Bestimmte Extraktstoffe aus thermisch modifizierter Buche weisen fungizide Eigenschaften auf. Methanol-Extrakte aus thermisch modifizierter Buche, die in Propanon wieder aufgelöst wurden, wiesen eine leichte pilzwachstumshemmende Wirkung auf. Die getränkten Prüfkörper aus Buche erreichten eine Zuordnung zur Dauerhaftigkeitsklasse 4, d. h. nicht dauerhaft. Prüfkörper, die mit anderen Extrakten aus thermisch modifizierter Buche getränkt wurden, dabei insbesondere Wasser-Extrakte, weisen dagegen keine signifikante Resistenzverbesserung auf. Die Analyse der Methanol-Extrakte mittels Gaschromatografie mit Massenspektrometrie-Kopplung (GC-MS) ließ einen erhöhten Anteil bestimmter phenolischer Verbindungen erkennen, die teilweise Resistenz fördernde Wirkungen haben. Das Vorhandensein dieser Verbindungen kann somit als Begründung der Verbesserung der Resistenz entsprechend imprägnierter Prüfkörper herangezogen werden. Die Endfassung des Artikels ist auf www.holztechnologie.de verfügbar. / Certain extractives from thermally modified beech have fungicidal properties. Methanol extracts, resolubilized in propanone, caused a significant retardation of fungal growth on native beech specimen. Beech specimen impregnated with these extractives could be assigned to the durability class 4, i. e. not permanent. Other extracts of thermally modified beech, in particular water extracts, did not show significant improvement in resistance. The analysis of methanol extracts using gas chromatography coupled with mass spectrometry (GC-MS) showed an increased amount of phenolic compounds known to increase resistance. Their presence in organic extracts of thermally modified wood may explain the improvement of the resistance of the impregnated specimen. The original publication is available at www.holztechnologie.de.

Im Rahmen des Forschungsprojektes wurden zwei Verfahren zur Herstellung thermisch modifizierter Furniere entwickelt. Nach Verfahren 1 erfolgt die Herstellung von Furnier durch Messern von thermisch modifizierten Blöcken, wobei der Hauptanteil der Untersuchungen an längs gemesserten Furnieren durchgeführt wurde. Ein Industrieversuch belegt die Machbarkeit der Herstellung thermisch modifizierter Furniere aus modifizierten Blöcken durch quer messern, also nach dem üblichen Verfahren zur Herstellung dekorativer Furniere. Nach Verfahren 2 erfolgt die Herstellung von thermisch modifizierten Furnieren durch thermische Modifizierung handelsüblicher dünner Messerfurniere (d=0,5...0,6 mm). Parameter für eine thermische Modifikation sind im Wesentlichen die Dauer der Behandlung sowie die Temperatur. Die Temperatur wurde im Bereich zwischen 170°C und 210°C variiert, die Dauer der Hochtemperaturbehandlung zwischen 2 h und 4 h. Als Holzarten wurden Rotbuche, Ahorn, Birke, Pappel und Esche untersucht. Die hergestellten Furniere wurden hinsichtlich verschiedener mechanischer Eigenschaften, farblicher Eigenschaften sowie verarbeitungstechnischer Eigenschaften untersucht und bewertet.

