No description available.

One of the major classes of polymer matrix resins under consideration for structural composite applications in the infrastructure and construction industries is the dimethacrylate matrix resin. An investigation of the relationships between the chemical structures and properties of these dimethacrylate/styrene networks has been conducted. Oligomer number average molecular weights of the polyhydroxyether ranging from 700 to 1200g/mole were studied with systematically varied styrene concentrations to assess the effects of crosslink density and chemical composition on glass transition temperatures, toughness, tensile properties and matrix strain. Network densities have been estimated from measurements of the rubbery moduli at Tg + 40°C. Within this rather small range in vinyl ester molecular weight, toughness of the resultant networks improved tremendously as the vinyl ester oligomer Mn was increased from 700g/mole to 1200g/mole due to improvements in the resistance to crack propagation. As styrene concentration was increased along all series' of materials, brittleness increased even though the molecular weight between crosslinks increased. This was attributed to the inherent relative brittleness of the polystyrene chemical structure relative to the polyhydroxyether component. This may also be related to the reactivity ratios dictating styrene and vinyl ester sequence length and warrants further investigation. As expected, the volume contraction upon cure also decreased significantly as styrene was decreased, and thus residual cure stresses may be reduced in fiber-reinforced composites. Vickers microhardness values decreased for each of the series when molecular weight increased and styrene content decreased. Two different cure procedures were compared to assess the effects of conversion on the physical and mechanical properties. All mechanical properties investigated (i.e. fracture toughness, tensile strength, and microhardness) were dependent on the cure procedure. Materials cured at 140°C were harder, more brittle, had lower elongations and higher rubbery moduli than those cured at 25°C followed by a 93°C postcure. A maximum in the degree of conversion occurred with increasing polymerization temperature and can be explained by the competition between the chemical reaction and molecular mobility. The overall shrinkage per moles of vinyl groups converted was the same when the materials were cured at 25°C or 140°C. However, in the room temperature cured samples, there was essentially no further densification of the network during postcure, regardless of the postcure temperature. A mono-methacrylate analogue of the dimethacrylate terminated poly(hydroxyether) oligomer was synthesized and copolymerized with styrene to study the effects of chain transfer during elevated temperature reactions. / Ph. D.

We report a method of increasing fracture toughness (KIc) and strain energy release rate (GIc) of vinyl-ester (VE) matrix by adopting a hybrid (dual) reinforcement strategy. The idea of using this strategy was to trigger intrinsic polymer-nanoparticle interaction such as carbon nanotube (CNT) pull-out and interface sliding to enhance energy absorption during fracture. Additionally, we included a second reinforcement, graphene nanoplatelets (GNP), to promote crack-deflection, crack bridging and cross-linking density. Both reinforcements were dispersed into the polymer in three states: non-functionalized (nf>); functionalized with COOH (f>); surface-treated with Triton X-100 (TX100). We embarked on numerous experiments with many combinations of these variables. We measured KIc and GIc using ASTM D5045-14. We conducted an exhaustive iterative investigation with three systems (f>CNT-VE; f>GNP-VE; f>CNT-f>GNP-VE) to determine the best weight-percentage for the nanocomposite system that produced the highest KIc and GIc values when compared to neat-VE. We found that 0.5wt% f>CNT with 0.25wt% f>GNP in the VE matrix resulted in the highest fracture toughness values and was termed the optimized hybrid nanocomposites (OHN) system. Subsequently, we explored further increasing the KIc and GIc of OHN through altering the nanoparticle surface characteristics, which led to four OHN groups: f>CNT-f>GNP-VE; f>CNT-f>GNP-TX100-VE; nf>CNT-nf>GNP-TX100-VE; nf>CNT-nf>GNP-VE. We discovered that the OHN group with non-functionalized nanofillers that were TX100 surface treated (0.5wt%nf>CNT-0.25wt%nf>GNP-TX100-VE) generated the greatest improvements in KIc and GIc. Ultimately, we observed that the KIc of neat-VE increased by 65%, from 1.14 to 1.88 MPa*(m½). The improvement in GIc was even greater with an increase of 166%, from 370 to 985 J/(m2). Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) studies showed a minor shift in glass transition temperature (Tg) by up to 8°C when comparing neat-VE specimens to OHN specimens. A similar increase in maximum thermal decomposition temperature (Tp) of up to 8°C was observed through thermogravimetric analysis (TGA) and derivative TGA (DTG). Scanning electron microscope (SEM) studies revealed that the source of improvements in fracture toughness and thermal properties was primarily the three-dimensional hybrid nanostructures (3DHN) that formed by binding CNT and GNP together, which caused an increase in nanoparticle surface area and inhibited agglomerations. / Includes bibliography. / Dissertation (Ph.D.)--Florida Atlantic University, 2018. / FAU Electronic Theses and Dissertations Collection

