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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.
1

Příprava a charakterizace biologicky rozložitelných kompozitů na bázi polyhydroxyalkanoátů a kávové sedliny / Preparation and characterization of biodegradable composites based on polyhydroxyalkanoates and coffee grounds

Cisáriková, Barbora January 2020 (has links)
This diploma thesis was focused on the preparation and characterization of biodegradable composites based on poly-3-hydroxybutyrate (PHB) and spent coffee grounds (SCG). The aim was to prepare biocomposites based on PHB and coffee grounds. Biocomposites were prepared by solution casting in chloroform. Films with a thickness of about 150-200 µm were prepared with the addition of 20% unmodified and modified coffee grounds. The PHB/SCG films were modified by an addition of a plasticizer and a crosslinking agent or by blending with polybutylene adipate terephthalate (PBAT). The thermal properties of the films were determined by differential scanning calorimetry. The compatibility filler/polymer matrix compatibility was assessed morphologically with the naked eye. It has been found that the direct addition of spent coffee grounds to the PHB is not suitable due to the deterioration of the morphology of the film surfaces and the formation of aggregates. The compatibility between the spent coffee grounds and the PHB was improved after the addition of the plasticizer and the crosslinking agent. However, the highest compatibility between SCG and PHB was achieved in the case of esterified coffee grounds. Another way to improve the resulting morphological properties of the films thus prepared was to use coffee grounds fractions.
2

Estrogenic activity target endocrine disrupting chemical levels and potential health risks of bottled water and water from selected distribution points in Pretoria and Cape Town

Van Zijl, Catherina January 2016 (has links)
Endocrine disrupting chemicals (EDCs) are ubiquitous in the environment and have been detected in drinking water. Although various water treatment processes can remove EDCs, chemicals can migrate from pipes that transport water and contaminate drinking water. Globally bottled water consumption is steadily rising as an alternative to tap water, but EDCs have also been detected in bottled water. Sources of EDCs in bottled water include contamination of the water source, contamination through the production process or the migration of EDCs from the packaging material. There is limited information on EDCs in drinking water and bottled water from South Africa. The aim of this study was to determine the estrogenic activity, levels of selected EDCs and the potential health risks associated with the consumption of water from selected distribution points in Pretoria (City of Tshwane) and Cape Town as well as bottled water. The study consisted of 3 phases. Phase 1 included the analysis of drinking water samples from ten water distribution points in Pretoria and Cape Town collected over four sampling periods. In phase 2, ten brands of bottled water were analysed after exposure to different storage conditions (20°C, 40°C, light and dark) for 10 days. Samples were extracted using a C18 solid phase extraction method. Estrogenic activity was assessed using the recombinant yeast estrogen screen (YES) bioassay and the T47D-KBluc reporter gene bioassay. The extracts were analysed for di(2-ethylhexyl) adipate (DEHA), di(2-ethylhexyl) phthalate (DEHP), diisononylphthalate (DINP), dibutyl phthalate (DBP), bisphenol A (BPA), nonylphenol (NP), 17β-estradiol (E2), estrone (E1) and ethynylestradiol (EE2) using UPLC-MS. Phase 3 consisted of a scenario based health risk assessment to assess the carcinogenic and toxic human health risks associated with the consumption of distribution point and bottled water. All the samples were below the detection limit (dl) in the YES bioassay, but estrogenic activity was detected in bottled and distribution point water using the T47D-KBluc bioassay. All samples were below the 0.7 ng/L trigger value for estrogenic activity in drinking water. NP was below the dl for all the samples, E2 was detected in five distribution point samples and E1, EE2, DEHA, DEHP, DINP, DBP and BPA were detected in distribution point and bottled water samples. The estrogenic activity and levels of target chemicals were comparable to the levels found in other countries. Hazard quotients for BPA, DEHA and DINP were higher in bottled water compared to distribution point water. The greatest non-carcinogenic health risk was posed by E1 in distribution point water from Pretoria and the highest cancer risk by levels of DEHP in distribution point water from Cape Town. However, overall, health risk assessment revealed acceptable health and carcinogenic risks associated with the consumption of distribution point and bottled water. Although the potential health risks posed by the EDCs found in the water samples in this study were low, the fact that potential EDCs were found in the water samples are still of concern. A monitoring strategy that also includes water from other municipalities and other brands of bottled water are therefore recommended. / Thesis (PhD)--University of Pretoria, 2016. / School of Health Systems and Public Health (SHSPH) / PhD / Unrestricted
3