Thermally activated delayed fluorescence (TADF) has been proposed as a pathway to achieve high efficiency organic light-emitting diodes (OLEDs) without the use of heavy metal atoms in molecular structures. Many different factors can be decisive for efficient light emission from TADF emitters. However, a complete picture of the working mechanisms behind TADF is still missing and further research exploring novel material and device ideas is required. This thesis aims to extend the understanding of TADF emitter and OLED design considerations by investigating photophysical properties of novel materials as well as fabricating, optimizing and characterizing devices. TADF emitters have great potential of being used in OLEDs because they allow for high quantum efficiencies by utilizing triplet states via reverse intersystem crossing (RISC). In small molecules this is done by spatially separating the frontier orbitals, forming an intramolecular charge-transfer state (iCT) and leading to a small energy difference between lowest excited singlet and triplet states (Δ𝐸ST). In polymer emitters, sufficient frontier orbital separation is harder to achieve, and typical strategies usually include adding known TADF units as sidechains onto a polymer backbone. In this thesis, a novel pathway of TADF polymer design is explored. A shift from a non-TADF monomer to TADF oligomers is explored. The monomer shows non-TADF emission and the delayed emission is shown to be of triplet-triplet annihilation (TTA) origin. An iCT state is formed already in the dimer, leading to a much more efficient TADF emission. This is confirmed by an almost two-fold increase of photoluminescence quantum yield (PLQY), a decrease in the delayed luminescence lifetime and the respective spectral line shapes of the molecules. Recently, intermolecular effects between small-molecule TADF emitters have been given more attention, revealing strong solid-state solvation or aggregation induced changes of sample performance. Implications of this on device performance are not yet fully covered. A thorough investigation of a novel TADF emitter 5CzCO2Me is conducted. Steady-state emission spectra reveal a luminescence redshift with increasing emitter concentration in a small molecule host. In all investigated concentrations, the emission profile remains the same, thus the redshift is attributed to the solid-state solvation effect. The highest photoluminescence quantum yield (PLQY) is achieved in the 20 wt% sample, reaching 66 %. The best OLED in terms of current-voltage-luminance and external quantum efficiency parameters is the device with 60 wt% emitter concentration, reaching maximal EQE values of 7.5 %. It is shown that the emitter transports holes and that charge carrier recombination does not take place on the bandgap of the host, but rather, a mixed host-guest concentration dependent recombination is seen. The hole transporting properties of 5CzCO2Me allows for a new dimension in tuning the device performance by controlling the emitter concentration.

No description available.

Thermally developing, electro-osmotically generated flow has been analyzed for a circular microtube under imposed constant wall temperature (CWT) and constant wall heat flux (CHF) boundary conditions. Established by a voltage potential gradient along the length of the microtube, the hydrodynamics of such a flow dictate either a slug flow velocity profile (under conditions of large tube radius-to-Debye length ratio, a/lambda_d) or a family of electro-osmotic flow (EOF) velocity profiles that depend on a/lambda_d. The imposed voltage gradient results in Joule heating in the fluid with an associated volumetric source of energy. For this scenario coupled with a slug flow velocity profile, the analytical solution for the fluid temperature development has been determined for both thermal boundary conditions. The local Nusselt number for the CHF boundary condition is shown to reduce to the classical slug flow thermal development for imposed constant wall heat flux, and is independent of Joule heating source magnitude. For the CWT boundary condition, a local minimum in the streamwise variation in local Nusselt number for moderate positive dimensionless inlet temperature is predicted. For negative dimensionless inlet temperature, which arises if the fluid entrance temperature is below the tube wall temperature, the fluid is initially heated, then cooled, resulting in a singularity in the local Nusselt number at the axial location of the heating/cooling transition. The thermal development length is considerably larger than for traditional pressure-driven flow heat transfer, and is a function of the magnitudes of Peclet number and dimensionless inlet temperature. For the EOF velocity profile scenario, numerical techniques were used to predict the fluid temperature development for both wall boundary conditions by utilizing a finite control volume approach. In addition to Joule heating as an energy source, viscous dissipation is also considered. The results predict that for decreasing a/lambda_d, the local Nusselt number decreases for all axial positions and the thermal development shortens for both wall boundary conditions. Viscous dissipation has significant effect only at intermediate values of a/lambda_d. Results predict local Nusselt numbers to increase for a CWT boundary condition and to decrease for an imposed constant wall heat flux with increasing viscous dissipation.