In this thesis the static and fatigue characteristics of glass filament wound plastic pipes and joints are examined by experiments and numerical analysis. A hydraulic fatigue test rig, capable of exerting static or cyclic pressures of up to 70 MPa, was designed and built to enable pressure tests to be carried out on glass reinforced epoxy and glass reinforced vinyl ester composite pipes incorporating various joints. Static weepage and burst tests were performed on tubular specimens with and without rubber liners to determine their weepage and burst strengths under internal hydraulic pressure and to investigate the influence of the joints. Fatigue weepage tests were performed to determine the fatigue life and failure modes of glass fibre/epoxy and glass fibre/vinyl ester pipes and joints. For each material system, three types of specimen were tested. These were plain pipes, pipes with coupler-bonded joints (or laminate joints in the case of vinyl ester resin based pipes) and pipes with spigot/socket bonded joints. All specimens were commercial products with nominal diameters of two inches (50 mm). A family of curves showing pressure versus life was obtained. It was observed that weepage mostly occurred close to the pipe joints when pipes were subjected to internal pressure. Optical microscopy was used to investigate the damage initiation and propagation mechanisms in the specimens after testing. Finally, two-dimensional and three-dimensional finite element analyses were carried out to calculate the stress and strain distributions, to predict the strength, to interpret the experimental results and to examine the failure modes of the specimens. Ply-by-ply stress analysis and the Tsai-Wu failure criterion were employed for the strength prediction.

[Abstract]: With the increasing use of fibre reinforced polymer (FRP) composites in civil engineering structures, there is a growing realisation of the need to develop newstructural systems which can utilise the unique characteristics of these materials in a more efficient and economical manner. In many instances this will require thedevelopment of new materials tailored to address the unique performance and economic parameters of mainstream construction. Over recent years, researchers at the University of Southern Queensland have pioneeredthe use of a new type of particulate filled polymer core material which greatly improves the robustness and cost effectiveness of FRP structural systems. These compositematerials are composed of small hollow spherical fillers (microspheres) in a thermosetting polymer matrix. Initial research into these materials, including theirfeasibility in prototype structural elements, have shown these materials to have major potential for widespread application in structural composite systems.One of the most promising classes of these materials investigated to date are vinyl ester / cenosphere composites, which utilise cenospheres derived from fly ash in a vinyl ester matrix. Previously reported studies into these materials have been restricted to initialsurveys of material behaviour which sought to identify key parameters in achieving desired performance outcomes in the composite. This dissertation presents the first in-depth investigation of these materials specifically as a core material option for civil infrastructure applications. The particular focus of this work is on the relationship of the vinyl ester matrix to the characteristics of the resultingcomposite. Several key matrix parameters were identified and assessed as to their influence on cure characteristics, fabrication operations, mechanical properties and theretention of such properties under elevated service temperatures. The outcomes of this work have significantly improved the understanding of matrix influences on the behaviour of these composite systems and have been drawn together to provide a number of recommendations on the application of this new technology to new structural systems.

No description available.

M. Tech. Polymer Technoliogy. / Studies the basic curing, rheological and thermomechanical behaviours of hybrids composed of a VE resin and acrylated epoxidised soyabean oil (AESO). The hybrid systems were cured by free radical initiated radical copolymerisation with styrene. The prospective outcomes were: To find suitable initiators/accelerators for the VE/AESO hybrids which work within the entire composition range? To contribute to the selection of VE resins for AESO modification To establish the optimal quantity of AESO required obtaining the best cure characteristics, the most acceptable reduction in Tg, and stiffness as compared with the parent VE resin.

Mechanical properties of (woven carbon fiber / vinyl ester matrix) composites can be greatly improved if the interphase between the reinforcing high-strength low-weight fiber and the thermoset resin is made more compliant. In order to improve the adhesion of the vinyl ester matrix to the carbon fiber, a thermoplastic coating such as poly(vinyl pyrrolidone) (PVP) can be used as an intermediate between the matrix and the fiber. The extent of mutual diffusion at the (sizing material / polymer matrix) interphase plays a critical role in determining the mechanical properties of the composite. In this research, the molecular interdiffusion across a poly(vinyl pyrrolidone))/vinyl ester monomer (PVP/VE) interface is being investigated by Fourier Transform Infrared Attenuated Total Reflectance (FTIR-ATR) spectroscopy. The ATR method which can be used to characterize the transport phenomena, offers several advantages, such as the ability to monitor the diffusion <I>in situ</I> or to observe chemical reactions. In order to separate the effects of the vinyl ester monomer diffusion and the crosslinking reaction, ATR experiments were carried out at temperatures below the normal curing temperature. Diffusion coefficients were determined by following variations in infrared bands as a function of time, and fitting this data to a Fickian model. The values of the diffusion coefficients calculated were consistent with values found in the literature for diffusion of small molecules in polymers. The dependence of diffusion coefficients on temperature followed the Arrhenius equation. Hydrogen bonding interactions were also characterized. The diffusion model used in this study, however, does not seem to be appropriate for the particular (PVP/VE) system. Because the glass transition temperature of the PVP changed as diffusion proceeded, one would expect that the mutual diffusion coefficient did not stay constant. In fact, it was shown that the Tg can drop by 140oC during the diffusion process. A more suitable model of the (PVP/VE) system should take into account plasticization, hydrogen bonding, and especially a concentration dependent diffusion coefficient. Further analysis is therefore needed. / Master of Science

