Dans cette étude, nous avons préparé deux matériaux composites conducteurs par le procédé d’électropolymérisation. Lebut de la première partie de la thèse était l’élaboration de films composites polyaniline /LiMn2O4 pour leur applicationcomme matériau de cathode dans les batteries lithium-ion. Les analyses par diffraction des rayons X, analyse EDX etspectrométrie IRTF ont confirmé l'incorporation de LiMn2O4 dans les films composites. Les analyses électrochimiquesdes films obtenus ont mis en évidence une conductivité plus élevée des films composites comparée à la conductivité desfilms de PANI. La deuxième partie a été consacrée à la préparation de l’oxyde de graphène (OG) à partir de graphiteselon 2 méthodes de synthèse dérivées de la méthode de Hummers. Les résultats obtenus ont montré que le de gréd’oxydation des feuillets n’était pas le seul critère à prendre en compte pour évaluer la stabilité du OG dans l’eau. Lesfeuillets d’OG obtenus ont été incorporés à la polyaniline par électropolymérisation d’une suspension d’OG et d’anilineen milieu neutre. Le milieu électrolytique neutre conduit à des chaînes oligomères de PANI de faible masse molaire avecune proportion significative d’unités aromatiques mono et 1,2-disubstituées dans la structure finale. Différents substratsmétalliques ont été testés et les films ont été en particulier déposés sur fer afin d’évaluer leur protection anticorrosion. / In this study, we prepared two conductive composite materials based on polyaniline (PANI) byelectrodeposition. First, we investigated the development of new polyaniline/LiMn2O4 composite films forapplication as cathode material in lithium-ion batteries. Analysis by X-ray diffraction, EDS analysis and FTIRspectroscopy confirmed the incorporation of LiMn2O4 in composite films. The electrochemical analysis of thefilms obtained showed a higher conductivity of the composite films compared to the conductivity of the filmsof PANI. The second part was devoted to the preparation of oxidized graphene (GO) from graphite by 2methods of synthesis derived from the method of Hummers. The results showed that the degree of oxidation ofthe graphene sheets was not the only criterion in assessing the stability of GO in water. Electropolymerizationof aniline in a neutral electrolyte containing GO sheets was carried out to prepare PANI-GO composite films.The neutral electrolytic medium leads to PANI oligomer chains of low molecular weight with a significantproportion of aromatic mono units and 1,2-di-substituted units in the final structure. The electrodeposition wasperformed on inert and oxidizable metals. The corrosion protection efficiency of PANI/GO composite filmswas studied in HCl corrosion medium.

