The high functionality epoxy resins tetraglycidyl-4,4’-diaminodiphenyl-methane(TGDDM) and triglycidyl-p-aminophenol (TGPAP) are the main components in most aerospace grade epoxy resin formulations. Owing to their high reactivity and high viscosity, TGDDM and TGPAP pose difficulties when used in wet layup composite manufacturing. As such, these resins are often modified to achieve the desired performance both in the liquid and cured states. The main objective of this thesis is to optimise a low viscosity multi-component epoxy resin formulation suitable for use as an aerospace grade composite matrix. The formulation will allow for the addition of high levels of thermoplastic to improve the fracture toughness of the resin whilst also maintaining resin processability. Through the use of thermal analytical techniques this thesis aims to study the effects of varying the TGDDM/TGPAP ratio, incorporation of a low viscosity bi-functional epoxy resin, the diglycidyl ether of bisphenol F (DGEBF) and changes to the stoichiometric ratio (r)between reactive groups of the epoxy resin and amine hardener (4,4’-diaminodiphenylsulphone, DDS) in multi-component epoxy resin formulations. Resin formulations were optimised using factorial experimental design (FED). Results from two FED’s showed curing multi-component resins at a low stoichiometric ratio significantly increased the processing window whilst also increasing the glass transition temperature (Tg) of the cured resin. No apparent benefit could be assigned to the inclusion of TGDDM owing to its poor processability and a Tg similar to TGPAP. Up to 60% DGEBF was incorporated in a multi-component resin formulation whilst still attaining a Tg greater than 220°C. Its inclusion at 60% had the additional benefit of increasing the processing window by 48 minutes over TGPAP, an increase of 62%. Two optimised resin formulations, 100% TGPAP (100T) and a binary mix of 60% DGEBF and 40% TGPAP (60D) were taken forward to study the effects of adding a thermoplastic toughener (polyethersulphone, PES) in incremental amounts up to 50wt%. SEM images showed all toughened 100T resins had a phase separated morphology whilst all 60D resins were homogenous. The phase separation seen in 100T did not improve the matrix fracture toughness when loaded at 10 wt% and 30 wt% PES. Only when 50 wt% PES was added did fracture toughness increase in comparison to the homogenous 60D resins. Through factorial experimental design two epoxy resin formulations which excluded TGDDM were optimised with a low stoichiometric ratio. The optimum aerospace formulation is dependent on the desired processability and fracture toughness of the resin. High DGEBF-containing formulations give the longest processing windows whilst the 100% TGPAP formulation toughened with 50% PES has the highest fracture toughness.

A commercial epoxy, diglycidyl ether of bisphenol-A, was modified by two different routes. One was the addition of silica to produce epoxy composites. Three different silane coupling agents, glycidyloxypropyl trimethoxy silane (GPS), -methacryloxypropyl trimethoxy silane (MAMS) and 3-mercaptopropyltriethoxy silane (MPS), were used as silica-surface modifiers. The effects of silica content, together with the effects of chemical surface treatment of silica, were studied. The results indicate that epoxy composites with silica exhibit mechanical and tribological properties as well as curing kinetics different than the pure epoxy. The optimum silica content for improved mechanical and tribological properties (low friction coefficient and wear rate) was different for each type of silane coupling agent. An unequivocal correlation between good mechanical and improved tribological properties was not found. Activation energy of overall reactions was affected by the addition of silica modified with MAMS and MPS, but not with GPS. The second route was modification by fluorination. A new fluoro-epoxy oligomer was synthesized and incorporated into a commercial epoxy by a conventional blending method. The oligomer functioned as a catalyst in the curing of epoxy and polyamine. Thermal stability of the blends decreased slightly at a high oligomer content. Higher wear resistance, lower friction coefficient and higher toughness were found with increasing oligomer content; thus in this case there was a correlation between good mechanical and improved tribological properties. The results indicated that increasing toughness and formation of a transfer film contribute to improved tribological performances.

The diploma thesis describes the influence of humid conditions on the curing of epoxy resins by multifunctional amines. The aim of the experimental part was the identification of degradation products and their quantification, as well as the determination of the influence of humid conditions on the degree of hardening, modulus of elasticity, and flexural strength. Another goal was to optimize the formulation of the reactive mixture for the preparation of epoxy resin with lower susceptibility to carbamate bloom. The degradation products were evaluated by determining the mechanical properties by bending test according to the standard ČSN EN 179-1. The degree of hardening was monitored through temperature modulated differential scanning calorimetry (TMDSC). Degradation products were identified by Fourier transform infrared spectroscopy (FTIR) and quantified by UV-VIS spectroscopy. The morphology of the surface layer was monitored by confocal laser scanning microscopy (CLSM). The dependence of the relative humidity of the environment on the curing process of the epoxy resin and its resulting mechanical properties was determined. Based on the analyzes, a modification of the formulation for the suppression of spurious carbamate during the curing of the epoxy matrix was designed and experimentally verified.

