The mechanical characterization of the interfacial shear strength (IFSS) of carbon nanotube (CNT) coated carbon fibers and the interlaminar fracture toughness of woven fabric carbon fiber/epoxy composites toughened with CNT/epoxy interleave films is presented. The deposition of multiwalled carbon nanotubes (MWCNT) onto the surface of carbon fibers through thermal chemical vapor deposition (CVD) was used in an effort to produce a graded, multifunctional interphase region used to improve the interfacial strength between the matrix and the reinforcing fiber. Characterization of the IFSS was performed using the single-fiber fragmentation test. It is shown that the application of a MWCNT coating improves the interfacial shear strength between the coated fiber and matrix when compared with uncoated fibers. The effect of CNT/epoxy thin interleave films on the Mode I interlaminar fracture toughness of woven fabric carbon/epoxy composites is examined using the double-cantilever beam (DCB) test. Initiation fracture toughness, represented by critical strain energy release rate (GIC), is shown to improve over standard un-toughened composites using amine-functionalized CNT/epoxy thin films. Propagation fracture toughness is shown to remain unaffected using amine-functionalized CNT/epoxy thin films with respect to standard un-toughened composites.

Research is presented which encompasses a study of epoxies based on diglycidyl ether of bisphenol A (DGEBA) cured with 2-ethyl-4-methylimidazole (EMI-24) in the presence of the nonionic surfactant Triton X-100. Interest in this epoxy system is due partially to the potential application as a waterborne replacement for solvent cast epoxies in E-glass laminated printed circuit boards. This research has revealed that the viscoelastic behavior of the cured epoxy is altered when serving as the matrix in a glass composite. The additional constraining and coupling of the E-glass fibers to the segmental motion of the epoxy matrix results in an increased level of viscoelastic cooperativity. Current research has determined that the cooperativity of an epoxy/E-glass composite is also sensitive to the surface chemistry of the glass fibers. Model single-ply epoxy/E-glass laminates were constructed in which the glass was pretreated with either 3-aminopropyltriethoxysilane (APS) or 3-glycidoxypropyltrimethoxysilane (GPS) coupling agents. Dynamic mechanical analysis (DMA) was then used to create master curves of the storage modulus (E') in the frequency domain. The frequency range of the master curves and resulting cooperativity plots clearly varied depending on the surface treatment of the glass fibers. It was determined that the surfactant has surprisingly little effect in the observed trends in cooperativity of the composites. However, the changes in cooperativity due to the surface pretreatment of the glass were lessened by the aqueous phase of the waterborne resin. Moisture uptake experiments were also performed on epoxy samples that were filled with spherical glass beads as well as multi-ply laminated composites. No increases in the diffusion constant could be attributed to the surfactant. However, the surfactant did enhance the final equilibrium moisture uptake levels. These equilibrium moisture uptake levels were also sensitive to the surface pretreatment of the E-glass. / Ph. D.

Master of Science / Department of Mechanical and Nuclear Engineering / Kevin Lease / Carbon fiber reinforced composites (CFRP’s) are a mainstay in many industries, including the aerospace industry. When composite components are damaged on an aircraft, they are typically repaired with a composite patch that is placed over the damaged material and cured into the existing composite material. This curing process involves knowledge of the curing time necessary to sufficiently cure the patch. The inexact nature of curing composites on aircraft causes a significant waste of time and material when patches are unnecessarily redone. Knowing how differences in cure cycle affect the strength of the final material could reduce this waste. That is the focus of this research. In this research, the interfacial shear strength (IFSS) of carbon fiber/epoxy composites was investigated to determine how changes in cure cycle affect the overall material strength. IFSS is a measure of the strength of the bond between the two materials. To measure this, the microbond method was used. In this method, a drop of epoxy is applied to a single carbon fiber. The specimen is cured and the droplet is sheared from the fiber. The force required to debond the droplet is recorded and the data is analyzed. The IFSS of AS4/Epon828, T650/Epon828, and T650/Cycom 5320-1 composites were evaluated. For the former two material systems, a cure cycle with two steps was chosen based on research from others and then was systematically varied. The final cure time was changed to determine how that parameter affected the IFSS. It was found that as the final cure time increased, so did the IFSS and level of cure achieved by the composite to a point. Once the composite reached its fully cured state, increasing the final cure time did not noticeably increase the IFSS. For the latter material system (T650/Cycom 5320-1), the two cure cycles recommended by the manufacturer were tested. These had different initial cure steps and identical final cure steps. Although both cure cycles caused high IFSS, the cycle with the higher initial temperature, but shorter initial cure time achieved a higher level of cure than that with a longer time, but shorter temperature.