Polymer matrix composites (PMC's) are now being used more and more extensively and over wider ranges of service conditions. Large changes in pressure, chemical environment or temperature influence the mechanical response of such composites. In the present effort, we focus on temperature, a parameter of primary interest in almost all engineering applications. In order to design composite structures without having to perform extensive experiments (virtual design), the necessity of establishing theoretical models that relate the macroscopic response of the structure to the microscopic properties of the constituents arises. In the first part of the present work, a new stiffness versus temperature model is established. The model is validated using data from the literature. The influence of the different polymer's properties (Molecular weight, crystallinity, and filler content) on the model are studied by performing experiments on different grades of four polymers PMMA, PEEK, PPS, and PB. This statistical model is proven to be applicable to very different polymers (elastomers, thermoplastics, crystalline, amorphous, cross-linked, linear, filled, unfilledâ ¦) over wide temperature ranges (from the glassy state to the flow region). The most attractive feature of the proposed model is the capability to enable a description of the polymer's mechanical behavior within and across the property transition regions. In order to validate the feasibility of using the model to predict the mechanical response of polymer matrix composites, the stiffness-temperature model is used in various micromechanical models (rule of mixtures, compression models for the life prediction of unidirectional PMC's in end-loaded bendingâ ¦). The model is also inserted in the MRLife prediction code to predict the remaining strength and life of unidirectional PMC's in fatigue bending. End-loaded fatigue experiments were performed. A good correlation between theoretical and experimental results is observed. Finally, the model is used in the Classical Lamination Theory; some laminates were found to exhibit stress reversals with temperature and behaved like thermally activated mechanical switches. / Ph. D.

Thermally modified wood (TMW) contains no toxic components and is recommended for its durability, levels of equilibrium of moisture content, and dimensional stability performance. A limitation of TMW is the lack of market acceptance and products due to insufficient information regarding the performance of commercially available products. The goal of this project was to improve the market penetration and industrial processes of TMW. The first objective was to study the perception of TMW products from architects in North America using a survey instrument. Results revealed that information regarding TMW is not reaching the audience for TMW, and that providing knowledge regarding technical and marketing aspects of TMW is essential to increase the market share. The second objective consisted of the evaluation of the variability of the physical and mechanical properties of three thermally treated species manufactured in North America. Results showed that the performance of the commercially produced material was similar among the three companies, where only in seven out of 24 properties had statistical differences. Properties that were significantly different, did not have large enough differences in means to be realistically noticed by customers and all were highly different from untreated wood. The final objective involved the implementation of Lean thinking to the manufacturing process of TMW with the goal of improving the process with a direct impact on cost and waste reductions. Three companies were used as case studies for the production process. The implementation of Lean thinking in the process proposed a reduction in lead times from 55.47 days to 23.20 days, with an increase in value-added activities from 1% to 6%. Most of these gains were obtained through a reduction in inventory levels. / Master of Science / Thermally modified wood (TMW) contains no toxic components and is recommended for its durability, levels of equilibrium of moisture content, and dimensional stability performance. The current market for TMW encounters a lack market acceptance, due to insufficient information and performance measures. The main goal of this study was to increase market penetration and study the industrial processes for manufacturing TMW, using three specifics objectives. For the first objective, a survey was conducted to study the perception of TMW among architects. The results showed a that there was a lack of information regarding the technical and marketing aspects of TMW products, which needs to be addressed by distributors and producers. The second objective consisted of the evaluation of the variability of mechanical and physical properties of three thermally treated species manufactured in North America. The results showed that the performance from the commercial processes were similar, where only seven out of 24 cases showed statistical differences based on the Analysis of Variance (ANOVA). The final objective consisted of a Lean process strategy to produce TMW, improving the process with a direct impact on cost and waste reduction. To study the production process, three case study companies were used. The proposed Lean process reduced the lead times and value-added activities increased. The primary gain was seen in reducing inventory levels.

