De par ses propriétés thermomécaniques proches des polyoléfines, le poly(butylene succinate)est l’un des polymères biosourcés les plus attractifs pour la substitution de matériaux pétro-sourcés pour des applications automobiles. L’incorporation de fibres de chanvre, via une étape d’extrusion,renforce la matrice et permet de tendre vers les propriétés cibles exigées par les cahiers des charges automobiles pour les applications visées dans cette étude. Afin d’améliorer les propriétés thermomécaniques de ce matériau, trois sujets ont été développés dans cette étude :1- Qualification de l’interface PBS / fibres de chanvre : via une nouvelle méthodologie basée sur l’analyse de la contribution effective des fibres sur la contrainte (CFC) durant une sollicitation mécanique, il est montré que les liaisons hydrogène formées entre le PBSet la fibre influent fortement sur les mécanismes de transfert de charge. Couplée au modèle de Bowyer et Bader, cette approche permet d’identifier les mécanismes d’endommagement de l’interface et de quantifier la contrainte interfaciale (τchanvre/PBS=25,2MPa).2 - Signification du ratio L/D d’une fibre naturelle : au cours des procédés de mises en oeuvre (extrusion et injection), la morphologie d’une fibre végétale évolue et apparait complexe due à la structure branchée engendrée par la fibrillation. A partir d’une nouvelleméthodologie d’analyse d’images spécifiquement développée, il est montré que la fibrillation contribue au renforcement de la matrice au même titre que le défibrage.3 -Synthèse de PBS-co-amides : afin de couvrir les contraintes thermomécaniques exigées,l’introduction de groupements amide dans le PBS est étudiée pour augmenter le point de fusion du polymère. Afin de contourner notamment la réaction parasite de cyclisation entre l’acide succinique et les amines, une stratégie de synthèses multi-étapes de monomères et de poly(ester-amide) est étudiée permettant d’obtenir un PEA de faible masse molaire dont le point de fusion atteint 172°C. / With its thermomechanical properties closed to polyolefins, poly(butylene succinate) is one ofthe most interesting bio-based polymers for substitution of oil-based polymers for automotive applications. Addition of hemp fibers, through an extrusion process step, reinforces matrix and enables to fit with the targeted technical profile required by automotive specifications. In order to improve thermomechanical properties, three main topics have been investigated in this study:1 - PBS / hemp fibers interface qualification: through a new methodology based on the analysis of the effective fiber contribution on stress during mechanical solicitation, it was shown that hydrogen bonds between PBS and fibers play a major role in load transfer.Combined with the Bowyer and Bader model, this approach enables to highlight interface damages and to determine the interfacial shear strength (τhemp/PBS=25,2 MPa)2 - Meaning of natural fiber L/D ratio: during processes (extrusion and injection), vegetal fiber morphology changes and becomes complex due to the fibrillated structure. With anew developed image analysis tool, it was shown that fibrillation contributes to matrix einforcement as well as defibering.3 - Synthesis of PBS-co-amide: to reach the targeted thermomechanical performances,introduction of amide groups into PBS was studied to increase the melting point. In order to avoid the cyclic imide formation between succinic acid and amines, synthesis of monomers and poly(ester amide) were studied through a multistep strategy, enabling to get low molecular weight PEA with melting temperature around 172°C.