Ruminal Degradation of Polyhydroxyalkanoate and Poly(butylene succinate-co-adipate)

Galyon, Hailey Roselea 21 June 2022 (has links)
The occurrence of plastic impaction in ruminants is a growing concern. As indiscriminate feeders, cattle may consume plastic foreign materials incorporated into their diets and it is currently estimated that 20% of cattle contain plastic foreign materials in their rumen. These materials are indigestible and accumulate for the lifetime of the animal. As these materials accumulate, they may reduce feed efficiency and production by erosion and ulceration of rumen epithelium, stunting of papillae, blockage of the reticulo-omasal orifice, and leaching of toxic heavy metals. It is necessary to reduce the incidences of plastic impaction in domestic ruminants. Using polyhydroxyalkanoate (PHA) and poly(butylene succinate-co-adipate) (PBSA) biodegradable materials for feed storage products such as bale netting could reduce the incidences and effects of polyethylene-based plastic impaction in ruminants. The objectives of these studies were to evaluate the degradability of PHA and PBSA materials in the reticulorumen via in vitro, in situ, and in vivo methods. Our hypothesis was that these materials would degrade in the rumen and that a melt-blend of PHA and PBSA may degrade faster than its individual components. An in vitro study incubated a proprietary PHA-based polymer, PBSA, and PBSA:PHA melt blend nurdles, and forage controls in rumen fluid for up to 240h in DaisyII Incubators. Mass loss was measured, and digestion kinetic parameters were estimated. Thermogravimetric and differential scanning calorimetry analyses were conducted on incubated samples. Results indicated that the first stage of degradation occurs within 24h and PHA degrades slowly. Degradation kinetics demonstrated that polymer treatments were still in the exponential degradation phase at 240h with a maximum disappearance rate of 0.0031%/h, and mass loss was less than 2% for all polymers. Melting temperature increased and onset thermal degradation temperature decreased with incubation time, indicating structural changes to the polymers starting at 24h. Further in situ degradation, however, indicated these biodegradable materials degrade at more accelerated rates in the rumen. Polyhydroxyalkanote, PBSA, PBSA:PHA blend, and low-density polyethylene (LDPE) films were incubated in the rumens of three cannulated, non-lactating Holsteins for 0, 1, 14, 30, 60, 90, 120, and 150d. In situ disappearance (ISD) and residue length were assessed after every incubation time. Polyhydroxyalkanoate achieved 100% degradation by 30d, with initiation occurring at 14d indicated by ISD and a reduction in residue length. The fractional rate of disappearance of PHA was 7.84%/d. Poly(butylene succinate-co¬-adipate) and Blend did not achieve any significant ISD, yet fragmentation of PBSA occurred at 60d and the blend at just 1d likely due to abiotic hydrolysis. Low-density polyethylene achieved no ISD and residue length did not change over incubation time. From these results, we proposed a PBSA:PHA blend is a valid alternative to polyethylene single-use agricultural plastic products based on its fragmentation within 1d of incubation. Administration of PBSA:PHA film boluses compared to LDPE films and a control further supported this dissemination. Holstein bull calves (n = 12, 62 ± 9d, 74.9 ± 8.0kg) were randomly allocated to one of three daily bolus treatments: 13.6g of PBSA:PHA in 4 gelatin capsules (Blend), 13.6g of LDPE in 4 gelatin capsules (LDPE), or 4 empty gelatin capsules (Control) for 30d. Hemograms were conducted on blood samples collected on d0 and d30. On d31, animals were sacrificed to evaluate gross rumen measurements and pathology, determine papillae length, and characterize polymer residues present in rumen contents. Feed intake, body weight, body temperature, and general health were determined throughout the study. No animals presented any symptoms related to plastic impaction and animal health was not particularly affected by treatment. Daily grain and hay intake, body weight, rectal temperature, hematological parameters, gross rumen measurements and pathology, and rumen pH and temperature were not affected by treatment. There was evidence that degradation of PBSA:PHA may release byproducts that support rumen functionality. Methylene blue reduction time of Blend calves tended to be decreased by 30% compared to LDPE calves, and caudal ventral papillae length of Blend calves were 50% longer than those of Control animals. Though studies are needed to specifically elucidate the production of byproducts due to degradation of PBSA:PHA and their correlations. Polymer accumulation and residue length differed among treatments. Calves dosed with LDPE retained 6.7% of the dosed polymer, undegraded, while Blend calves retained 0.4% of the dosed polymer. The polymer residues in Blend calves were 10% of their original size. Single-use agricultural plastics developed from PBSA:PHA may be a suitable alternative to LDPE-based products in the case of ingestion in ruminants due to no acute health inflictions, fragmentation of polymers with 1d, and improved clearance from the reticulorumen. As such, utilization of these materials may reduce the incidences of plastic impaction in ruminants in commercial operations. Further long-term