Active Pharmaceutical Ingredients with poor solubility have presented significant difficulties in drug product design and development including slow and ineffective absorption leading to inadequate and variable bioavailability. Therefore it has become increasingly desirable to overcome the low aqueous solubility of drug candidates and develop more novel and innovative formulation approaches to increase the dissolution rate of the poorly soluble drugs. This work focuses on the formulation of novel amorphous ibuprofen-polymer nanoconjugates based on the polymer-drug complexation in order to improve its physical and dissolution characteristics without the use of toxic organic solvents. Plain and ibuprofen-loaded binary and ternary nanoconjugates were prepared using four modified co-precipitation techniques including melt solubilization; alkaline solubilization; surfactant solubilization and hydrotropic complexation techniques. A remarkably high loading capacity was achieved ranging from 89.05 to 99.49% across the four techniques and polymer-polymer ratio of 50:50 was found to be most efficient. All the four techniques reduced the size of ibuprofen (2.87 μm) significantly in the presence of 2.0 x10-3 mM of Diethylaminoethyl Dextran (DEAE-Dextran) in the order melt solubilization (203.25 nm) > alkaline solubilization (185.68 nm) > surfactant (Tween 80) solubilization (122.17 nm) > hydrotropic complexation (77.92 nm). 5.0 x 10-4 mM of chitosan also reduced the size of ibuprofen from 2872.12 to 10.70 nm (268-fold reduction). The FTIR spectroscopic analysis revealed electrostatic, hydrophobic and hydrogen bonding interaction between solubilized ibuprofen and the cationic polymers (DEAE-Dextran and chitosan) to form a new product (an amide). Polymer-polymer complexation also occurred between DEAE-Dextran and gellan as well as chitosan and gellan to a different extent depending on the mixing ratios. 1H and 13C NMR analysis confirmed the conjugation between ibuprofen and each of the cationic polymers as well as the formation of a new amide product. DSC thermal analysis showed that the nanoconjugates exhibited new broad and diffuse peaks confirming that they did exist in amorphous state as multiple complexes. The TGA thermograms of the binary nanoconjugates exhibited one step degradation profile compared with the physical mixture which exhibited two steps. However the ternary nanoconjugates exhibited two steps degradation profile confirming the formation of multiple complexes. Marked enhancement of drug release was achieved by the four techniques compared with the ibuprofen control. All the DG (DEAE-Dextran - Gellan) complexes exhibited a higher release profile than ibuprofen control. Fickian and non-Fickian anomalous mechanisms were deduced for the drug release of ibuprofen from the binary conjugates. The ternary nanoconjugates exhibited non-Fickian (anomalous) diffusion, Fickian diffusion and Super Case II transport release mechanisms. The ternary nanoconjugate hydrogels exhibited complete release (100%) within 48 h. The lowest concentration of DEAE-Dextran, Gellan - Ibuprofen - DEAE-Dextran (GIbDD) 2:0.125, increased the release of ibuprofen by 13.4% however higher concentrations of DEAE-Dextran decreased the release profile steadily. It was concluded that DEAE-Dextran has potentials in the formulation of modified (extended) release of ibuprofen. The most prominent mechanism of release of ibuprofen from the nanoconjugate hydrogel was Super Case II transport. SEM and AFM micrographs of the drug loaded composite pharmaceutical films exhibited concentric spheres with two and three layers for the binary and ternary films respectively. This supports the evidence of internalization of ibuprofen by the polyelectrolyte complex. The FTIR and DSC results confirmed electrostatic and hydrophobic interactions between ibuprofen and DEAE-Dextran as well as between gellan and DEAE-Dextran. Thermal analysis revealed that plain bilayer films were thermally more stable than composite films. The addition of ibuprofen significantly increased (p < 0.05, n = 4) the swelling ratio of the films compared with films without the drug. The drug loaded bilayer films exhibited Fickian diffusion mechanism while the dominating mechanism for composite films was anomalous (Non-Fickian) transport. From the foregoing, it was evident that ibuprofen-polymer nanoconjugate present a novel tool for the delivery of ibuprofen with potential application for transdermal delivery.

Thesis (Ph. D.)--University of California, San Diego, 2000. / Vita. Includes bibliographical references.

The global market for fluoropolymers, including polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), and poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), is growing rapidly due to their copious applications in the construction, automotive, medical, chemical, and electrical industries. Fluoropolymers owe their popularity partly to their excellent chemical and thermal stability and useful mechanical, piezoelectric, and ferroelectric properties. They are made into films or coatings that are used for corrosion protection or surface property enhancement. Electrophoretic deposition (EPD) has generated increasing interest in manufacturing advanced films for various applications due to its low cost, versatility, simple apparatus, and good film quality compared with other deposition techniques like dip coating, spin coating, electrospinning, or spay coating. Moreover, EPD facilitates uniform deposition on the substrates of complex shapes at a high deposition rate. The aim of this research is to develop novel biomimetic strategies for fabricating polymer films and their composite films with multifunctional particles through EPD. This method involves the electrophoresis of charged particles in a stable colloidal suspension towards an electrode, forming deposition. Fluoropolymers, however, are electrically neutral and chemically inert, and their EPD presents difficulties. Therefore, successful EPD depends on understanding how to modify the surface of polymer particles using advanced biosurfactants to impart charge and form a well dispersed, stable colloidal suspension. One strategy is to leverage the unique dispersing power of bile acids and salts as biosurfactants for EPD of PTFE and PVDF films and composite films. When doing so, it was found that the amphiphilic structure of bile salts such as sodium deoxycholate (DChNa) facilitated adsorption on the chemically inert, hydrophobic surfaces of PTFE, diamond, and carbon dots. In this strategy, DChNa acted as a charging, dispersing, film-forming agent for the co-deposition of PTFE composite films from an aqueous suspension. Water insoluble bile acids (BAs) were found to be biosurfactants for the EPD of PTFE and PVDF from organic solvents, in which lithocholic acid (LCA) was used as a co-dispersant for the fabrication of composite PTFE-diamond coatings and PTFE coatings provided corrosion protection for stainless steel in 3% NaCl solutions. The dispersing performance of four other bile acids, chenodeoxycholic acid (CDCA), deoxycholic acid (DCA), ursodeoxycholic acid (UDCA), and cholic acid (ChA), was analyzed and compared with LCA on the deposition performance of PVDF. It was found that the PVDF deposition yield obtained using different BAs increased in the order of LCA<CDCA<DCA<UDCA<ChA. This was attributed to the difference in number, position, and orientation of OH groups in the structures of the BAs. Another biomimetic strategy for the EPD of polymers and composites was inspired by the strong adsorption of mussel protein on rock surfaces in sea water. Catecholate-type molecules, caffeic acid (CA) and catechol violet (CV), were found to be biosurfactants for dispersing, charging, and depositing PVDF films and composites. Analyses of the deposition yield data, the chemical structure of the CA and CV, and the microstructure and composition of the films suggested that the aromatic rings on the CA and CV had hydrophobic interactions with the PVDF particles and that the phenolic groups formed bidentate chelating or bridging bonding to inorganic particle surfaces. The study demonstrated the feasibility of co-depositing PVDF with nanoparticles of TiO2, MnO2, and NiFe2O4. CA was also used for preparing PVDF-HFP particles and as a co-dispersant for the co-deposition of PVDF-HFP with NiFe2O4 and CuFe2O4 nanoparticles in order to make composite films that combine the ferrimagnetic properties of spinel ferrites with the multifunctional properties of ferroelectric polymers. / Dissertation / Doctor of Philosophy (PhD)