Poly(butylene succinate) (PBSu) and two poly(butylene succinate-co-propylene succinate)s (PBPSu 95/5 and PBPSu 90/10) were synthesized via the direct polycondensation reaction. The copolyesters were characterized as having 7.0 and 11.5 mol% propylene succinate (PS) units, respectively, by 1H NMR. Copolyesters were characterized as random, based on 13C NMR spectra. They were fully investigated during nonisothermal crystallization and thermal degradation through various approaches in this study. A differential scanning calorimeter (DSC) and a polarized light microscope (PLM) adopted to study the nonisothermal crystallization of these polyesters at a cooling rate of 1, 2, 3, 5, 6 and 10 ºC/min. Morphologies and the isothermal growth rates of spherulites under PLM experiments were monitored and obtained by curve-fitting, respectively. These continuous rate data were analyzed with the Lauritzen-Hoffman equation. A transition of regime II ¡÷ III was found at 95.6, 84.4, and 77.3 ºC for PBSu, PBPSu 95/5, and PBPSu 90/10, respectively. DSC exothermic curves show that all of the nonisothermal crystallization occurred in regime III. DSC data were analyzed using modified Avrami, Ozawa, Mo, Friedman and Vyazovkin equations. Ozawa equation does not accurately describe the nonisothermal crystallization kinetics of this polyester because part of the crystallization is secondary crystallization. All the results of PLM and DSC measurements indicate that incorporation of minor PS units into PBSu markedly inhibits the crystallization of the resulting polymer. The melting behavior of nonisothermally crystallized samples presents a continuous melting¡Vrecrystallization¡Vremelting process. Additionally, three absorption bands during the nonisothermal crystallization were identified for PBSu and two PBPSu copolyesters, namely, 916, 955, 1045 cm-1 in the attenuated total reflectance FTIR spectra. Thermogravimetric analysis (TGA)-FTIR was heated at 5 ºC/min under N2 to monitor the degradation products of these three polyesters. FTIR spectra revealed that the major products were anhydrides, which were obtained following two cyclic intramolecular degradation mechanisms by breaking the weak O-CH2 bonds around a succinate group. Thermal stability at heating rates of 1, 3, 5, and 10 ºC/min under N2 was investigated using TGA. The model-free methods of Friedman and Ozawa equations are useful for studying the activation energy of degradation in each period of mass loss. The results reveal that the random incorporation of minor PS units into PBSu did not markedly affect their thermal resistance. Two model-fitting mechanisms were used to determine the loss mass function f(£\), the activation energy and the associated mechanism. The mechanism of autocatalysis nth-order, with f(£\)=£\m(1-£\)n, fitted the experimental data much more closely than did the nth-order mechanism given by f(£\)=(1-£\)n. The obtained activation energy was used to estimate the failure temperature (Tf). The values of Tf for a mass loss of 5% and an endurance time of 60,000 hr are 160.7, 155.5, and 159.3 ºC for PBSu and two the copolyesters, respectively.

Three series copolyesters [poly(butylene succinate-co-propylene succinate) (PBPSu), poly(butylene succinate-co-2-methyl-1,3-propylene succinate) (PBMPSu) and poly(ethylene succinate-co-butylene succinate) (PEBSu)] and their homopolyesters [poly(butylene succinate) (PBSu), poly(ethylene succinate) (PESu), poly(propylene succinate) (PPSu) and poly(2-methyl-1,3-propylene succinate) (PMPSu)] were synthesized by a two-step reaction (esterification and polycondensation) with titanium tetraisopropoxide as the catalyst. Molecular weights of all synthesized polyesters were determined by intrinsic viscosity and gel permeation chromatography (GPC) measurements. The values of intrinsic viscosity (0.97 ~ 1.62 dL/g) and relative molecular weight (2.4x10000 ~ 11.9x10000 g/mol) indicate that these polyesters can be made into films without complications. Compositions and sequence distributions of copolyesters were determined by analyzing the spectra of 1H NMR and 13C NMR. The randomness values of these copolyesters are closed to 1.0 that represents random sequence distribution of the comonomers. Thermal properties and stabilities were characterized using differential scanning calorimeter (DSC) and thermogravimetric analyzer (TGA), respectively. All copolyesters exhibited a single glass transition temperature (Tg). For PBPSu copolyesters, incorporating propylene succinate units to PBSu not only narrows the window between Tg and melting temperature (Tm), but also retards the cold crystallization ability, thereby lowering the crystallinity to a considerable extent. This phenomenon also occurred in PBMPSu and PEBSu copolyesters when the 2-methyl-1,3-propylene succinate (MPS) and butylene succinate (BS) units were incorporated into PBSu and PESu, respectively. Tstart is the temperature of first detectable deviation from the derivative curve of weight loss. Tstarts of all synthesized polyesters around 240 £jC, higher than the temperature of polycondensation reaction (220 £jC), demonstrates that there is no necessity of using a thermal stabilizer during the synthesis of these polyesters. Additionally, the thermal stability does not vary significantly with compositions in the same series polyester. Wide-angle X-ray diffractograms (WAXDs) at room temperature were obtained from polyesters crystallized isothermally at a temperature around 5-20 £jC below their melting temperatures. WAXD patterns of two series polyesters elucidated that the incorporation of PS or MPS units into PBSu markedly inhibits the crystallization behavior of PBSu. The phenomenon also occurred in PEBSu copolyesters when BS units were incorporated into PESu. Results of WAXD and DSC measurements showed that PMPSu is a amorphous polyester. The retarding effect on crystallization by methyl substituents on the polymer chain is efficient.