feeding studies are needed to evaluate specific byproduct production of PBSA:PHA and their potential influences on rumen function and animal health and production in normal commercial conditions. / Master of Science in Life Sciences / Plastic feed-storage materials may unintentionally be incorporated into animal feeds. Net wraps and bale twines may be stuck or left on forages when they are ground and incorporated into mixed rations. As cattle are largely non-selective, they may inadvertently consume these plastic materials. Approximately 20% of cattle contain plastic foreign materials in their rumen. These materials are indigestible and accumulate for the animal's lifetime. As plastics build up in the rumen, they may reduce feed efficiency, body weight, and milk production by damaging the rumen lining, blocking the digestive tract, and leaching toxic heavy metals. Therefore, it is necessary to reduce the incidences of plastic impaction in domestic ruminants to improve their health and productivity. Using biodegradable materials that degrade by bacteria, such as polyhydroxyalkanoate (PHA) and poly(butylene succinate-co-adipate) (PBSA), for feed storage products could reduce the occurrence and effects of plastic impaction in ruminants due to the materials' potential degradation in and passage from the rumen. The objectives of these studies were to evaluate the breakdown of PHA and PBSA materials in the rumen. Our hypothesis was that these biodegradable materials would degrade in the rumen and that a blend of PHA and PBSA may degrade faster than its individual components. In our first study, PHA, PBSA, a PBSA:PHA blend, and forage controls were incubated in rumen fluid for up to 240h. Mass loss, degradation rate, and the structure of polymers were determined over incubation time. Results indicated that biodegradable polymers may begin to break down within 24h. Polymer treatments were still in the early stages of degradation at 240h with a maximum degradation rate of 0.0031%/h, and mass loss of polymers was less than 2%. However, within 24h, the structures of polymers may have altered to promote future degradation at longer incubation times. Accelerated degradation was observed when PHA, PBSA, PBSA:PHA (Blend), and polyethylene (LDPE) films were incubated in the rumens of three Holstein cows up to 150d. Mass loss and the length of the remaining polymers were assessed monthly. Polyhydroxyalkanoate began to degrade by 14d and completely degraded by 30d with a disappearance rate of 7.84%/d. The remaining polymer did not achieve any mass loss. However, PBSA and Blend residue size began to decrease by 60d and 1d, respectively. Based on Blend's structural degradation within 1d of incubation that may promote its clearance from the rumen if ingested, we proposed that the material may be an alternative to polyethylene single-use agricultural plastic products. When Blend films were fed to calves, breakdown of the material further supported our dissemination that PBSA:PHA may be a suitable alternative to LDPE in the case of animal ingestion. Holstein bull calves (n = 12, 62 ± 9d, 74.9 ± 8.0kg) were randomly allotted to one of three daily bolus treatments: 13.6g of PBSA:PHA (Blend), 13.6g of polyethylene (LDPE), or no polymer (Control) distributed over 4 gelatin capsules for 30d. Feed intake, body weight, body temperature, and general health were determined throughout the study. Blood analyses were conducted on blood samples collected before and after the experimental period. On d31, animals were sacrificed to evaluate rumen growth and health, measure rumen papillae length, and describe polymers that may reside in the rumen. No animals presented any signs related to plastic impaction and animal health was not particularly affected by treatment. Daily grain and hay intake, body weight, rectal temperature, blood parameters, and rumen growth and health were not affected by treatment. There was evidence that degradation of Blend may support rumen function. Methylene blue reduction time of Blend calves tended to be decreased by 30% compared to LDPE calves, which indicates the rumen microbiome of Blend calves may better ferment feeds. Papillae length of Blend calves were also 50% longer than those of Control animals, which would improve the absorption of nutrients. Byproduct formation from Blend degradation could explain this; however, studies are needed to specifically elucidate the production of byproducts and their relationship to rumen function. Polymer accumulation and residue length differed among treatments. Calves dosed with LDPE retained 6.7% of the dosed polymer, undegraded, while Blend calves retained 0.4% of the dosed polymer. The polymer residues in Blend calves were 10% of their original size. Single-use agricultural plastics developed from PBSA:PHA may be a suitable alternative to polyethylene-based products in the case of ingestion in ruminants due to no short-term health inflictions, the reduced polymer size within 1d, and improved clearance from the rumen. As such, utilization of these materials may reduce the incidences of plastic impaction in ruminants in commercial operations. Further long-term feeding studies are needed to evaluate specific byproduct production of PBSA:PHA and their potential influences on rumen function and animal health and production in normal commercial conditions.
4

