Cellulose based Lithium ion polymer electrolytes for Lithium batteries

The separator membrane in batteries and fuel cells is of crucial importance for the function of these devices. In lithium ion batteries the separator membrane as well as the polymer matrix of the electrodes consists of polymer electrolytes which are lithium ion conductors. To overcome the disadvantage of currently used polymer electrolytes which are highly swollen with liquids and thus mechanically and electrochemically unstable, the goal of this work is a new generation of solid polymer electrolytes with a rigid backbone and a soft side chain structure. Moreover the novel material should be based on cheap substrates and its synthesis should not be complicated aiming at low overall costs. The new materials are based on hydroxypropylcellulose and oligoethyleneoxide derivatives as starting materials. The grafting of the oligoethyleneoxide side chains onto the cellulose was carried out following two synthetic methods. One is based on a bromide derivative and another based on p-toluolsulfonyl as a leaving group. The side chain reagents were prepared form tri(ethylene glycol) monoethyl ether. In order to improve the mechanical properties the materials were crosslinked. Two different conceptions have been engaged based on either urethane chemistry or photosensitive dimethyl-maleinimide derivatives. PEO - graft - cellulose derivatives with a high degree of substitution between 2,9 and 3,0 were blended with lithium trifluoromethane-sulfonate, lithium bis(trifluorosulfone)imide and lithium tetrafluoroborate. The molar ratios were in the range from 0,02 to 0,2 [Li]/[O]. The products have been characterized with nuclear magnetic resonance (NMR), gel permeation chromatography (GPC) and laserlight scattering (LS) with respect to their degree of substitution and molecular weight. The effect of salt concentration on ionic conductivity, thermal behaviour and morphology has been investiga-ted with impedance spectroscopy, differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The crosslinking reactions were controlled with dynamic mechanical analysis (DMS). The degree of substitution of our products is varying between 2,8 and 3,0 as determined by NMR. PEO - graft - cellulose derivatives are highly viscous liquids at room temperature with glass transition temperatures around 215 K. The glass transition temperature for the Lithium salt complexes of PEO - graft - cellulose deri-vatives increase with increasing salt content. The maximum conductivity at room temperature is about 10-4 and at 100°C around 10-3 Scm-1. The presence of lithium salt decreases the thermal stability of the complexes in comparison to pure PEO - graft - cellulose derivatives. Complexes heated over 140 – 150°C completely lose their ionic conductivity. The temperature dependence of the conductivity presented as Arrhenius-type plots for all samples is similar in shape and follows a VTF behaviour. This proofs that the ionic transport is closely related to the segmental motions of the polymer chains. Novel cellulose derivatives with grafted oligoethylen-oxide side chains with well-defined chemical structure and high side chain grafting density have been synthesized. Cellulose was chosen as stiff, rod like macromolecule for the backbone while oligoethylen-oxides are chosen as flexible side chains. A maximum grafting density of 3.0 have been obtained. The best conductivity reaches 10-3 Scm-1 at 100°C for a Li-triflate salt complex with a [Li]/[O] ratio of 0.8. The cross-linked complexes containing the lithium salts form elastomeric films with convenient mechanical stability. Our method of cellulose modification is based on relatively cheap and commercially available substrates and as such appears to be a promising alternative for industrial applications.