Poly butylene succinate (PBS) is a biodegradable plastic polymer that has physical and mechanical properties similar to common petroleum plastics like polypropylene (PP) and polyethylene (PE). PBS may be produced from petroleum or bio-based feedstocks, or by a hybrid combination of petroleum and bio-based resources. Producers are reducing content of petroleum components used for the production of PBS, and by doing so are seeking potential environmental performance improvements. In this study, ???hybrid??? PBS refers to the production of PBS polymer from bio-based succinic acid (SAC) sourced from sorghum and petroleum-based 1, 4-butanediol (BDO). Given its biodegradability, PBS is commercially used for compostable bags and agricultural mulching film applications. A recent study in Ontario identified composite materials made with PBS blended with natural fibres like switchgrass (SG) as promising for applications in automotive products. Such novel composite materials are touted as potential bio-based alternatives to conventional petroleum-based plastics. Of the few studies that have considered the environmental performance of PBS materials, none have assessed the potential environmental impacts of a hybrid PBS composite. Therefore, this study undertook a life cycle assessment (LCA) of SG reinforced hybrid PBS composite (hybrid composite). LCA is an environmental management technique that is used to assess environmental aspects (inputs and outputs) and potential environmental impacts of a product or service throughout its life cycle. The analysis considered a cradle-to-gate system boundary and evaluated eleven environmental performance indicators. The environmental performance of the hybrid composite was compared to a conventional glass fibre (GF) reinforced polypropylene (PP) composite (baseline composite), a material that is widely used in automotive components. Results showed that the production of the hybrid composite in comparison to the baseline composite decreased potential impact for most of the assessed indicators: cumulative energy demand by 40%, waste heat by 23%, global warming potential by 35%, smog by 2%, carcinogens by 54%, non-carcinogens by 172%, respiratory effects by 22% and ecotoxicity by 45%. Increases in the values of impact indicators were apparent for ozone depletion, acidification, and eutrophication by 43%, 16%, and 322%, respectively. Analysis revealed that dominant influences on results were not related directly to the bio-based make-up. Rather, the biggest influence on the environmental performance of composite production were the sources of heat used in petroleum-based materials, the energy mix in electricity for bio-based materials, the type of reinforcing fibre and the co-product treatment methodology used. The study helps fill a gap in knowledge regarding bio-based chemicals and hybrid biodegradable plastic composites, and points to opportunities for future research on feedstocks for industrial composite materials. The importance of this study is that it helps to identify the environmental strengths and weaknesses associated with the production of the hybrid composite specifically, and bio-based materials more generally. It points to alternative material substitution options for use in the automotive industry. In this study, life cycle assessment exemplifies multidisciplinary methodologies, which seek to traverse the boundaries between the social and natural sciences and disciplines to support more sustainable policy decisions for a bio-economy. The systematic nature and the widely applicable consequences of this LCA study have the potential to contribute to industrial and business management, and reach the public policy arena in an effort to drive environmental and social change.

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.

<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>

In this study, traditional Japanese washi paper was sandwiched with poly(butylene succinate)(PBS) in order to produce a paper-based composite material that can be biologically degraded. Specimens were prepared using a hot press, and the mechanical properties of the washi paperand the new composite material were investigated by tensile tests. The cross-sections of specimens were then observed with a digital microscope as well as by scanning electron microscope (SEM) analysis. The microscope images indicated that therelatively hollow washi provides a structure for the polymer to settle into, which could contribute to the improved strength of the composite material. Specimens made from three layers of washipaper and combined with two layers of PBS film had remarkable mechanical propertiesincluding a UTS of 95 MPa.The composite material was incubated in compost and a MODA C-S (Microbial Oxidative Degradation Analyzer) was used to evaluate its biodegradability. The material showed good biodegradability with significant losses of mass (-32 %) as well as major loss of mechanical strength after four weeks of incubation. The biodegradability of the material will be further investigated.