Bioplastic research has become more diverse and different types of research on bioplastic production have been conducted from fruits and vegetable waste, for example, orange waste. The wastes that come from oranges contain more than just vitamins, it has soluble sugars, starch, hemicellulose, cellulose, and pectin. The intention of this project was to study the possibility to produce bio-composite films from orange waste, after removing the soluble sugars. It was also to analyze the properties of the material by tensile strength, visual observation, and to find a methodology that suits this study. An ultrafine grinder was used to mechanically separate the cellulose fibres, with the intention to compare the fibrillation cycles on the properties of the bio-composite films. A total of 30fibrillation cycle was performed. In addition, different film casting strategies were performed and evaluated. The primary plan was to produce a biofilm without the use of chemicals. After the observing the results three new routes for the methodology was developed where the usage of chemicals was be included. The citric acid was used as a solvent for pectin and glycerol was used as a plasticizer. In the first method, different concentration of citric acid and glycerol were added and observed. The combination which gave uniformed films that contained 0.3 g of citric and 0.375 g of glycerol for a 75 ml hydrogel. The second method was to infuse citric acid before grinding the orange waste suspension. Lastly, the third method was to bleach the orange waste before grinding. The films that were produced gave interesting results and from the tensile testing implied that an impact was made on the strength by every fibrillation. The amount of glycerol was consistent throughout the project, but by adding different amount of citric acid gave the films differentIIproperties. The same happened when changing the mould of the film. The best values of the films were from the 30th fibrillation, gave the mean value of 31.6 MPa in tensile strength, and had a strain in elongation at 6.1 %. The tensile strength and elongation had increased drastically compared the fifth fibrillation which had 9.8 MPa and 7.6%.

No description available.