Polymer surfaces on small length- and short time-scales

The behaviour of a polymer depends strongly on the length- and time scale as well as on the temperature rnat which it is probed. In this work, I describe investigations of polymer surfaces using scanning probe rnmicroscopy with heatable probes. With these probes, surfaces can be heated within seconds down to rnmicroseconds. I introduce experiments for the local and fast determination of glass transition and melting rntemperatures. I developed a method which allows the determination of glass transition and melting rntemperatures on films with thicknesses below 100 nm: A background measurement on the substrate was rnperformed. The resulting curve was subtracted from the measurement on the polymer film. The rndifferential measurement on polystyrene films with thicknesses between 35 nm and 160 nm showed rncharacteristic signals at 95 ± 1 °C, in accordance with the glass transition of polystyrene. Pressing heated rnprobes into polymer films causes plastic deformation. Nanometer sized deformations are currently rninvestigated in novel concepts for high density data storage. A suitable medium for such a storage system rnhas to be easily indentable on one hand, but on the other hand it also has to be very stable towards rnsurface induced wear. For developing such a medium I investigated a new approach: A comparably soft rnmaterial, namely polystyrene, was protected with a thin but very hard layer made of plasma polymerized rnnorbornene. The resulting bilayered media were tested for surface stability and deformability. I showed rnthat the bilayered material combines the deformability of polystyrene with the surface stability of the rnplasma polymer, and that the material therefore is a very good storage medium. In addition we rninvestigated the glass transition temperature of polystyrene at timescales of 10 µs and found it to be rnapprox. 220 °C. The increase of this characteristic temperature of the polymer results from the short time rnat which the polymer was probed and reflects the well-known time-temperature superposition principle. rnHeatable probes were also used for the characterization of silverazide filled nanocapsules. The use of rnheatable probes allowed determining the decomposition temperature of the capsules from few rnnanograms of material. The measured decomposition temperatures ranged from 180 °C to 225 °C, in rnaccordance with literature values. The investigation of small amounts of sample was necessary due to the rnlimited availability of the material. Furthermore, investigating larger amounts of the capsules using rnconventional thermal gravimetric analysis could lead to contamination or even damage of the instrument. rnBesides the analysis of material parameters I used the heatable probes for the local thermal rndecomposition of pentacene precursor material in order to form nanoscale conductive structures. Here, rnthe thickness of the precursor layer was important for complete thermal decomposition. rnAnother aspect of my work was the investigation of redox active polymers - Poly-10-(4-vinylbenzyl)-10H-rnphenothiazine (PVBPT)- for data storage. Data is stored by changing the local conductivity of the material rnby applying a voltage between tip and surface. The generated structures were stable for more than 16 h. It rnwas shown that the presence of water is essential for succesfull patterning.

Local dynamics and bending mechanics of mesostructured materials

Die vorliegende Arbeit behandelt die Anwendung der Rasterkraftmikroskopie auf die Untersuchung mesostrukturierter Materialien. Mesostrukturierte Materialien setzen sich aus einzelnen mesoskopen Bausteinen zusammen. Diese Untereinheiten bestimmen im Wesentlichen ihr charakteristisches Verhalten auf äußere mechanische oder elektrische Reize, weshalb diesen Materialien eine besondere Rolle in der Natur sowie im täglichen Leben zukommt. Ein genaues Verständnis der Selbstorganisation dieser Materialien und der Wechselwirkung der einzelnen Bausteine untereinander ist daher von essentieller Bedeutung zur Entwicklung neuer Synthesestrategien sowie zur Optimierung ihrer Materialeigenschaften. Die Charakterisierung dieser mesostrukturierten Materialien erfolgt üblicherweise mittels makroskopischer Analysemethoden wie der dielektrischen Breitbandspektroskopie, Thermogravimetrie sowie in Biegungsexperimenten. In dieser Arbeit wird gezeigt, wie sich diese Analysemethoden mit der Rasterkraftmikroskopie verbinden lassen, um mesostrukturierte Materialien zu untersuchen. Die Rasterkraftmikroskopie bietet die Möglichkeit, die Oberfläche eines Materials abzubilden und zusätzlich dazu seine quantitativen Eigenschaften, wie die mechanische Biegefestigkeit oder die dielektrische Relaxation, zu bestimmen. Die Übertragung makroskopischer Analyseverfahren auf den Nano- bzw. Mikrometermaßstab mittels der Rasterkraftmikroskopie erlaubt die Charakterisierung von räumlich sehr begrenzten Proben bzw. von Proben, die nur in einer sehr kleinen Menge (<10 mg) vorliegen. Darüberhinaus umfasst das Auflösungsvermögen eines Rasterkraftmikroskops, welche durch die Größe seines Federbalkens (50 µm) sowie seines Spitzenradius (5 nm) definiert ist, genau den Längenskalenbereich, der einzelne Atome mit der makroskopischen Welt verbindet, nämlich die Mesoskala. In dieser Arbeit werden Polymerfilme, kolloidale Nanofasern sowie Biomineralien ausführlicher untersucht.rnIm ersten Projekt werden mittels Rasterkraftmikroskopie dielektrische Spektren von mischbaren Polymerfilmen aufgenommen und mit ihrer lokalen Oberflächenstruktur korreliert. Im zweiten Projekt wird die Rasterkraftmikroskopie eingesetzt, um Biegeexperimente an kolloidalen Nanofasern durchzuführen und so ihre Brucheigenschaften genauer zu untersuchen. Im letzten Projekt findet diese Methode Anwendung bei der Charakterisierung der Biegeeigenschaften von Biomineralien. Des Weiteren erfolgt eine Analyse der organischen Zusammensetzung dieser Biomineralien. Alle diese Projekte demonstrieren die vielseitige Einsetzbarkeit der Rasterkraftmikroskopie zur Charakterisierung mesostrukturierter Materialien. Die Korrelation ihrer mechanischen und dielektrischen Eigenschaften mit ihrer topographischen Beschaffenheit erlaubt ein tieferes Verständnis der mesoskopischen Materialien und ihres Verhaltens auf die Einwirkung äußerer Stimuli.rn