The objective of this study was to develop a model to predict the viscoelastic material functions of a vinyl ester (VE) polymer (Derakane 441-400, Ashland Co.,) with variations in its material properties. Short-term tensile creep/creep recovery experiments were conducted at two stress levels and at four temperatures below the glass transition temperature of the VE polymer, with 10 replicates for each test configuration. Experimental strains in both the longitudinal and transverse directions were measured using a digital image correlation technique. The measured creep strain versus time responses were subsequently used to determine the creep compliances using the generalized viscoelastic constitutive equation with a Prony series representation. The variation in the creep compliances of Derakane 441-400 was described by formulating the probability density functions (PDFs) and the corresponding cumulative distribution functions (CDFs) of the creep compliances using the two-parameter Weibull and log-normal distributions. The maximum likelihood estimation technique was used to obtain the Weibull shape and its scale parameters and the log-normal location and its scale parameters. The goodness-ofit of the distributions was determined by performing Kolmogorov-Smirnov (K-S) hypothesis tests. Based on the K-S test results, the Weibull distribution is a better representation of the creep compliances of Derakane 441-400 when compared to the log-normal distribution. Additionally, the Weibull scale and shape parameters of the creep compliance distributions were shown to be time and temperature dependent. Therefore, two-dimensional quadratic Lagrange interpolation functions were used to characterize the Weibull parameters to obtain the PDFs and subsequently the CDFs of the creep compliances for the complete design temperature range during steady state creep. At each test temperature, creep compliance curves were obtained for CDF values of 0.05, 0.50 and 0.95 and compared with the experimentally obtained lowest, mean and highest creep compliances, respectively. The predicted creep compliances of Derakane 441-400 in the design space are in good agreement with the experimental data.

A data analytic materials informatics methodology is proposed after applying different data mining techniques on some datasets of particular domain in order to discover and model certain patterns, trends and behavior related to that domain. In essence, it is proposed to develop an information mining tool for vapor-grown carbon nanofiber (VGCNF)/vinyl ester (VE) nanocomposites as a case study. Formulation and processing factors (VGCNF type, use of a dispersing agent, mixing method, and VGCNF weight fraction) and testing temperature were utilized as inputs and the storage modulus, loss modulus, and tan delta were selected as outputs or responses. The data mining and knowledge discovery algorithms and techniques included self-organizing maps (SOMs) and clustering techniques. SOMs demonstrated that temperature had the most significant effect on the output responses followed by VGCNF weight fraction. A clustering technique, i.e., fuzzy C-means (FCM) algorithm, was also applied to discover certain patterns in nanocomposite behavior after using principal component analysis (PCA) as a dimensionality reduction technique. Particularly, these techniques were able to separate the nanocomposite specimens into different clusters based on temperature and tan delta features as well as to place the neat VE specimens in separate clusters. In addition, an artificial neural network (ANN) model was used to explore the VGCNF/VE dataset. The ANN was able to predict/model the VGCNF/VE responses with minimal mean square error (MSE) using the resubstitution and 3olds cross validation (CV) techniques. Furthermore, the proposed methodology was employed to acquire new information and mechanical and physical patterns and trends about not only viscoelastic VGCNF/VE nanocomposites, but also about flexural and impact strengths properties for VGCNF/ VE nanocomposites. Formulation and processing factors (curing environment, use or absence of dispersing agent, mixing method, VGCNF fiber loading, VGCNF type, high shear mixing time, sonication time) and testing temperature were utilized as inputs and the true ultimate strength, true yield strength, engineering elastic modulus, engineering ultimate strength, flexural modulus, flexural strength, storage modulus, loss modulus, and tan delta were selected as outputs. This work highlights the significance and utility of data mining and knowledge discovery techniques in the context of materials informatics.