Crosslinking soft tissue has become more common in tissue engineering applications, and recent studies have demonstrated that soft tissue mechanical behavior can be directly altered through crosslinking, but increased understanding of how crosslinking affects intervertebral disc mechanical behavior is needed. In vitro testing of bovine disc and motion segments was used to characterize several important aspects of disc behavior in response to crosslinking after both soaking and injection treatment. The first study was a comparison of different crosslinkers to determine the effect on tensile properties of disc tissue. Circumferential specimens were taken from bovine annulus and then soak treated with an optimized crosslinking formulation or sham solution. A non-contacting laser micrometer was used to measure cross sectional area, after which tension testing until failure was performed to determine yield strain, yield stress, ultimate stress, peak modulus, and resilience. The crosslinkers were observed to produce different changes in the properties, with the measured properties generally increasing. The second study used bilateral annular injections to simulate a clinically relevant delivery method. The dose response of the motion segment’s neutral zone stability metrics against injection concentration was mapped. Concentrations of 20 mM and less had no significant effects on the stability metrics. 40mM demonstrated a change in neutral zone stiffness, while at least 80mM was required to significantly affect neutral zone length. Thus, meaningful changes in joint neutral zone stability were demonstrated using clinically relevant injection and chemical formulations. The third study used combinations of biochemical and accelerated mechanical cyclic loading to degrade gelatin and annulus fibrosus specimens with and without genipin treatment. Genipin crosslinking attenuated changes during cyclic loading to specimen geometry and compliance relative to control samples. Full recovery of genipin treated samples appeared to be hampered, at least partially from continued crosslinking during the accelerated testing. The fourth study tested the effect of genipin crosslinking to resist interlamellar shearing of the annulus lamella. Using a recently reported test method that shears adjacent lamella, crosslinked specimens were noted to have significantly higher yield force, peak force, and resilience compared to sham treated controls, supporting the hypothesis that crosslinking would increase the load bearing ability of the interface.

The objective of this study is to analyze theoretically the laminar film condensation of water vapor flowing on a sphere. For this purpose, the problem was handled by including all of the two-phase boundary layer parameters such as gravity, effect of vapor shear, inertia, energy convection and pressure gradient. For this full two-phase boundary layer system, the boundary layer equations, boundary conditions and the interfacial conditions were first analyzed, and then discretized. A computer program in Mathcad, solving these discretized equations, was written to obtain the velocity and temperature profiles within the condensate, the velocity profiles within the vapor, the condensate film thickness and the local Nusselt number. The effects of pressure gradient, gravity, vapor oncoming velocity and sphere radius on these parameters were examined. By alternating the formulation of the problem, the results for the flow over a horizontal cylinder were obtained. These results were then compared with those for the sphere. Finally, the results for the system with Mercury vapor flowing on a sphere were obtained. All of these results were represented as diagrams and tables, and were discussed at the end of the study.

Fiber sizings are used to improve the performance of fiber-reinforced polymer composites made from low-cost fiber and matrix materials. Evaluation of three sizings, poly(vinylpyrrolidone) (PVP), a carboxyl modified polyhydroxyether (PHE), and a standard industrial sizing (G'), have revealed tremendous improvements in static mechanical and enviro-mechanical properties. The focus of this work is to determine if these improvements in performance can be ascertained from a micromechanical test for interfacial shear strength (IFSS) on as-processed materials. The accomplishment of this goal would create more information with fewer experiments and a need for less experimental materials. In this study, a nanoindenter uniquely outfitted with a blunt tip is effectively used to obtain microindentation results where the debond load is extracted directly from the experimental load-deflection curve. Shear lag and finite element analyses are used to evaluate the mechanics of the system, but both methods show limitations with regard to determining interfacial stresses in an experimental system. In the results obtained, the PHE and Gâ materials outperform the PVP in IFSS, but the bulk properties for PVP and PHE outperform the Gâ material, suggesting the presence of another dominant mechanism. Despite better retention of bulk properties after hygrothermal exposure, PHE experiences degradation in IFSS that PVP does not. The PHE loses 10% of its original IFSS after 576 hours of 65ºC moisture exposure, while PVP improves by 25%. The tensile strengths for PHE and PVP decrease 7% and 10% respectively at 576 hours exposure. Finite element modeling shows that matrix swelling due to moisture absorption increases interfacial shear stresses, a finding supported by a comparison of wet and dry specimens subjected to equivalent aging times. Matrix swelling is not, however, responsible for the increase in IFSS of the PVP material. The relationship between tensile strength and IFSS proves to be small as predicted by a tensile strength model, but processing defects and other failure processes that are not included in the tensile strength model appear to have strong influences over the experimental results. IFSS is important in composite materials, but in the case of the G', PHE and PVP materials, other factors dominate fiber direction tensile performance. Therefore, this one simple micromechanical test provides significant insight into the composite material behavior, but it does not provide the same magnitude of information as from bulk composite experiments. / Master of Science

