systems: Subproject 2: Geochemical behavior and transport of radionuclides in saline systems in the presence of repository-relevant organicsSchmeide, Katja, Fritsch, Katharina, Lippold, Holger, Poetsch, Maria, Kulenkampff, Johannes, Lippmann-Pipke, Johanna, Jordan, Norbert, Joseph, Claudia, Moll, Henry, Cherkouk, Andrea, Bader, Miriam 15 March 2016 (has links)
The objective of this project was to study the influence of increased salinities on interaction processes in the system radionuclide – organics – clay – aquifer. For this purpose, complexation, redox, sorption, and diffusion studies were performed under variation of the ionic strength (up to 4 mol/kg) and the background electrolyte.
The U(VI) complexation by propionate was studied in dependence on ionic strength (up to 4 mol/kg NaClO4) by TRLFS, ATR FT-IR spectroscopy, and DFT calculations. An influence of ionic strength on stability constants was detected, depending on the charge of the respective complexes. The conditional stability constants, determined for 1:1, 1:2, and 1:3 complexes at specific ionic strengths, were extrapolated to zero ionic strength.
The interaction of the bacteria Sporomusa sp. MT-2.99 and Paenibacillus sp. MT-2.2 cells, isolated from Opalinus Clay, with Pu was studied. The experiments can be divided into such without an electron donor where biosorption is favored and such with addition of Na-pyruvate as an electron donor stimulating also bioreduction processes. Moreover, experiments were performed to study the interactions of the halophilic archaeon Halobacterium noricense DSM-15987 with U(VI), Eu(III), and Cm(III) in 3 M NaCl solutions.
Research for improving process understanding with respect to the mobility of multivalent metals in systems containing humic matter was focused on the reversibility of elementary processes and on their interaction. Kinetic stabilization processes in the dynamics of humate complexation equilibria were quantified in isotope exchange studies. The influence of high salinity on the mobilizing potential of humic-like clay organics was systematically investigated and was described by modeling.
The sorption of Tc(VII)/Tc(IV) onto the iron(II)-containing minerals magnetite and siderite was studied by means of batch sorption experiments, ATR FT-IR and X-ray absorption spectroscopy. The strong Tc retention at these minerals could be attributed to surface-mediated reduction of Tc(VII) to Tc(IV). An influence of ionic strength was not observed.
The influence of ionic strength (up to 3 mol/kg) and background electrolyte (NaCl, CaCl2, MgCl2) on U(VI) sorption onto montmorillonite was studied. The U(VI) sorption is influenced by the background electrolyte, the influence of ionic strength is small. Surface complexation modeling was performed applying the 2SPNE SC/CE model. Surface complexation constants were determined for the NaCl and CaCl2 system and were extrapolated to zero ionic strength. Surface complexation in mixed electrolytes can be modeled applying surface complexation constants derived for pure electrolytes.
The influence of citrate on U(VI) diffusion in Opalinus Clay was studied using Opalinus Clay pore water as background electrolyte. The diffusion parameter values obtained for the HTO through-diffusion and the U(VI) in-diffusion in the absence of citric acid were in agreement with literature data. In the presence of citric acid, U(VI) diffusion was significantly retarded, which was attributed to a change in speciation, probably U(VI) was reduced to U(IV).
Larger-scale heterogeneous material effects on diffusive transport were investigated with PET. Diffusion parameters were derived by optimum fit of a FEM-model to the measurement. These parameters are in accordance with the results from 1D-through-diffusion experiments. Deviations from the simple transversal-isotropic behavior, which are identified as residuals from the model, are indications for heterogeneous transport on the mm-scale.
PET measurements were also conducted in order to display the improvement of the EDZ with waterglass injections. These experiments enable to draw conclusions on the complex reactive transport process and thus an estimation of the achieved improvement of the barrier function. The image reconstruction procedure was largely improved, mainly with the aid of Monte-Carlo simulations, and now allows quantitative analysis and error estimation.
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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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Zakládání na objemově nestálých zeminách / Foundations in Volume Unstable SoilsLegut, Dana Unknown Date (has links)
This dissertation is concerned with the foundations in volume unstable soils and objects disorders which are related to this. The thesis was focused on the study of clay and loess soils which are abundant in the geological profile of the Czech Republic. First, the formation of the two groups of soils is introduced, then their properties are examined and finally the influence of vegetation on the former type and the influence of collapsibility in the latter type are investigated. The conclusion is, in fact, a recommendation on the design of structures so that the system of clay / structure is not damaged and that structures are not subject to renovations. Several instance of problems with structures are discussed which were subject to structural repairs employing both a civil and geotechnical engineers.
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