SÃntese de Derivados de Vitamina A utilizando Lipase de Candida antartica Imobilizada (Novozyme 435) / Vitamin A derivatives synthesis using immobilized lipase from Candida antarctica (Novozyme 435)

Ana Karine Pessoa Bastos Siqueira 31 August 2007 (has links)
O objetivo desta dissertaÃÃo foi sintetizar derivados de vitamina A por rota enzimÃtica, como alternativa à rota quÃmica, que à caracteristicamente mais agressiva ao meio ambiente. A sÃntese do palmitato de retinila resultaria em produto com melhor aceitaÃÃo de mercado, jà que à mais estÃvel do que o Ãster que foi utilizado como substrato, acetato de retinila. Jà a sÃntese de adipato de retinila, tinha como principal finalidade, disponibilizar um novo derivado de vitamina A. Para ambos, visava-se a aplicaÃÃo nas indÃstrias farmacÃutica, cosmÃtica e alimentÃcia. Nesse contexto, utilizou-se lipase de Candida antarctica tipo B imobilizada (Novozyme 435 com 571,48 UI/g  55,47) e os substratos acetato de retinila, Ãcidos palmÃtico e adÃpico. AlÃm destes, peneira molecular (PM) 3Ǻ tambÃm foi adicionada, jà que as reaÃÃes propostas liberam Ãgua para o meio reacional, desfavoredendo a sÃntese do Ãster desejado. Dois planejamentos foram realizados para se avaliar a sÃntese de palmitato de retinila, ambos em volume reacional total de 2 mL. No primeiro, trÃs variÃveis foram analisadas: proporÃÃo entre os substratos, solvente e temperatura. A quantidade de acetato de retinila foi mantida em 0,1 mmol e a do Ãcido palmÃtico variando entre 0,1 e 0,5 mmol. Levando em consideraÃÃo o coeficiente de partiÃÃo do Ãcido utilizado, foram testados tolueno e hexano. As temperaturas variaram entre 25 e 40ÂC, de acordo com o planejamento fatorial 23 blocado com ponto central. No segundo, estudou-se a influÃncia da quantidade de lipase (25, 50 e 75 mg) e PM (20, 50, 80 mg) em tolueno e hexano, conforme planejamento fatorial 32. Ensaios em maior escala foram realizados nÃo apenas para o palmitato, o qual foi submetido a teste de estabilidade tÃrmica, mas tambÃm para o adipato, que por nÃo ser comercializado precisou ser separado da reaÃÃo e identificado por ressonÃncia magnÃtica nuclear. Com uma anÃlise estatÃstica dos resultados, pÃde-se observar que os parÃmetros que tiveram efeito significativo no primeiro planejamento, foram a temperatura e a interaÃÃo desta com a razÃo molar entre os substratos. No segundo, tanto a enzima como a relaÃÃo quadrÃtica da PM foram significantes no rendimento de sÃntese com tolueno, e apenas a enzima, quando utilizado o hexano. A separaÃÃo do palmitato de retinila foi realizada em coluna de sÃlica C18, tendo sido avaliada em calorimetria exploratÃria diferencial (do inglÃs, differencial screening calorimetry - DSC) e observado eventos tÃrmicos por volta de 6,54ÂC. Quanto ao adipato de retinila, nenhum procedimento de separaÃÃo foi eficaz para a separaÃÃo da mistura formada entre o mesmo e o adipato de diretinila. / The main objective of this work was to synthesize vitamin A derivatives through an enzymatic route, as an alternative to chemistry route, more aggressive to the environment. The conversion of retinyl acetate into retinyl palmitate would result in a product with better market acceptance, since it is more stable than the ester used as substrate. Retinyl adipate synthesis, on the other hand, was studied in order to prepare a new vitamin A derivative. Both Vitamin A derivatives synthesized in this work were aiming the industrial production of cosmetics and foods. In this context, immobilized Candida antarctica type B lipase (Novozyme 435 with 571,48 UI/g  55,47) was used to catalyze the conversion of the substrates retinyl acetate, palmitic and adipic acids. In addition to these, molecular sieves was also added since the proposed reactions release water to the reaction media, which is not favorable to the desired ester synthesis. The retinyl palmitate synthesis was