A General Approach Towards the Synthesis of Amido-Functionalized Biodegradable Polyesters

The thesis presented here describes methodologies to produce pendant group functionalized polyesters from amido-functionalized α-hydroxy acids. The synthetic methods used to produce the functionalized α-hydroxy acids are compatible with a wide array of functional groups, making this technique highly versatile. The synthesis of functionalized polyesters was investigated to develop polymers with properties that may improve the capabilities of existing biodegradable polyesters for applications in controlled release pharmaceuticals. Chemically modified a-hydroxy acids were synthesized by reacting glyoxylic acid with a primary or secondary amide. To demonstrate the utility of this reaction, fourstructurally dissimilar amide substituents were examined including 2-pyrrolidione, benzamide, acetamide and acrylamide. The reaction is synthetically simple, provides high yields and is uniquely flexible, functionalized monomer. The compatibility of this procedure with the collection of functional groups mentioned circumvents the need for syntheses. The amido-functionalized monomers were polymerized by two different techniques: melt polycondensation and solution polymerization. Melt polycondensation was conducted by heating the monomer past its melting temperature under reduced pressure. Oligomeric functionalized polyesters (= 800 g/mol) with low PDIs (= 1.05) were obtained by melt polycondensation. Melt polycondensation was not compatible with all of the synthesized monomers. Two of the monomers (containing benzamide and acrylamide functionalities) degraded before the polycondensation reaction occurred. Thermal gravimetric analysis confirmed that a process other than polyesterification was occurring, indicating that some amido-functionalized α-hydroxy acids cannot be synthesized in the melt.Solution polymerization was conducted to polymerize functionalized α-hydroxy acids that were incompatible with melt polycondensation. Several modified Steglich polyesterifications were tested including p-toluenesulfonic acid mediated and scandium (III) triflate catalyzed. Only oligomeric functionalized polyesters were formed bythis method. A number of possible side reactions including the formation of an N-acylurea and a cyclic polymer ring were possible. The utility of this procedure appears to be limited due to the complexity of the reaction and its inability to produce high molecular weight polymer.