This dissertation focuses on the synthesis and characterization of high performance polymers, specifically polybenzimidazoles (PBIs) for gas separation applications and polyimides (PI) for water purification and as interfacial agents for thermoplastic carbon fiber composites. Two methods for improving the gas transport properties (for H2/CO2 separation) of a tetraaminodiphenylsulfone (TADPS)-based polybenzimidazole were investigated. Low molecular weight poly(propylene carbonate) (PPC) and poly(ethylene oxide) (PEO) were incorporated as sacrificial additives that could be removed via a controlled heat treatment protocol. PBI films containing 7 and 11 wt% PPC (blend) and 13 wt% PEO (graft) were fabricated and the gas transport properties and mechanical properties after heat treatment were measured and compared to the PBI homopolymer. After heat treatment, the 7 wt% PPC blend exhibited the highest performance while retaining the toughness exhibited by the PBI homopolymer. Novel sulfonated polyimides and their monomers were synthesized for use as interfacial agents and water purification membranes. Polyimides are high performance polymers that have high thermal, mechanical, and chemical stability. The objective was to assess structure-property relationships of novel sulfonated polyimides prepared by direct polymerization of the diamine monomers. A series of sulfonated polyimides was synthesized using an ester-acid polymerization method with varying degrees of sulfonation (20%, 30%, and 50% disulfonated and 50% and 100% monosulfonated polyimides). The results showed that the toughness of the polyimides in the fully hydrated state was much better than current commercial cation exchange membranes. A 100% disulfonated polyimide (sPI) and poly(amic acid) salt (PAAS) using the same monomers used for the synthesis of Ultem® were utilized as suspending agents for the fabrication of coated sub-micron polyetherimide (PEI) particles. Sub-micron particles were obtained using 1 wt% PAAS and 4 wt% sPI to coat the PEI. The PEI particles were coupled onto ozone treated carbon fibers using a silane coupling agent. SEM images showed a significant amount of particle coating on the treated carbon fibers compared to the non-silane treated carbon fibers. / PHD / This dissertation describes synthetic and processing techniques used to fabricate materials for applications such as, water purification and gas separation. The polymers included in this dissertation include polybenzimidazoles and polyimides, which are materials that have exceptional mechanical and thermal properties. The polybenzimidazoles were specifically used for gas separation, while the polyimides were synthesized for use as water purification membranes and surfactants for coating polyimides and carbon fibers. Gas separation membranes are effective tools for purifying gas mixtures (e.g. H₂/N₂, O₂/N₂, CO₂/CH₄). Additionally, they offer the advantage of being economical and environmentally-friendly compared to other methods of separation (e.g. cryogenic distillation). Many synthetic membranes made from polymers are used commercially, however, very few polymers can be used for elevated temperature separations. Because polybenzimidazoles exhibit high thermal stability, they are excellent candidates for high temperature gas separations (specifically H₂/CO₂ gas mixture). However, polybenzimidazoles have inherently low gas permeabilities. Thus, the focus of this research was to develop a simple method to introduce “pores” into the polymer membrane to improve gas permeability. Water purification is a very important process as the demand for clean water increases with the growing global population. Currently, one-third of the global population experience water scarcity, and by 2025, two-thirds of the world’s population may face water shortages. Multi-stage flash distillation is the most widely used method for water desalination from sea water but it is also the most energy intensive process. Water desalination using polymer membranes (e.g. reverse osmosis, nanofiltration, electrodialysis) has been developed as low energy and environmentally-friendly alternatives for producing clean water. The current state-of-the-art membranes used for water purification lack mechanical integrity and chemical resistance, which complicate and reduce the overall efficiency of the separation process. Thus, the focus of the research was to synthesize polyimide membranes with improved toughness and chemical stability.