This thesis deals with processing of nanocellulose originating from pulps, with focus on mechanical pulp fibres and fines fractions. The nanocellulose materials produced within this research project were tested for different purposes ranging from strength additives in paper and paperboard products, via composite films to foam materials. TAPPI (Technical Association of Pulp &amp; Paper Industry) has recently suggested a standard terminology and nomenclature for nanocellulose materials (see paper I). In spite of that we have decided to use the terms nano-ligno-cellulose (NLC), microfibrillated cellulose (MFC), nanofibrillated cellulose (NFC) and nanocellulose (NC) in this thesis . It is well-known that mainly chemical pulps are used as starting material in nanocellulose production. However, chemical pulps as bleached sulphite and bleached kraft are quite expensive. One more cost-effective alternative can be to use fibres or fines fractions from thermo-mechanical pulp (TMP) and chemi-thermomechanical pulp (CTMP).   In paper II-IV, fractionation has been used to obtain fines fractions that can easily be mechanically treated using homogenisation. The idea with this study was to investigate the possibility to use fractions of low quality materials from fines fractions for the production of nanocellulose. The integration of a nanocellulose unit process in a high-yield pulping production line has a potential to become a future way to improve the quality level of traditional products such as paper and paperboard grades.   Paper III describes how to utilise the crill measurement technique as a tool for qualitative estimation of the amount of micro- and nano-material produced in a certain process. The crill values of TMP- and CTMP-based nanocelluloses were measured as a function of the homogenisation time. Results showed that the crill values of both TMP-NLC and CTMP-NLC correlated with the homogenisation time. In Paper V pretreating methods, hydrogen peroxide and TEMPO are evaluated. Crill measurement showed that hydrogen peroxide pretreatment (1% and 4%) and mechanical treatment time did not improve fibrillation efficiency as much as expected. However, for TEMPO-oxidised nanocelluloses, the crill value significantly increased with both the TEMPO chemical treatment and mechanical treatment time. In paper V-VII TEMPO-mediated oxidation systems (TEMPO/NaBr/NaClO) are applied to these fibres (CTMP and Sulphite pulp) in order to swell them so that it becomes easy to disrupt the fibres into nanofibres with mechanical treatment.   The demand for paperboard and other packaging materials are steadily increasing. Paper strength properties are crucial when the paperboard is to withstand high load. A solution that are investigated in papers IV and VI, is to use MFC as an alternative paper strength additive in papermaking. However, if one wish to target extremely higher strength improvement results, particularly for packaging paperboards, then it would be fair to use MFC or cationic starch (CS). In paper VI CS or TEMPO-based MFC was used to improve the strength properties of CTMP-based paperboard products. Results here indicate significant strength improvement with the use of different levels of CS (i.e., 20 and 10 kg t–1) and 5% MFC. The strengthening impact of 5% MFC was approximately equal to that of 10 kg t–1 of CS.   In paper VII, NFC and nanographite (NG) was used when producing composite films with enhanced sheet-resistance and mechanical properties. The films produced being quite stable, flexible, and bendable. Realising this concept of NFC-NG composite film would create new possibilities for technological advancement in the area of high-yield pulp technology.  Finally, in paper VIII, a new processing method for nanocellulose is introduced  where an organic acid (i.e., formic acid) is used. This eco-friendly approach has shown to be successful, a nanocellulose with a uniform size distribution has been produced. / <p>Vid tidpunkten för disputationen var följande delarbeten opublicerade: delarbete 5 och 7 inskickade, delarbete 6 och 8 manuskript.</p><p>At the time of the doctoral defence the following papers were unpublished: paper 5 and 7 submitted, paper 6 and 8 manuscripts.</p>