Synthesis of bone-like micro-porous calcium phosphate/iota-carrageenan composites by gel diffusion

Brushite and octacalcium phosphate (OCP) crystals are well-known precursors of hydroxylapatite (HAp), the main mineral found in bone. In this report, we present a new method for biomimicking brushite and OCP using single and double diffusion techniques. Brushite and OCP crystals were grown in an iota-carrageenan gel. The aggregates were analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD), infrared spectroscopy (IR) and thermal gravimetric analysis (TGA). SEM revealed different morphologies of brushite crystals from highly porous aggregates to plate-shaped forms. OCP crystals grown in iota-carrageenan showed a porous spherical shape different from brushite growth forms. The XRD method demonstrated that the single-diffusion method favors the formation of monoclinic brushite. In contrast, the double diffusion method was found to promote the formation of the triclinic octacalcium phosphate OCP phase. By combining the different parameters for crystal growth in carrageenan, such as ion concentration, gel pH and gel density, it is possible to modify the morphology of composite crystals, change the phase of calcium phosphate and modulate the amount of carrageenan inclusion in crystals. This study suggests that iota-carrageenan is a high-molecular-weight polysaccharide that is potentially applicable for controlling calcium phosphate crystallization.

Glutamic acid inducing kidney stone biomimicry by a brushite/gelatin composite

Brushite is a well known precursor of calcium oxalate monohydrate, the main mineral found in kidney stones having a monoclinic crystal structure. Here, we present a new method for biomimicking brushite using a single tube diffusion technique for gel growth. Brushite crystals were grown by precipitation of calcium hydrogen phosphate hydrate in a gelatin/glutamic acid network. They are compared with those produced in gel in the presence of urea. The aggregates were analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD), infrared spectroscopy (IR) and thermal gravimetric analysis (TGA). SEM revealed a change of morphology by glutamic acid from spherulitic growth to plate-shaped and mushroom-like forms consisting of crystal plates and highly ordered prismatic needles, respectively. Furthermore, brushite crystals grown in a gelatin/glutamic acid/urea network showed needle-shaped morphology being different from other brushite growth forms. The XRD method showed that cell parameters for brushite specimens were slightly larger than those of the American Mineral Society reference structure. The mushroom-like biomimetic composite bears a strong resemblance to the brushite kidney stones which may open up new future treatment options for crystal deposition diseases. Hence, suitable diets from glutamic acid rich foods could be recommended to inhibit and control brushite kidney stones.

Effect of nano-Si2O and nano-Al2O3 on cement mortars for use in agriculture and livestock production

The effect of nano-silica, nano-alumina and binary combinations on surface hardness, resistance to abrasion and freeze-thaw cycle resistance in cement mortars was investigated. The Vickers hardness, the Los Angeles coefficient (LA) and the loss of mass in each of the freeze–thaw cycles to which the samples were subjected were measured. Four cement mortars CEM I 52.5R were prepared, one as control, and the other three with the additions: 5% nano-Si, 5% nano-Al and mix 2.5% n-Si and 2.5% n-Al. Mortars were tested at 7, 28 and 90 d of curing to determine compression strength, total porosity and pore distribution by mercury intrusion porosimetry (MIP) and the relationship between the CSH gel and Portlandite total by thermal gravimetric analysis (TGA). The capillary suction coefficient and an analysis by a scanning electron microscope (SEM) was made. There was a large increase in Vickers surface hardness for 5% n-Si mortar and a slight increase in resistance to abrasion. No significant difference was found between the mortars with nano-particles, whose LA was about 10.8, classifying them as materials with good resistance to abrasion. The microstructure shows that the addition of n-Si in mortars refines their porous matrix, increases the amount of hydrated gels and generates significant changes in both Portlandite and Ettringite. This produced a significant improvement in freeze–thaw cycle resistance. The effect of n-Al on mortar was null or negative with respect to freeze–thaw cycle resistance.