<div> As hybrid 2D materials are incorporated into next-generation device designs, it becomes more and more pertinent that methods are being developed which can facilitate large-area structural control of noncovalent monolayers assembled at 2D material interfaces. Noncovalent functionalization is often leveraged to modulate the physical properties of the underlying 2D material without disrupting the extended electronic delocalization networks intrinsic to its basal plane. The bottom-up nanofabrication technique of self-assembly permits sub-10-nm chemical patterning with low operational costs and relatively simple experimental designs.</div><div> The Claridge Group is interested in leveraging the unique chemical orthogonality intrinsic to the cellular membrane as a means of creating sub-10-nm hydrophilic-hydrophobic striped patterns across 2D material interfaces for applications ranging from interfacial wetting to large-area molecular templates to guide heterogeneous nanoparticle assembly. Using Langmuir–Schaefer conversion, standing phases of polymerizable amphiphiles at the air-water interfaces of a Langmuir trough are converted (through rotation) to lying-down phases on 2D material substrates. Using room temperature substrates, transfer of amphiphiles to a lowered substrate results in small domains and incomplete surface coverage.</div><div> Recognizing that heating the substrate during the LS conversion process may lower the energy barriers to molecular reorientation, and promote better molecular domain assembly, we developed a thermally controlled heated transfer stage that can maintain the surface temperature of the substrate throughout the deposition process. We found that heating during transfer results in the assembly of domains with edge lengths routinely an order of magnitude larger than transfer using room temperature substrates that are more stable towards rigorous repeat washing cycles with both polar and nonpolar solvents.</div><div> To promote the effectiveness of the LS conversion technique beyond academic environments for the noncovalent functionalization 2D material substrates for next-generation device designs, we designed and built a thermally controlled rotary stage to address the longstanding scaling demerit of LS conversion. First, we report the development of a flexible HOPG substrate film that can wrap around the perimeter of the heated disk and can be continuously cycled through the Langmuir film. We found that thermally controlled rotary (TCR) LS conversion can achieve nearly complete surface coverage at the slowest translation speed tested (0.14 mm/s). TCR–LS facilitates the assembly of domains nearly 10,000 μm² which were subsequently used as molecular templates to guide the assembly of ultranarrow AuNWs from solution in a non-heated rotary transfer step. Together, these findings provide the foundation for the use of roll-to-roll protocols to leverage LS conversion for noncovalent functionalization of 2D materials. A true roll-to-roll thermally controlled LS conversion system may prove to be advantageous and a cost-efficient process in applications that require large areas of functional surface, or benefit from long-range ordering within the functional film.</div>

Ce travail a porté sur la préparation et l'étude de matériaux magnétiques fonctionnels en couches dans l'optique d'une utilisation dans des micro-systèmes magnétiques. Deux systèmes de matériaux ont été étudiés: le FePt, qui est un matériau magnétique dur, et le FeRh, qui a une transition antiferromagnétique-ferromagnétique proche de la température ambiante. Dans le cas du FePt, les influences de la concentration en Pt, de l'ajout de Cu et des traitements thermiques, sur la transition de la phase A1 désordonnée, de faible anisotropie, à la phase L10 ordonnée, de forte anisotropie, ont été étudiées. Les dépendances en température de l'aimantation spontanée et du champ d'anisotropie de la phase L10 ont été déduites de l'analyse des courbes d'aimantation. Le pic d'Hopkinson qui est lié aux processus d'aimantation de la phase L10 à l'approche de la température de Curie a été modélisé. Dans le cas du FeRh, les influences de la concentration en Rh et des traitements thermiques ont été étudiées. Une analyse thermodynamique des mesures d'aimantation et des mesures de calorimétrie différentielle a été effectuée. Enfin, des couches hybrides de FePt-FeRh ont été déposées sur des substrats pré-gravés, pour démontrer la potentialité d'utiliser le FeRh pour contrôler thermiquement le champ de fuite généré par le FePt. / The aim of this work was the preparation and study of thin films of functional magnetic materials of interest for use in magnetic micro-systems. Two material systems have been studied: FePt, which is a hard magnetic material, and FeRh, which has an antiferromagnetic - ferromagnetic transition near room temperature. For the case of FePt, the influence of the film composition, the addition of Cu, and the annealing conditions, on the transition from the disordered, low anisotropy A1 phase to the ordered, high anisotropy L10 phase has been studied. The temperature dependence of the spontaneous magnetisation and the anisotropy field of the L10 phase were deduced from an analysis of magnetisation curves. The Hopkinson peak which characterises the susceptibility of the demagnetized L10 phase close to its Curie temperature has been modelled. In the case of FeRh, the influence of film composition and annealing conditions on the antiferromagnetic - ferromagnetic transition was studied. A thermodynamic analysis of magnetisation measurements and differential calorimetry measurements has been carried out. Finally, hybrid FePt-FeRh films have been deposited on patterned wafers, to demonstrate the potential use of FeRh for the thermal control of the stray field generated by the FePt.