Crystallisation of epoxy resins based on bisphenol A and bisphenol F is the natural property of these oligomers. However, manufacturers of paints and other systems based on these epoxy resins, strive to slow down the crystallisation process as much as possible, thereby prolonging the shelf life and improving the competitiveness of their products. The main aim of the thesis is generalisation of the factors influencing the crystallisation process of epoxy resins based on bisphenol A and bisphenol F, verifying new approaches to the possibility of influencing the crystallisation process and determining the possibility of using a certain degree of epoxy resins crystallinity based on bisphenol A and bisphenol F in the preparation and production of epoxy resinbased coating systems.

Work was carried out in collaboration with SYNPO, Inc. Pardubice, which provided samples resins with various additives for measurement. The work is divided into three theoretical and one practical chapters. The first chapter focuses on dielectrics in general. It deals with their properties and storyline running in them. The second chapter discusses epoxy resins, their formulation, production and application in manufacturing. The third chapter offers a view of the measurement methods used for diagnosing electrical dielectrics. The practical part describes the preparation of samples and their composition, and consequently their measurement with the evaluation of measurement data.

Lastabtragende Klebverbindungen stellen im Konstruktiven Glasbau einen wesentlichen Forschungsgegenstand der vergangenen Jahre dar. Getrieben von gestalterischen Gesichtspunkten sind dabei die transparenten Klebstoffe von besonderem wissenschaftlichem und wirtschaftlichem Interesse. Die vorliegende Arbeit widmet sich ausschließlich der Klebstoffgruppe der zweikomponentigen Epoxidharze, da diese im Konstruktiven Glasbau bisher kaum Beachtung finden. Detaillierte Informationen zu den Eigenschaften und zum Verhalten fehlen fast vollständig und werden innerhalb der vorliegenden Arbeit geschaffen. Die durchgeführten Untersuchungen gliedern sich in die Untersuchungen zur Wahl eines geeigneten Epoxidharzes, in die Untersuchungen der Verarbeitungsbedingungen und in die Charakterisierung der optimierten Klebverbindung. Ferner wurden auch konstruktive Maßnahmen zum Schutz der Klebschicht in die Untersuchungen eingebunden. Innerhalb des Untersuchungsprogramms wurde großer Wert auf eine ausgewogene Gewichtung unterschiedlicher Kriterien gelegt. In die engere Auswahl kamen acht Epoxidharzklebstoffe, die grundlegend untersucht und analysiert wurden. Im Ergebnis konnte ein vielversprechender Klebstoff ausgewählt werden. Die weiterführenden Untersuchungen zu den Verarbeitungsbedingungen hatten die Optimierung des Eigenschaftsprofils zum Ziel. Sowohl die thermische Stabilität des Klebstoffs als auch das Anfangs- und das Restbruchverhalten der Glas-Metall-Verbindungen konnten nennenswert verbessert werden. Ebenso wurde die Wirksamkeit der konstruktiven Schutzmaßnahmen erfolgreich nachgewiesen. Aus den Ergebnissen und deren Wertung konnten abschließend Handlungsempfehlungen für den Einsatz transparenter Epoxidharze in Glastragwerken abgeleitet werden. Die sich nach den eigenen Untersuchungen ergebenden, weiteren offenen wissenschaftlichen Fragestellungen und deren zugehöriger Forschungsbedarf werden am Ende ebenfalls erörtert.

No description available.