Production and Electrical Characterization of Low Density Polyethylene-based Micro- and Nano-dielectrics containing Graphene Oxide, Functionalized Graphene and Carbon Black additives

Oggigiorno la ricerca di nuovi materiali per gradatori di campo da impiegarsi in accessori di cavi ha iniziato a studiare alcuni materiali nano dielettrici con proprietà elettriche non lineari con la tensione ed aventi proprietà migliorate rispetto al materiale base. Per questo motivo in questo elaborato si sono studiati materiali nanostrutturati a base di polietilene a bassa densità (LDPE) contenenti nano polveri di grafene funzionalizzato (G*), ossido di grafene (GO) e carbon black (CB). Il primo obiettivo è stato quello di selezionare e ottimizzare i metodi di fabbricazione dei provini. La procedura di produzione è suddivisa in due parti. Nella prima parte è stata utilizzatala tecnica del ball-milling, mentre nella seconda un pressa termica (thermal pressing). Mediante la spettroscopia dielettrica a banda larga (BDS) si sono misurate le componenti reali e immaginarie della permettività e il modulo della conducibilità del materiale, in tensione alternata. Il miglioramento delle proprietà rispetto al provino di base composto dal solo polietilene si sono ottenute quando il quantitativo delle nanopolveri era maggiore. Le misure sono state effettuate sia a 3 V che a 1 kV. Attraverso misurazioni di termogravimetria (TGA) si è osservato l’aumento della resistenza termica di tutti i provini, soprattutto nel caso quando la % di nanopolveri è maggiore. Per i provini LDPE + 0.3 wt% GO e LDPE + 0.3 wt% G* si è misurata la resistenza alle scariche parziali attraverso la valutazione dell’erosione superficiale dei provini. Per il provino contenente G* è stato registrato una diminuzione del 22% del volume eroso, rispetto al materiale base, mentre per quello contenente GO non vi sono state variazioni significative. Infine si è ricercata la resistenza al breakdown di questi ultimi tre provini sopra citati. Per la caratterizzazione si è fatto uso della distribuzione di Weibull. Lo scale parameter α risulta aumentare solo per il provino LDPE + 0.3 wt% G*.

Double-walled carbon nanotubes synthesized using carbon black as the dot carbon source

Double- walled carbon nanotubes (DWNTs) were synthesized used carbon black as the dot carbon source by a semi-continuous hydrogen arc discharge process. High-resolution transmission electron microscopy (HRTEM) observations revealed that most of the tubes were DWNTs with outer and inner diameters in the range of 2.67 - 4 nm and 1.96 - 3.21 nm, respectively. Most of the DWNTs were in a bundle form of about 10 - 30 nm in diameter with high purity ( about 70%) from thermal gravimetric analysis (TGA), resonant laser Raman spectroscopy, scanning electron microscopy (SEM) and TEM characterizations. It was found that carbon black as the dot carbon source could be easy controlled to synthesize one type of nanotube. A simple process combining oxidation and acid treatment to purify the DWNT bundles was used without damaging the bundles. The structure of carbon black, as the key element for influencing purity, bundle formation and purification of DWNTs, is discussed.

Micropartículas de quitosana estruturadas com aerosil®: estabilidade, adsorção, encapsulação e liberação de substâncias ativas

Biodegradable microspheres used as controlled release systems are important in pharmaceutics. Chitosan biopolymer represents an attractive biomaterial alternative because of its physicochemical and biological characteristics. Chitosan microspheres are expected to become promising carrier systems for drug and vaccine delivery, especially for non-invasive ways oral, mucosal and transdermal routes. Controlling the swelling rate and swelling capacity of the hydrogel and improving the fragile nature of microspheres under acidic conditions are the key challenges that need to be overcomed in order to enable the exploration of the full pharmaceutical potential use of these microparticles. Many studies have focused on the modification of chitosan microsphere structures with cross-linkers, various polymers blends and new organic-inorganic hybrid systems in order to obtain improved properties. In this work, microspheres made of chitosan and nanosized hydrophobic silica (Aerosil R972) were produced by a method consisting of two steps. First, a preparation of a macroscopically homogeneous chitosan-hydrophobic silica dispersion was prepared followed by spray drying. FTIR spectroscopy, X-ray powder diffraction, differential scanning calorimetry, thermal gravimetric analysis, scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (TEM) were used to characterize the microspheres. Also, the were conducted acid stability, moisture sorption capacity, release properties and biological assays. The chitosan-hydrophobic silica composite microspheres showed improved thermal degradation, lower water affinity, better acid stability and ability to retard rifampicin and propranolol hydrochloride (drug models) release under simulated physiological conditions. In vitro biocompatibility studies indicated low cytotoxicity and low capacity to activate cell production of the pro-inflammatory mediator nitric oxide. The results show here encourage further studies on the use of the new chitosan-hydrophobic silica composite microspheres as drug carrier systems via oral or nasal routes.