Master of Science / Department of Mechanical and Nuclear Engineering / Kevin B. Lease / This research was intended to measure the interfacial shear strength between fiber/ matrix systems and to investigate the relation between structure-mechanical properties and performance of fiber/matrix systems. This work conducted a systematic study on model fiber/matrix systems to enhance the fundamental understanding on how variation of polymeric compositions (and hence, different structures), different curing conditions, and fiber surface treatments influence the interactions between the fiber and matrix. In order to measure the interfacial shear strength of fiber/matrix systems, the microdroplet technique was used. In this technique a polymer droplet was deposited on a fiber in the liquid state. Once the droplet was cured a shear force was applied to the droplet in order to detach the droplet from the fiber. The amount of the force needed to de-bond the droplet was directly related to the strength of the bonds formed between the fiber and matrix during the curing process. In addition, the micro-droplet technique was used to evaluate effects of different crosslinker ratio of fiber/ matrix system and also to see if different curing conditions affect the interfacial shear strength of fiber/ matrix system. Surface treatment was also conducted to evaluate its effects on the interfacial shear strength of the fiber/ matrix system using microdroplet technique. The interfacial shear strength of fiber/ matrix system increased along with the increase of crosslinker ratio to a limiting value, and it decreased as long as the crosslinker ratio increased. Curing condition also caused the interfacial shear strength of fiber/ matrix system to increase when it was cured at higher temperature. Fiber surface treatment exhibited a significant effect to the interfacial shear strength as well as the fiber/ matrix contact angle measurement.

The objective of this research work was to develop a methodology for experimentally estimating the interfacial properties at slag-metal interfaces. From previous experiments carried out in the division, it was decided to use surface active elements like sulfur or oxygen to trace any motion at the interface. For this purpose the following experimental investigations were carried out. Firstly the density of slag was estimated using the Archimedes Principle and the Sessile Drop technique. The density of the slag would give the molten slag height required for the surface active element to travel before reaching the slag-metal interface. Diffusivity measurements were uniquely designed in order to estimate the sulfur diffusion through slag media. It was for the first time that the chemical diffusivity was estimated from the concentration in the metal phase. Experiments carried out validated the models developed earlier. The density and diffusivity value of sulfur in the slag was used to accurately capture the time for sulfur to reach the slag-metal interface. The oscillations were identified by calculating the contact angle variations and the interfacial velocity was estimated from the change in the surface area of the liquid iron drop. The interfacial tension was estimated from the contact angles and the interfacial dilatational modulus was calculated. Based on cold model experiments using water as well as mercury, an equation of the dependence of the interfacial shear viscosity on the interfacial velocity and interfacial tension was established. This paved way for the estimation of the interfacial shear viscosity at the slag-metal interface. The present study is expected to have a strong impact on refining reactions in pyometallurgical industries where slag/metal interfaces play an important role. From a fundamental view point, this provides a deeper insight into interfacial phenomena and presents an experimental technique to quantify the same. / QC 20101130