[pt] Um tipo de resina epoxídica (RE) foi modificada com polibutadieno líquido hidroxilado (PBLH) a partir da mistura física de ambos os componentes (EPH) ou a partir da obtenção de copolímeros em bloco da resina epoxídica com PBLH funcionalizado com grupos isocianato (EPI) e carboxila (EPA). Foi realizado um estudo do comportamento mecânico desses sistemas epoxídicos, após a cura com um endurecedor a base de aminas, antes e após envelhecimento. Também foram avaliadas as propriedades adesivas, antes e após envelhecimento, através de ensaios com juntas de topo e juntas sobrepostas simples fabricadas com esses adesivos e com substratos de aço. O estudo do envelhecimento abrangeu absorção de água a temperatura ambiente e envelhecimento térmico. Foi possível concluir que a condição de pós-cura estabelecida em um trabalho anterior não acarretou na densidade máxima de ligações cruzadas dos sistemas e isto afetou o comportamento dos mesmos após os envelhecimentos. Para as condições de cura e pós-cura aplicadas, a água, no período de tempo estudado, acarretou na plastificação dos sistemas, mas não afetou as propriedades adesivas das juntas fabricadas com os adesivos RE, EPA e EPI. Já o tratamento de envelhecimento térmico a 150oC por 7 dias acarretou na queda de algumas propriedades mecânicas, mas teve o efeito distinto de melhorar as propriedades adesivas das juntas fabricadas com EPI, EPH e EPA em relação à carga de ruptura, todavia resultando num aumento da rigidez efetiva dessas juntas. / [en] A kind of epoxy resin was modified with hydroxyl- terminated polybutadiene (HTPB), using a physical blend of both components (EPH) or using a block copolymer of HTPB-RE. The block copolymers were prepared by reacting RE with isocyanate-funcionalized HTPB (EPI) or carboxyl- funcionalized HTPB (EPA). The cure agent was a blend of amines. A study of the mechanical behavior of these systems was carried out, before and after aging. Also the adhesive properties were evaluated, before and after aging, testing bonded joints (both butt and single-lap) manufactured with these adhesives and employing a steel adherent. This ageing study enclosed water absorption, at ambient temperature, and thermal aging. It can be concluded that the condition of post-cure, established in a previous work, did not promote the maximum crosslink density of the systems and this affected the behavior of these systems after aging. Considering the conditions of cure and post-cure and the period of time applied in this work, the water caused the plasticization of the systems, but it did not affect the adhesive properties of the joints manufactured with the adhesives RE, EPA and EPI. Considering the thermal aging treatment at 150oC during 7 days, it caused the decrease of some mechanical properties, but it had the distinct effect to improve the adhesive properties of the joints manufactured with EPI, EPH and EPA regarding the rupture load, however resulting in an increase of the joints stiffness.

Master of Science / Department of Grain Science and Industry / Xiuzhi Susan Sun / Soybean oil-based resin for transparent flexible coating applications were formulated by dihydroxyl soybean oil (DSO) with commercial epoxy monomers (i.e., epoxidized soybean oil (ESO) and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (ECHM)). The resin was formed to thermoset polymers using cationic ring-opening photopolymerization. The ether crosslinking and post-polymerization of the polymeric network were observed using Fourier transform infrared spectroscopy. Thermal properties of the bio-based coating materials and their copolymerization behaviors were examined using a differential scanning calorimetry and a thermogravimetric analyzer. Crosslink density and molecular weight between crosslink were obtained from dynamic mechanical analysis. ECHM/DSO (1: 1.43 weight ratio) films showed the highest elongation at break (49.2 %) with a tensile strength of 13.7 MPa. After 2 months storage, the elongation at break and tensile strength of films were 32 % and 15.1 MPa, respectively. ESO/DSO films (w/w ratios of 1:0.1, 1:0.15, and 1:0.2) exhibited stable flexibility around 11-13 % of elongations at break without significant reductions of tensile strengths (2.5 to 4.4 MPa) during 2-months shelf life. Optical transparencies of the films were comparable to commercial glass and polymers, and water uptake properties (0.72 and 2.83%) were significantly low.

The aim of the work reported here was to determine the influence of an amine curing agent, and postcure cycle on the mechanical and thermal properties of diglycidyl ether of bisphenol A (DGEBA) epoxy resin. The results of this initial study were then used as the basis for selecting material to obtain optimum toughness in epoxy/glass fibre systems. These basic materials were further used to make comparisons with the properties of modified resin systems which contained commercial elastomers. Differential Scanning Calorimetry (DSC), Dynamic Mechanical Thermal Analysis (DMTA), Fourier Transform Infrared Spectroscopy (FTIR), flexural and interlaminar shear tests, Instrumented Falling Weight Impact (IFWI), visual observation, Scanning Electron Microscopy (SEM), and Transmission Electron Microscopy (TEM) were all used to investigate various properties and the structures which gave rise to them. The properties of cured products were found to be affected by the amounts of curing agent, curing times and temperatures, and the structure of the elastomers. Not surprisingly the maximum thermal and mechanical properties tended to be found in the stoichiometric (standard) mix systems. However, postcuring at higher than room temperature, which was used as the basic curing temperature, led to more conversion. This effect improved the thermal and mechanical properties of both the unmodified and modified resin systems. The maximum flexural strength of 104 MPa of the unreinforced resins was found in the stoichiometric mix ratio after postcure at 150°C for 4 hr. However, the maximum flexural modulus and glass transition temperature (Tg) were found after postcuring at the same temperature for 48 hr. This was believed to be due to increased crosslinking, but unfortunately the longer curing time led to degradation of the resins. In the systems modified with -20 phr of polyetheramine elastomers, the one modified with the lowest molecular weight (2000) was found to have the highest flexural strength (85.8 MPa) and modulus (2.5 GPa). The impact properties of all the composites with modified resin matrices were found to be higher than the unmodified resin matrix composites. The best impact properties were, however, obtained with the elastomer modifier with a molecular weight of 4000. The impact energy at maximum force increased from 11.9 to 16.4 J, and energy at failure increased from 18.7 to 21.6 J. This increase in impact properties was due to the increase in areas of phase separated elastomer particles over similar systems with lower molecular weight modifier.