Thesis (Ph.D.)--University of Delaware, 2006. / Principal faculty advisor: Jack R. Vinson, Dept. of Mechanical Engineering. Includes bibliographical references.

The increasing use of composite materials in many industries such as aerospace, automotive, and civil industries has increased the need for the development of effective techniques to detect defects in the bondlines of adhesive joints in composite structures. Currently, composite structures used in commercial applications such as modern aircraft use mechanical fasteners in redundancy to adhesive bonds to ensure structural integrity due to a lack of methods to reliably detect defects in the bondline of composite structure. As such, this thesis facilitates the development of nondestructive evaluation techniques for detecting bondline defects by using finite element (FE) modeling to simulate the effects of disbond defects caused by contamination of the bondline. These models were developed for single-lap joint specimens made of metal, composite, and dissimilar materials (metal bonded with composite) with contamination induced disbonds. The created FE models were used to generate whole-field strain data for single-lap joints under tensile loading. This generated strain data was then used to provide a model for evaluating and interpreting experimental strain measurements captured by digital image correlation (DIC). Finally, conclusions were drawn outlining the observed capability of strain measurement in the evaluation of bondline contamination in single-lap joints.

This study demonstrates an experimental investigation into the efficacy of a novel surface pre-treatment technique to improve the toughness and energy dissipation of composite CFRP T-joints. This novel technique optimizes CO2 laser irradiations to remove surface contaminations and modify the surface morphology of CFRP T-joint adherents. Pull-off tests were performed on T-joints that experienced peel-ply (PP) treatment and to those that were ablated with 10% (LC) and 30% (LA) laser power respectively. A further developed alternative pattern between LA and LC surface pre-treatment was examined. Two different quasi-isotropic stacking sequences have been studied by having surface fibers aligned in 0° and 45° direction. A series of surface roughness analysis, optical microscopy, SEM, CT scan and pictorial findings have been carried out to characterize the surface morphologies and failure modes prior to and after the failure. The patterning technique promoted non-local damage mechanisms which resulted in large improvements in the toughness and energy dissipation as compared to the other pre-treatment techniques. Up to ~12 times higher energy dissipation compared to peel-ply pre-treated T-joint were achieved with patterned T-joint structures that are stacked with a 0° surface fiber direction.

Nowadays, Carbon Fiber-Reinforced Polymers (CFRPs) have been widely applied in the aerospace and automotive industries. Secondary adhesive bonding, instead of using rivets or bolts in conventional mechanical fastenings, is promising in joining CFRPs because it is simple and applicable for cured parts, widely applied for repairing structures, and of light weight. However, the mechanical performance of secondary bonding is very sensitive to the treatment of CFRP parts. Besides, another concern arises from the fact that secondary bonded specimen often prematurely fails due to delamination and leads to a catastrophic structural collapse. While enhancing the joint strength and toughness is important, limiting the progression of damage is crucial, to ensure confidence in the design and allow enough time for maintenance and repair. Therefore, it is significant to introduce a crack arrest feature into the joints, to slow down (or even stop) the crack growth and achieve progressive failure. In this thesis, we employ advanced surface preparation strategies to enhance the strength, toughness, and safety of adhesively bonded CFRP joints. Globally uniform surface pretreatments, using conventional mechanical abrasion, peel-ply, and pulsed CO2 laser irradiation, are employed at first to improve the mechanical responses of adhesively bonded CFRP joints. Then, to better understand damage mechanisms and guide the joint design, characterizations of surface chemistry, surface energy, and surface morphology are correlated with obtained strength and toughness. Next, trench patterns, ablated by pulsed CO2 laser irradiation, are applied to CFRP substrate to further analyze the role of surface roughness on increased mode I energy release rate. Finally, a novel surface patterning strategy is proposed to achieve superior toughness enhancement in adhesively bonded CFRP joints to improve the joint safety. Such surface preparation strategy is assessed through 2D numerical models and realized experimentally by patterning of pulsed CO2 laser irradiation, illustrating its potential in toughening the joint and successfully delaying the crack propagation.