investigated by two factorial experimental design, using a total reactional volume of 2 mL. In the first, three variables were analyzed: rate between substrates, type of solvent and temperature. Retinyl acetate was kept in 0,1 mmol and palmitic acid varied between 0,1 and 0,5 mmol. Considering the acid partition coefficient, toluene and hexane were tested as solvents. The temperatures varied between 25 and 40ÂC, following a 23 factorial experimental design blocked with central points. In the second design, the influence of lipase (25, 50 e 75 mg) and molecular sieves (20, 50, 80 mg) amounts were studied using toluene or hexane as solvent, in accordance with a 32 factorial design. Experiments in a larger scale were performed not only to the produce retinyl palmitate, which was submitted to termic stability tests, but also to retinyl adipate, which is not commercially available and thereof it was recovered from the reactional media and identified by nuclear magnetic resonance. The statistical analysis of the results allowed the observation of significant effects. In the first planning, temperature and their interaction with the molar rate between the substrates were the significant variables. In the second, enzyme and the molecular sieves quadratic relation were significant in the yield of synthesis with toluene, but only the enzyme was significant when hexane was utilized. The retinyl palmitate separation was performed in silica C18 column and the purified sample was analyzed by differential scanning calorimetric â DS with a thermal event around 6.54ÂC. In the case of retinyl adipate, no separation procedure was effective since there is a mixture formed between retinyl and diretinyl adipates.
5

Environmentally Friendly Plasticizers for PVC : Improved Material Properties and Long-term Performance Through Plasticizer Design

Lindström, Annika January 2007 (has links)
Linear and branched poly(butylene adipate) polyesters with number-average molecular weights ranging from 700 to 10 000 g/mol, and degrees of branching ranging from very low to hyperbranched were solution cast with PVC to study the effects of chemical structure, molecular weight, end-group functionality, and chain architecture on plasticizing efficiency and durability. Miscibility was evaluated by the existence of a single glass transition temperature and a shift of the carbonyl group absorption band. Desirable mechanical properties were achieved in flexible PVC films containing 40 weight-% of polyester plasticizer. Methyl-ester-terminated polyesters with a low degree of branching and an intermediate molecular weight enhanced the plasticizing efficiency, as shown by greater elongation, good miscibility, and reduced surface segregation. A solid-phase extraction method was developed to extract the low molecular weight products that migrated from pure poly(butylene adipate) and PVC/ poly(butylene adipate) films during aging in water. The effects of branching, molecular weight, end-group functionality, and polydispersity on plasticizer permanence were evaluated by quantification of low molecular weight hydrolysis products, weight loss, surface segregation, and the preservation of material properties during aging. A more migration-resistant polymeric plasticizer was obtained by combining a low degree of branching, hydrolysis-protecting end-groups, and higher molecular weight of the polyester. Films plasticized with a slightly branched polyester showed the best durability and preservation of material and mechanical properties during aging. A high degree of branching resulted in partial miscibility with PVC, poor mechanical properties, and low migration resistance. The thermal stability of polyester-plasticized films was higher than that of films containing a low molecular weight plasticizer, and the stabilizing effect increased with increasing plasticizer concentration. / QC 20100805
6