<p>Predmet doktorske disertacije je ispitivanje mogućnosti karakterizacija novih biorazgradivih kompozitnih filmova na<br />bazi biljnih proteina. Osnovno istraživanje se bazira na<br />ispitivanju mogućnosti dobijanja kompozitnih filmova na bazi<br />obnovljivih sirovina, vlažnim postupkom (&quot;casting&quot; metoda),<br />karakterizaciji dobijenih filmova i modifikaciji uslova dobijanja<br />radi pobolj&scaron;anja osobina formiranog filma. Istraživanja se<br />zasnivaju na dobijanju filmova na bazi pogače uljane tikve<br />golice (Cucurbita pepo L. c. v. Olinka) (pumpkin oil cake &ndash;<br />PuOC), njenog proteinskog izolata i njihove kombinacije sa<br />drugim filmogenim polimerima (proteinima i polisaharidima).<br />Istraživanje podrazumeva procenu mogućnosti primene PuOC<br />radi delimične zamene op&scaron;te poznatih filmogenih materijala,<br />kao i produkciju filmova od PuOC i od proteinskog izolata<br />PuOC. Za produkciju filmova, od važnosti je ispitivanje<br />procesnih parametara (temperatura, pH, period denaturacije,<br />uslovi su&scaron;enja, itd.) i komponenti koje formiraju film (količina<br />polimera sa sposobno&scaron;ću formiranja filma, količina i vrsta<br />plastifikatora, količina i vrsta agenasa za umrežavanje, itd.). S<br />obzirom na velik broj parametara koji utiču na formiranje filma,<br />kao i na osobine formiranih filmova, ispitano je međusobno<br />delovanja vi&scaron;e faktora na mogućnost produkcije i osobine<br />dobijenog filma. Odabir i optimizacija procesnih parametara i modelovanje produkcije filmova izvedeno je implementiranjem<br />nove kompjuterske i analitičke metodologije. Osobine značajne<br />za dalju primenu dobijenih filmova podrazumevaju mehaničke<br />osobine (zateznu jačinu i izduženje pri kidanju), barijerne<br />(propustljivost gasova) i fizičko-hemijske karakteristike<br />(rastvorljivost, količinu rastvorljivih proteina, biolo&scaron;ku<br />aktivnost u vidu antioksidantne aktivnosti), a ispitane su u cilju<br />deklarisanja potencijalne aplikacije filma. Dodatno, ispitana je<br />mogućnost produkcije kompozitnih filmova proteinski<br />izolat/hitozan, kao i primena enzimskog umrežavanja (crosslinking)<br />enzimom transglutaminaza (TGaza), radi dobijanja<br />filmova sa unapređenim karakteristikama. Istraživanja su<br />vođena i u smeru karakterizacije strukture nastalih filmova,<br />primenom tehnika elektron skenirajuće mikroskopije,<br />deferencijalne skening kalorimetrije, gasne hromatografije i<br />Furije transformi&scaron;uće infracrvene spektrofotometrije.</p> / <p>The subject of the doctoral dissertation is to examine the possibility of<br />production and characterization of new biodegradable composite<br />films based on plant proteins. The research is based on an<br />examination of the possibility of obtaining composite films based on<br />renewable raw materials, using the casting method, on the<br />characterization of the obtained films and the requirement for the<br />modification to improve the properties of the formed film. The<br />research is aimed to evaluate the possibility of the production<br />the new biodegradable films based on hull-less pumpkin<br />(Cucurbita pepo L. c. v. Olinka) oil cake (pumpkin oil cake -<br />PuOC), its protein isolates and their combinations with other<br />filmogenous polymers (proteins and polysaccharides). The<br />study involves partial replacement of commonly well-known<br />filmogenous materials with PuOC, and production of films<br />based on the whole PuOC and the protein isolates from PuOC.<br />For film production, it is important to investigate the process<br />parameters (temperature, pH, denaturation period, drying conditions,<br />etc.), film-forming components (the amount of polymer with filmforming<br />ability, the amount and type of plasticizer, the amount and<br />type of cross-linking agents, etc..). As the large number of parameters<br />influence the film formation, as well as the properties of formed<br />films, the interaction of several factors which affect the possibility of<br />the production and properties of the obtained film, was examined.<br />Selection and optimization of process parameters and modeling of<br />film production will be carried out by implementing a new computer<br />and analytical methodology. Characteristics important for further<br />application of the obtained films include mechanical properties<br />(tensile strength and elongation at break), barrier (gas permeability)<br />and physical-chemical properties (solubility, the amount of soluble<br />proteins, biological activity in the form of antioxidant activity) and<br />were tested for the purpose of declaring potential application of the produced films. Additionaly, the possibility of production of composite films protein isolate/chitosan, and the application of enzymatic networks (cross-linking) by the enzyme<br />transglutaminase, in order to obtain films with improved<br />properties, was examined. Research was conducted in the<br />direction of the characterization of films formed by applying the<br />techniques of scanning electron microscopy, diferential<br />scanning calorimetry, gas chromatography and Fourier<br />transforming infrared spectrophotometry.</p>

The application of current soy protein films are limited due to their low mechanical strength and high moisture sensitivity compared to synthetic materials. This research studied several methods to improve the mechanical properties [tensile strength (TS), elongation at break (EAB), Young’s modulus of elasticity (YM)] of solvent cast soy protein isolate (SPI) films. Drying times were significantly reduced through the use of a heated casting surface. Neutral (pH 7) SPI films were prepared but were found to have lower TS, EAB and YM than control films prepared under alkaline conditions. Cellulose was extracted from soybean wastes and transmission electron microscopy (TEM) verified the existence of nano-sized fibres. Composite SPI films were prepared using either extracted cellulose fibres or titanium dioxide (TiO2) nanoparticles and their mechanical and barrier properties (water vapour, and oxygen permeability) were evaluated under different relative humidity (RH) conditions. In general, TS and YM decreased and EAB increased with increasing RH. Films with 5% (w/w) added cellulose exhibited significant (p-value < 0.05) improvements in TS and YM but decreased EAB. TiO2 composites possessed similar TS, YM, and EAB values to control films. Barrier properties were comparable across all samples, and decreased with increasing RH. Samples were characterized using Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and atomic force microscopy (AFM). Preliminary work investigating synthesis of filler materials using cross-linked sodium alginate particles increased the TS and YM of SPI films to a similar extent as extracted cellulose. A method for electrospinning cellulose using ionic liquids was developed, but requires further process optimization to be used for fibre/filler synthesis. / OMAFRA; Hannam Soy Utilization Fund

No description available.