Adhesive bonding has become an essential joining method in the automotive industry specially with the recent focus on lightweight reduction. A major limiting factor to the widespread implementation of this joining method is concerns about environmental durability. Many research projects have been conducted to investigate the effect environmental exposure on cured adhesive joints, however, the effect that this exposure has on uncured bonds has been overlooked. This study, conducted in collaboration with Volvo cars, aims to investigate the degradation of mechanical properties caused by environmental exposure on uncured bonds and to provide practical recommendations on how to minimize its detrimental effect.  To achieve these objectives adhesive joints were manufactured by a crash resistant epoxy based adhesive and exposed to different climates for different ageing times and conditions. Afterwards, curing and mechanical testing were performed to assess the degradation of mechanical properties: shear strength, peel strength and fatigue life. Analysis of the results showed harsher climates to be linked to an increase in degradation of mechanical properties, an open bond exposure to accelerate the degradation process. Defects were introduced as pores and a decrease in adhesion to the adherend. Practical recommendations were made to minimize open bond exposure and harsh climates.

Although bond-normal stresses have been shown to be responsible for the failure of most laboratory adhesive joint geometries, the measurement of these stresses has been accomplished only through the use of very sophisticated optical techniques. In order to develop a more versatile measurement technique, poly(vinylidene fluoride) film was used to develop piezoelectric stress sensors. The sensitivities of the film to normal stresses in the three principal material directions of the orthotropic film were accurately measured using a charge amplifier and a storage oscilloscope. These measured sensitivities comprised the calibration constants of the film. In order to reduce the detrimental effect on bond strength caused by embedding the low surface energy film into adhesive bondlines, surface treatment methods were investigated using contact angle studies, XPS analysis and 1800 peel and tapered double cantilever beam adhesion specimens. An acid etch using a mixture of acetic, phosphoric and nitric acids was found to greatly improve the bond strengths to an epoxy adhesive without reducing the piezoelectric activity of the film. The bond-normal stresses in both the elastomeric butt joint and the single lap shear joint were measured using the developed stress sensors. Comparison of the measured stresses with calculated values obtained from closed-form analytical solutions and finite element analysis for the stresses was excellent. The piezoelectric sensors do have several important limitations. The piezoelectric activity of the film is lost at temperatures above 100°C (210°F). Also, the sensors are only sensitive to dynamic loads. Nonetheless, the sensors provide an accurate means of measuring peel stresses in many adhesive joints of practical interest. / Ph. D.

This thesis contains the results of Phase-1 of a project funded by Ford Motor Company. The objective is to study the feasibility of Acousto-Ultrasonics (AU) as a nondestructive technique for assuring the quality of adhesively bonded sheet-metal used for automobiles. Other nondestructive (NDT) techniques were also applied viz., ultrasonics. radiography and thermography to supplement and verify the results of the AU technique. The AU Technique demonstrated the best results in terms of its sensitivity to the variations in the properties of the interface. Regions having kissing bonds or regions lacking adhesive were easily identified by this technique. These regions contribute to the mixed mode failure. A bond quality (BQ) model is suggested to take into account the mixed mode failure. Destructive testing results show fairly consistent correlation of BQ values with the breaking strength of the adhesive joint failing in mixed mode failure. The BQ values were calculated from the SWF (stress wave factor) values generated by the AU technique. No correlation was observed between the SWF values and the breaking strengths of the bonds failing cohesively. Cohesive failures occur at higher loads than those for mixed mode failures. These are, of course, governed by the maximum possible strength of a joint. More work needs to be done to develop a better way to analyze signals for differentiating total cohesive failure, at least for academic interest. The results strongly suggest the potential of this technique for quantitative evaluation of such types of bonding. Automation of this technique can be developed for application on the assembly line of the motor-car industry. Future work to make this technique more efficient and sensitive is suggested. / Master of Science