Poly (butylene succinate) and poly (butylene adipate) : quantitative determination of degradation products and application as PVC plasticizers

Lindström, Annika January 2005 (has links)
<p>A solid phase extraction (SPE) method was developed for simultaneous extraction of dicarboxylic acids and diols formed during hydrolysis of poly(butylene succinate), PBS, and poly(butylene adipate), PBA. The developed SPE method and subsequent GC-MS analysis were used to extract, identify and quantify low molecular weight products migrating from linear and branched poly(butylene adipate) (PBA) and poly(butylene succinate) (PBS) during aging in aqueous media. The combination of SPE and GC-MS proved to be a sensitive tool, able to detect small differences in the degradation rate during early stages of hydrolysis before any significant differences were observed by weight loss and molecular weight measurements. The detected low molecular weight products included monomers i.e. adipic acid and 1,4-butanediol for the PBA polymers and succinic acid and 1,4-butanediol for PBS. Several dimers and trimers i.e. hydroxybutyl adipate, hydroxybutyl succinate, di(hydroxybutyl) adipate, di(hydroxybutyl) succinate and hydroxybutyl disuccinate were also detected. Best extraction efficiency for 1,4-butanediol and succinic acid was achieved with a hydroxylated polystyrene-divinylbenzene resin as solid phase. Linear range for the extracted analytes was 1-500 ng/ml for adipic acid and 2-500 ng/ml for 1,4-butanediol and succinic acid. Detection and quantification limits for all analytes were between 1-2 ng/ml (S/N=3) and 2-7 ng/ml (S/N=10) respectively. Relative standard deviations were between 3 % and 7 %. Comparison of measured weight loss and the amount of monomeric products showed that weight loss during early stages of hydrolysis was mainly caused by the release of water-soluble oligomers that on prolonged ageing were further hydrolyzed to monomeric species. Significant differences in degradation rate could be assigned to degree of branching, molecular weight, aging temperature and degradation medium.</p><p>Linear and branched PBA was mixed with PVC in solution cast films to study the effects of molecular weight and branching on plasticizer efficiency. Used as polymeric plasticizer, PBA formed a semi-miscible two-phase system with PVC where the amorphous part exhibited one single glass transition temperature and the degree of polyester crystallinity was dependent on molecular weight, degree of branching and blend composition. Plasticizing efficiency was favored by higher degree of branching and a 40 weight-percent polyester composition.</p>
7

New Engineered Materials from Biobased Plastics and Lignin

Chen, Richard 11 January 2013 (has links)
The blending of lignin as a component in a thermoplastic blend poses a challenge in the form of dispersion and compatibility. Polyesters such as poly(lactic acid) and poly(butylene adipate-co-terephthalate) offer the best opportunity of compatibility in melt blending with lignin due to their ability to form hydrogen bonds. The fractionation of lignin into more homogeneous fractions offers better dispersion and more consistent properties, retaining the toughness of the original polymer in addition to bridging stress transfer between PLA and PBAT. Functionalization of lignin was done by lactic acid grafting. The resulting blend of PLA/PBAT/modified fractionated lignin showed improved interaction between lignin and PLA, but reduced compatibility between lignin and PBAT. This thesis provides a deeper understanding on the effect of lignin heterogeneity, its fractions, and the functionalization of lignin on lignin and bioplastic blends to further the use of a largely produced industrial by-product in high value applications. / Natural Sciences and Engineering Research Council (NSERC) – Lignoworks Biomaterials and Chemicals Strategic Research Network, Canadian Foundation for Innovation (CFI), Ontario Ministry of Agriculture, Food and Rural Affairs (OMAFRA)
8