The main objective in this work was to learn how the instrument, the Interfacial Shear Rheometer (ISR400), worked and to investigate how the rheological properties, storage modulus (elasticity), G' and loss modulus (viscous), G'', changes when the surface pressure at the air-liquid interphase changes. The second objective were to examine the different kind of magnetic needles used in the experiments and to conclude which type of needle is best for its specific field of analysis. It was concluded that the relative heavy needle with mass 70.6 mg and length 50 mm was best for systems where the viscous and elastic components are significantly large, where the inertia of the needle is not dominant. It also worked of using the heavier needle for a system of phospholipids. For the hydroxystearic acid (HSA) experiment that were tested on NaCl sub-phase there was a clear improvement after switching from the heavy needle (mass 41.5 mg; length 51 mm) to the relative lighter needle (mass 6.94 mg; length 34.7 mm). The values for the dynamic modulus therefore had a better agreement with reference literature. A spread layer of class II hydrophobins (HFBII) could be compressed to a surface pressure of 46 mNm-1. The G' and G'' values from the frequency sweep were discarded because the monolayer turned into a very viscous-like liquid, and the oscillating needle, after compression, was kind of stuck in the sub-phase and moved very staggering during a frequency sweep. The needle comparison experiment with silica particles 10 wt% Bindzil CC30 (BCC30), at pH 3.5 was done to see if there was any difference in the sensitivity for the needles at the interface which consisted of a pure 10 mM NaCl solution or a 10 mM NaCl solution with BCC30 added to it. The differences were negligible in terms of surface tension but there was a clear difference between the heavy needle and the light needle, when oscillating at higher frequencies (>≈6 rad/s). With this study, the understanding of ISR400 has increased largely. Several issues have been addressed and the results provide a good basis for further studies within the many areas the instrument can be used for. Despite the project's time limit, and the fact that the instrument was new and untested where the project was carried out, focus areas were prioritized so good results could be achieved within reasonable goals. / Huvudmålet med detta arbete var att lära sig hur instrumentet ytskiktsreometern (ISR400) fungerade och undersöka hur de reologiska egenskaperna, elasticitetsmodulen G' och viskositetsmodulen G'', kommer att förändras när det sker en förändring för yttrycket vid gränsskiktet mellan luft och vätska. Det sekundära målet var att undersöka vilken typ av magnetiska nålar som är bäst att använda för respektive gränsskiktssystem. Av att använda den tyngre nålen med massan 70.6 mg och längden 50 mm kunde man dra slutsatsen att den är bäst att använda för system där de viskösa och elastiska komponenterna är signifikant stora, där nålens tröghet inte är dominant. Den fungerade även att mäta med i ett fosfolipidsystem. I experimentet med 12-hydroxy-stearinsyra (HSA) som utfördes på en subfas av NaCl, syntes en klar förbättring efter att byta från en tyngre nål (massa 41.5 mg; längd 51 mm) till en lättare (massa 6.94 mg; längd 34.7 mm). Värdena för dynamiska modulen stämde därför bättre överens med referenslitteraturen. Det utspridda lagret av klass II hydrophobins (HFBII) kunde komprimeras upp till yttrycket 46 mNm-1. Värdena för G' och G'' förkastades därför att monolagret förvandlades till en väldigt viskösliknande vätska, och den oscillerande nålen, efter kompressionen, satt fast i denna tröga vätska och rörde sig väldigt hackigt och oregelbundet under tiden ett frekvenssvep utfördes. Då en jämförelse av olika typer av nålar genomfördes med kiseldioxidpartiklar (10 % (viktsprocent) Bindzil CC30 med pH 3.5), för att se om det är någon skillnad i känslighet för nålarna vid gränssnittet, som bestod av en ren 10 mM NaCl-lösning eller en 10 mM NaCl-lösning med tillsatt BCC30. Skillnaderna var försumbara gällande ytspänningen, men det var en klar skillnad mellan den tunga nålen och den lätta nålen vid oscillering vid höga frekvenser (>≈6 rad/s). I och med detta arbete så har förståelsen för hur ISR400 fungerar förbättrats mycket sedan starten. Flera frågeställningar har behandlats och resultaten ger en bra grund för fortsatta studier inom de många områden som utrustningen kan användas till. Trots projektets tidsbegränsning, och det faktum att instrumentet var nytt och oprövat på platsen där detta arbete utfördes, så prioriterades fokusområden så att goda resultat kunde uppnås inom rimliga mål.

The non-reactive Dreiding and the reactive ReaxFF atomic potentials were applied within a family of atom molecular dynamics (MD) simulations to investigate and understand interfacial adhesion in graphene/vinyl ester composites. First, a liquid vinyl ester (VE) resin was equilibrated in the presence of graphene surfaces and then cured, resulting in a gradient in the monomer distribution as a function of distance from the surfaces. Then the chemically realistic relative reactivity volume (RRV) curing algorithm was applied that mimics the known radical addition regiochemistry and monomer reactivity ratios of the VE monomers during three-dimensional chain-growth polymerization. Surface adhesion between the cured VE resin and the graphene reinforcement surfaces was obtained at a series of VE resin “crosslink densities.” Both pristine and oxidized graphite sheets were employed separately in these simulations using a Dreiding potential. The pristine sheets serve as a surrogate for pure carbon fibers while oxidizing the outer graphene sheets serve as a model for oxidized carbon fibers. Hence, the effects of local monomer distribution and temperature on the interphase region formation and surface adhesion can be investigated. Surface adhesion was studied at various curing conversions and as a function of temperature. Uniaxial loading simulations were performed at different curing conversions for both models to predict the composites’ modulus of elasticity, Poisson’s ratio, and yield strength. The same analysis was performed for the neat cured matrix. The glass transition temperature (Tg) for the homogenized composite and neat VE matrix was determined at different degrees of curing. Subsequent MD simulations were performed to predict structural damage evolution and fracture in the neat VE matrix. The ReaxFF potential was used to quantify irreversible damage due to bond breakage in the neat VE matrix for different degrees of cure, stress states, temperatures, and strain rates. The predicted damage mechanisms in the bulk VE thermosetting polymer were directly compared to those for an amorphous polyethylene (PE) thermoplastic polymer.