Cette thèse porte sur l’étude multi-échelle du vieillissement d’assemblages collés à base de colle époxy employés dans le domaine aéronautique. Dans leurs conditions de service, ces matériaux sont soumis à un vieillissement humide, qui peut s’accompagner d’un vieillissement thermique essentiellement lors des phases de décollage des avions. De telles conditions rendent difficiles la prédiction de la durée de vie basée uniquement sur le suivi des propriétés mécaniques des assemblages (par des tests de cisaillement simple ou de clivage) lors d’essais de vieillissement normalisés qui prévalent, pour le moment, dans l’industrie. Notre objectif était donc une étude du vieillissement à l’échelle moléculaire afin d’en dériver, à terme, des lois cinétiques prédisant la vitesse de dégradation. Une première étape a mis en lumière les différences existantes entre le vieillissement humide (rupture adhésive) et thermique (rupture cohésive). La rupture cohésive observée en vieillissement thermique nous a conduits à étudier les mécanismes responsables de la chute de ténacité des époxys. Nous avons ainsi étudié les mécanismes de dégradation de l’adhésif, de deux de ses systèmes « représentatifs » (DGEBA-DDS et TGMDA-DDS). L’analyse des produits de dégradation dans ces réseaux et leurs composées modèles nous a conduits à élaborer un schéma cinétique intégrant la réactivité des principaux sites d’oxydation (sites au voisinage de certains hétéroatomes) qui peut décrire en partie l’oxydation des systèmes simples DGEBA-DDS et TGMDA-DDS mais devra être converti en modèle de co-oxydation (c’est-à-dire intégrant la participation simultanée de plusieurs sites) à la fois pour décrire plus complétement l’oxydation des systèmes simples mais surtout pour traiter des matériaux industriels de formulation complexe. Dans une dernière partie, nous nous sommes intéressés à la spécificité des assemblages collés lors d’un vieillissement humide. Cette dernière partie montre la nécessité de bien comprendre les phénomènes de diffusion à l’interface, et dans des matériaux oxydés, pour pouvoir prédire la durée de vie des adhésifs époxys employés pour les assemblages collés. / This thesis deals with a multi-scale study of the ageing of bonded assemblies based on epoxy adhesive used in the aeronautical field. In service conditions, these materials are subjected to humid ageing, which can be accompanied by thermal ageing essentially during the take-off phases of aircraft. Such conditions make it difficult to predict lifetime based only on the study of the mechanical properties of the assemblies (by single lap shear stress or wedge tests) in standardized ageing tests, which, for the moment, prevail in the industry. Our objective was therefore a study of ageing at the molecular scale in order to derive forward kinetic laws predicting the kinetics of degradation. A first step highlighted the differences between humid ageing (adhesive failure) and thermal aging (cohesive failure). The cohesive rupture observed in thermal ageing led us to study the mechanisms responsible for the decrease in toughness of the epoxies. We studied the mechanisms of degradation of the adhesive as well as two of its "representative" systems (DGEBA-DDS and TGMDA-DDS). The analysis of degradation products in these networks and their model compounds led us to develop a kinetic scheme introducing the reactivity of the main oxidation sites (site near certain heteroatoms) which can partly describe the oxidation of simple systems. In the future, DGEBA-DDS and TGMDA-DDS will have to be converted into a co-oxidation model (that means integrating the simultaneous participation of several sites) to describe entirely the oxidation of simple systems but especially for handled industrial materials of complex formulation. In a last part, we were interested in the specificity of bonded assemblies during humid aging. This last section displays the need to understand diffusion phenomena at the interface, and in oxidized materials, to predict the lifetime of epoxy adhesives used for bonded assemblies.