Structural Characterization and Quantitative Analysis by Interfacing Liquid Chromatography and/or Ion Mobility Separation with Multi-Dimensional Mass Spectrometry

Solak, Nilüfer 21 May 2010 (has links)
No description available.
9

Poly (butylene succinate) and poly (butylene adipate) : quantitative determination of degradation products and application as PVC plasticizers

Lindström, Annika January 2005 (has links)
A solid phase extraction (SPE) method was developed for simultaneous extraction of dicarboxylic acids and diols formed during hydrolysis of poly(butylene succinate), PBS, and poly(butylene adipate), PBA. The developed SPE method and subsequent GC-MS analysis were used to extract, identify and quantify low molecular weight products migrating from linear and branched poly(butylene adipate) (PBA) and poly(butylene succinate) (PBS) during aging in aqueous media. The combination of SPE and GC-MS proved to be a sensitive tool, able to detect small differences in the degradation rate during early stages of hydrolysis before any significant differences were observed by weight loss and molecular weight measurements. The detected low molecular weight products included monomers i.e. adipic acid and 1,4-butanediol for the PBA polymers and succinic acid and 1,4-butanediol for PBS. Several dimers and trimers i.e. hydroxybutyl adipate, hydroxybutyl succinate, di(hydroxybutyl) adipate, di(hydroxybutyl) succinate and hydroxybutyl disuccinate were also detected. Best extraction efficiency for 1,4-butanediol and succinic acid was achieved with a hydroxylated polystyrene-divinylbenzene resin as solid phase. Linear range for the extracted analytes was 1-500 ng/ml for adipic acid and 2-500 ng/ml for 1,4-butanediol and succinic acid. Detection and quantification limits for all analytes were between 1-2 ng/ml (S/N=3) and 2-7 ng/ml (S/N=10) respectively. Relative standard deviations were between 3 % and 7 %. Comparison of measured weight loss and the amount of monomeric products showed that weight loss during early stages of hydrolysis was mainly caused by the release of water-soluble oligomers that on prolonged ageing were further hydrolyzed to monomeric species. Significant differences in degradation rate could be assigned to degree of branching, molecular weight, aging temperature and degradation medium. Linear and branched PBA was mixed with PVC in solution cast films to study the effects of molecular weight and branching on plasticizer efficiency. Used as polymeric plasticizer, PBA formed a semi-miscible two-phase system with PVC where the amorphous part exhibited one single glass transition temperature and the degree of polyester crystallinity was dependent on molecular weight, degree of branching and blend composition. Plasticizing efficiency was favored by higher degree of branching and a 40 weight-percent polyester composition. / QC 20101209
10

Charakterizace vyfukovaných fólií z měkčeného polylaktidu / Characterization of blowing films from softened polylactide

Kubíček, Václav January 2020 (has links)
The master's thesis focuses on preparation of blown films from polylactid acid (PLA) which was blended with selected polyesteres – poly(butylene adipate-co-terephtalate) (PBAT), polycaprolactone (PCL) and polybutylene succinate (PBS) – and thermoplastic starch (TPS) in amount of 30% in order to soften PLA films. The influence of the aditives on static and mechanical tensile properties, on structure, morphology and thermal properties of the films was determined and the obtained parameters were compared to properties of films prepared from neat PLA and high density polyethylene (HDPE). The results showed that the additives increased crystalinity of PLA and thus significantly influenced the properties of the films. In contrast to the film from neat PLA, softening in terms of lowering glass transition temperature occured only by adding PBS and TPS, in terms of increasing ductility only by adding PBAT. All PLA films showed nearly constant elastic modulus up to the beginning of glass transition enabling their potential application till 50 °C. Preparation of the film with TPS was problematic and the film showed the worst mechanical properties. Preparation of other films was without any problems. The most promising additive from the tested ones was PBAT which showed comparable mechanical properties as the film from HDPE.

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