Contribuição da poliacrilamida parcialmente hidrolisada em associação com a bentonita em fluidos de perfuração aquosos

In this study, we investigated the effect of addition of partially hydrolyzed polyacrylamide (HPAM) and bentonite in the physicochemical properties of acquous drilling fluids. Two formulations were evaluated: F1 formulation, which was used as reference, containing carboxymethylcellulose (CMC), magnesium oxide (MgO), calcite (calcium carbonate - CaCO3 ), xanthan gum, sodium chloride (NaCl) and triazine (bactericidal); and F2, containig HPAM steady of CMC and bentonite in substituition of calcite. The prepared fluids were characterized by rheological properties, lubricity and fluid loss. Calcite was characterized by granulometry and thermal gravimetric analysis (TGA). The formulation F2 presented filtration control at 93◦C 34 mL while F1 had total filtration. The lubricity coefficient was 0.1623 for F2 and 0.2542 for F1, causing reduction in torque of 25% for F1 and 52 % for F2, compared to water. In the temperature of 49 ◦C and shear rate of 1022 s −1 , the apparent viscosities were 25, 5 and 48 cP for F1 and F2 formulation, respectively, showing greater thermal resistance to F2. With the confirmation of higher thermal stability of F2, factorial design was conducted in order to determine the HPAM and of bentonite concentrations that resulted in the better performance of the fluids. The statistical design response surfaces indicated the best concentrations of HPAM (4.3g/L) and bentonite (28.5 g/L) to achieve improved properties of the fluids (apparent viscosity, plastic viscosity, yield point and fluid loss) with 95% confidence, as well as the correlations between these factors (HPAM and bentonite concentrations). The thermal aging tests indicated that the formulations containing HPAM and bentonite may be used to the maximum temperature until 150 ◦C. The analyze of the filter cake formed after filtration of fluids by X-ray diffraction showed specific interactions between the bentonite and HPAM, explaining the greater thermal stability of F2 compared to the fluid F1, that supports maximum temperature of 93 ◦C.

Synthesis and characterization of nanocomposites based on PANI and carbon nanostructures prepared by electropolymerization

Nanocomposites based on polyaniline (PANI) and carbon nanostructures (CNSs) (graphene (G) and multiwall carbon nanotubes (MWCNTs)) were prepared by in situ electrochemical polymerization. CNSs were inserted into the PANI matrix by dispersing them into the electrolyte before the electropolymerization. Electrochemical characterization by means of cyclic voltammetry and steady state polarization were performed in order to determine conditions for electro- polymerization. Electro-polymerization of the PANI based nanocomposites was carried out at 0.75 V vs. saturated calomel electrode (SCE) for 40 and 60 minutes. The morphology and structural characteristics of the obtained nanocomposites were studied by scanning electron microscopy (SEM) and Raman spectroscopy, while thermal stability was determined using thermal gravimetric analysis (TGA). According to the morphological and structural study, fibrous and porous structure of PANI based nanocomposites was detected well embedding both G and MWCNTs. Also, strong interaction between quinoidal structure of PANI with carbon nanostructures via π–π stacking was detected by Raman spectroscopy. TGA showed the increased thermal stability of composites reinforced with CNSs, especially those reinforced with graphene.