Die moderne Architektur ist durch gläserne Fassaden und ausgefallene Konstruktionen aus Glas geprägt. Dabei wird Glas nicht nur als raumabschließendes Element verwendet, sondern auch konstruktiv eingesetzt und zunehmend an der Lastabtragung beteiligt. Die Integration von Glaselementen in die Baukonstruktion erfolgt über linien- oder punktförmige Lagerungen. Dabei können mechanisch ausgeführte Halterungen lokale Beanspruchungen und damit Glasversagen verursachen. Eine Alternative bilden Klebverbindungen, welche ein materialgerechtes Konstruieren im Glasbau ermöglichen. Kommerziell wird hierfür eine Vielzahl von Klebstoffen angeboten. Neben der Auswahl eines geeigneten Klebstoffsystems können dauerhafte adhäsive Verbindungen aber meist nur mit Hilfe von Oberflächenvorbehandlungen der Fügeteile gewährleistet werden. Aufgrund der langen Standzeiten von Bauwerken sind große Beständigkeiten von geklebten Verbindungen notwendig, welche nur durch den Aufbau von möglichst hohen Haftungskräften zwischen Fügeteiloberflächen und Klebstoffpolymer erreichbar sind. Spezielle Vorbehandlungsverfahren sorgen für eine bessere Benetzbarkeit der Oberflächen und schaffen zudem energetisch aktive Zentren, die mit den Klebstoffen in Wechselwirkung treten können. Viele der insbesondere für metallische Materialien industriell etablierten Oberflächenvorbehandlungen sind allerdings wenig zukunftsträchtig, da diese Verfahren häufig den Einsatz ätzender, hochgiftiger und umweltgefährdender Substanzen notwendig machen. Hierin liegt der Ansatzpunkt der vorliegenden Arbeit. In verschiedenen Industriebereichen, wie dem Automobilbau, der Elektrotechnik und der Dentalmedizin werden bereits neu entwickelte Oberflächenvorbehandlungsverfahren auf Basis von Plasma- und Abscheidungstechnologien eingesetzt. Daraus ergibt sich die Fragestellung nach der Anwendbarkeit solcher Verfahren auf Fügeteilmaterialien des Konstruktiven Glasbaus und nach dem Nutzen dieser Oberflächenvorbehandlungen in Bezug auf die Optimierung von strukturellen Klebungen. Für die Ermittlung optimaler Eigenschaften von Oberflächen für den klebtechnischen Prozess werden ausgewählte Fügeteile aus Edelstahl, Aluminium und Messing sowie Einscheibensicherheitglas aus Kalk-Natronsilikatglas physikalischen und chemischen Oberflächenanalysen vor und nach der Anwendung von vier verschiedenen Oberflächenvorbehandlungsverfahren unterzogen. Zudem werden die Haftungseigenschaften nach der Vorbehandlung an geklebten Prüfkörpern vor und nach Alterung untersucht. Aus den daraus erhaltenen Ergebnissen wird der Einfluss der Oberflächenbeschaffenheit auf die Festigkeit der Klebverbindungen bestimmt. Die durchgeführten Untersuchungen ergeben sehr unterschiedliche, stark substrat- und klebstoffabhängige Wirkungsweisen der einzelnen Oberflächenvorbehandlungen. Als geeignetes Verfahren in Bezug auf die Verbesserungen des Adhäsionsvermögens und der Alterungsbeständigkeit, die Integrierbarkeit in maschinelle Herstellungsprozesse und die Vermeidung optischer Veränderung der Oberflächen stellt sich die Flammensilikatisierung heraus. Die mit dieser Oberflächenvorbehandlung aufgebrachte, dichte Silikatschicht und deren chemische Aktivität sowie deren vollständige Benetzbarkeit bieten beste Voraussetzungen für die Verklebung verschiedener Fügeteilmaterialien mit unterschiedlichsten Klebstoffen. / The modern architecture is affected by glass facades and novel glass structures. Therein glass is not only used as space enclosing element, rather it finds more and more constructive application and it is increasingly involved in load transfer. State of the art for the integration of glass elements in buildings are mechanically designed point and linear fixings. But they may cause local stresses followed by glass breakage. An alternative to these fixations are adhesive joints which more respect the specific requirements of the fragile material glass. A wide variety of adhesives is already available for this purpose. For strong adhesive joints not only the selection of a suitable adhesive is essential. The surface quality, which can be enhanced by surface treatments, is just as important for a very good adhesion. Due to the long life expectancy of buildings, a permanently aging resistance of the adhesive joints is necessary. For that, a formation of the highest possible adhesion forces between adhesive polymer and adherend surface is essential. Special surface treatment processes ensure a better wettability of the surfaces and also create energetically active sites that can interact with the adhesive molecules. However, many of the industrially established surface pretreatments, especially those for metallic materials, are not sustainable, since these methods often use corrosive, highly toxic and environmentally hazardous substances. This is the basis of the present dissertation. In various industries, such as automotive, electrical engineering and dentistry, newly developed surface treatment methods based on plasma and deposition technologies are already used. This raises the question of the applicability of such methods on materials for glass constructions and of their benefit to the optimization of structural adhesive joints. The effect of four different surface treatment methods used on the surfaces of stainless steel, aluminum, brass and toughened safety glass made from soda-lime glass is investigated in experimental studies. Physical and chemical surface analyses are performed before and after the applications. In addition, the adhesion properties of bonded specimens with pretreated surfaces are examined before and after aging. The influence of the surface conditions on the strength of the adhesive joints is determined from the obtained results. The results show very different effects of the individual surface treatment methods with high dependences on substrate and adhesive. With regard to an increase of adhesion strength, a good aging resistance, an uncomplicated integration into automated production processes and an avoidance of changing the optical surface properties, the investigated combustion chemical vapour deposition is the most suitable method. With this pretreatment, a dense silicate layer is deposite on the surface. Its high chemical activity and its complete wettability offer the best conditions for bonding a variety of materials with different adhesives.