As nanocomposites provide considerable improvements in material properties, scientists and engineers are focussing on biodegradable nanocomposites having superior material properties as well as degradability. This thesis has investigated the properties of biodegradable nanocomposites of the aliphatic thermoplastic polyester, poly (lactide acid) (PLA) and the synthetic biodegradable polyester, poly (butylene succinate) (PBS). To enhance the properties of this blend, nanometer-sized clay particles, have been added to produce tertiary nanocomposite. High aspect ratio and surface area of clay provide significant improvement in structural, mechanical, thermal and barrier properties in comparison to the base polymer. In this study, a series of PLA/PBS/layered silicate nanocomposites were produced by using a simple twin-screw extruder. PLA/PBS/Cloisite 30BX nanocomposites were prepared containing 1, 3, 5, 7 and 10 wt% of C30BX clay, while PLA and PBS polymers compositions were fixed at a ratio of 80 to 20. This study also included the validation of a gas barrier model for these biodegradable nanocomposites. WAXD indicated an exfoliated structure for nanocomposites having 1 and 3 wt% of clay, while predominantly development of intercalated structures was noticed for nanocomposites higher than 5 wt% of clay. However, TEM images confirmed a mixed morphology of intercalated and exfoliated structure for nanocomposite having 1 wt% of clay, while some clusters or agglomerated tactoids were detected for nanocomposites having more than 3 wt% of clay contents. The percolation threshold region for these nanocomposites lied between 3-5 wt% of clay loadings. Liquid-like behaviour of PLA/PBS blends gradually changed to solid-like behaviour with the increase in concentration of clay. Shear viscosity for the nanocomposites decreased as shear rate increased, exhibiting shear thinning non-Newtonian behaviour. Tensile strength and Young's modulus initially increased for nanocomposites of up to 3 wt% of clay but then decreased with the introduction of more clay. At high clay content (more than 3 wt%), clay particles tend to aggregate which causes microcracks at the interface of clay-polymer by lowering the polymer-clay interaction. Percentage elongation at break did not show any improvement with the addition of clay. PLA/PBS blends were considered as immiscible with each other as two separate glass transition and melting temperatures were observed in modulated differential scanning calorimetry (MDSC) thermograms. MDSC showed that crystallinity of the nanocomposites was not much affected by the addition of clay and hence some compatibilizer is required. Thermogravimetric analysis showed that the nanocomposite containing 3 wt% of clay demonstrated highest thermal stability compared to other nanocomposites. Decrease in thermal stability was noticed above 3 wt% clay; however the initial degradation temperature of nanocomposites with 5, 7 and 10 wt% of clay was higher than that of PLA/PBS blend alone. Gas barrier property measurements were undertaken to investigate the transmission of oxygen gas and water vapours. Oxygen barrier properties showed significant improvement with these nanocomposites, while that for water vapour modest improvement was observed. By comparing the relative permeabilities obtained from the experiments and the model, it was concluded that PLA/PBS/clay nanocomposites validated the Bharadwaj model for up to 3 wt% of clay concentration.

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

Au cours des dernières décennies, l’utilisation de polymères biodégradables a connu un regain d’intérêt pour des applications agricoles. Dans cette étude, nous nous concentrons sur le développement de textiles biodégradables destinés à la protection anti-insecte des cultures. Actuellement, ces textiles doivent être collectés par des entreprises après la saison agricole et entraîne un coût non négligeable pour l’utilisateur. Une alternative serait d’avoir des agro-textiles qui pourraient être collectés par l’utilisateur et minéralisés après quelques mois. Les polymères biodégradables pourraient répondre à ces objectifs. Dans cette étude, nous nous sommes concentrés sur le poly(butylene succinate) un polymère biodégradable et biosourcé. Le PBS a été synthétisé sur un pilote de polycondensation. Néanmoins, le PBS issu de cette synthèse présente de faibles propriétés rhéologiques. La structure du PBS a donc été modifiée par l’incorporation de branchements ou d’allongeurs de chaines. Les propriétés mécaniques ont également été optimisées via la synthèse de systèmes PBS/PLA transréagits et de PBS nanocomposites. Ces PBS modifiés ont été testés au filage. Finalement un fil de PBS avec 0,5% de silice sphérique a été produit à plus grande échelle et un textile a été fabriqué. Le vieillissement de ces fils PBS a été étudié et la conservation des propriétés mécaniques durant l’utilisation du fil en extérieur a été validée. Enfin, une dernière approche plus exploratoire a été testée. Elle consiste en la modification du PBS par des interactions supramoléculaires réversibles en température. / In the last decade, biodegradable polymers have gained significant interest for agricultural applications. Here we focus on the development of biodegradable textiles for insect-proof nets. Currently these textiles must be collected by specialized companies after the growing season and generate disposal cost. An ideal agrotextile would be collected by the user at the end of the growing season, and undergo full mineralization within few months. These requirements can be achieved by using biodegradable polymers. In this study, poly(butylene succinate) (PBS), a biobased and biodegradable polymer was studied. PBS was synthesized by polycondensation on a pilot plant reactor. Because of low rheological properties of the synthesized polyester, the chemical structure of PBS was modified by several approaches like chain extension or branching. The mechanical properties were tuned with the synthesis of PBS/PLA transreacted systems and PBS nanocomposites. These modified PBS were tested upon fiber spinning. Finally a PBS yarn with 0,5% spherical silica was produced at higher scale and a textile was done. Ageing of the PBS yarns was also studied and the conservation of the mechanical properties during use of the textile was validated. Lastly a more exploratory approach was tested. It is synthesis of modified PBS by supramolecular interactions, which are reversible upon temperature.