Adhesive bonding which has been in use for long as a traditional joining method has gained ground in the last couple of decades due to the introduction of advanced composite materials into the aerospace industry. Bonded structures have advantages such as high corrosion and fatigue resistance, ability to join dissimilar materials, reduced stress concentration, uniform stress distribution, good damping characteristics etc. They also have certain limitations like environmental degradation, existence of defects like pores, voids and disbonds, difficulty in maintenance and repair etc. A serious drawback in the use of adhesively bonded structures has been that there are no established comprehensive non-destructive testing (NDT) techniques for their evaluation. Further, a reliable evaluation of the effect of the existing defects on strength and durability of adhesive joints is yet to be achieved. This has been a challenge for the research and development community over several decades and hence, been the motivation behind this piece of research work. Under the scope of the work carried out in the thesis, some of the primary factors such as the existence of defects, degradation of the adhesive, stress and strain distribution in the bonded region etc., have been considered to study the bond integrity in composite to composite lap shear joints. The problem becomes complex if all the parameters affecting the adhesive joint are varied simultaneously. Taking this into consideration, one of the key parameters affecting the bond quality, viz., the adhesive layer degradation was chosen to study its effect on the bonded joint. The epoxy layer was added with different, definite amount of Poly vinyl alcohol (PVA) to arrive at sets of bonded joint specimens with varied adhesive layer properties. A thorough review of different non destructive testing methods applied to this particular problem showed that ultrasonic wave based techniques could be the right choice. To start with, preliminary experimental investigations were carried on unidirectional glass fiber reinforced plastic (GFRP-epoxy) lap joints. The adhesive joints were subjected to non destructive evaluation (NDE) using ultrasonic through transmission and pulse echo techniques as also low energy digital X-ray techniques. The results obtained showed a variation in reflected and transmitted ultrasonic pulse amplitude with bond quality. Digital X-Ray radiography technique showed a variation in the intensity of transmitted x-rays due to variation in the density of adhesive. Standard mechanical tests revealed that the addition of PVA decreased the bond strength. A plot of coefficient of reflection from the first interface and the bond strength showed a linear correlation between them. After obtaining a cursory feel and understanding of the parameters involved with the preliminary experiments on GFRP adhesive joints which yielded interesting and encouraging results, further work was carried on specimens made out of autoclave cured carbon fiber reinforced plastic (CFRP)-epoxy bonded joints. Normal incidence ultrasound showed a similar trend. Analyses of the Acoustic Emission (AE) signals generated indicate early AE activity for degraded joints compared to healthy joints. Literary evidences suggest that the ultrasonic shear waves are more sensitive to interfacial degradation. An attempt was made to use oblique incidence ultrasonic interrogation using shear waves. The amplitude of reflected shear waves from the interface increased with an increase in degradation. Further, a signal analysis approach in the frequency domain revealed a shift in the frequency minimum towards lower range in degraded samples. This phenomenon was verified using analytical models. An inversion algorithm was used to determine the interfacial transverse stiffness which decreased significantly due to increase in degradation. Conventional ultrasonic evaluation methods are rendered ineffective when a direct access to the test region is not possible; a different approach with guided wave techniques can be explored in this scenario. Investigations on CFRP-epoxy adhesive joints using Lamb waves showed a decrease in the amplitude of ‘So’ mode in degraded samples. Theoretical dispersion curves exhibited a similar trend. Frequency domain studies on the received modes using Gabor wavelet transform showed a negative shift in frequency with increased degradation. It was also observed that the maximum transmission loss for the most degraded sample with 40 percent PVA occurred in the range of 650 – 800 kHz. Non linear ultrasonic (NLU) evaluation revealed that the nonlinearity parameter (β) increased with increased degradation. Kissing bonds are most commonly occurring type of defects in adhesive joints and are very difficult to characterize. A recent non-contact imaging technique called digital image correlation (DIC) was tried to evaluate composite adhesive joints with varied percentage of inserted kissing bond defects. The results obtained indicate that DIC can detect the kissing bonds even at 50 percent of the failure load. In addition, to different experimental approaches to evaluate the bonded joint discussed above, the effect of degradation on the stresses in the bond line region was studied using analytical and numerical approach. A linear adhesive beam model based on Euler beam theory and a nonlinear adhesive beam model based on Timoshenko beam theory were used to determine the adhesive peel and shear stress in the joint. Digital image correlation technique was used to experimentally obtain the bond line strains and corresponding stresses were computed assuming a plane strain condition. It was found that the experimental stresses followed a similar trend to that predicted by the two analytical models. A maximum peel stress failure criterion was used to predict failure loads. A failure mechanism was proposed based on the observations made during the experimental work. It was further shown that the critical strain energy release rate for crack initiation in a healthy joint is much higher compared to a degraded joint. The analytical models become cumbersome if a larger number of factors have to be taken into account. Numerical methods like finite element analysis are found to be promising in overcoming these hurdles. Numerical investigation using 3D finite element analysis was carried out on CFRP-epoxy adhesive joints. The adherend – adhesive interface was modeled using connector elements whose stiffness properties as well as the bulk adhesive properties for joints with different amounts of PVA were determined using ultrasonic inspection method. The peel and shear stress variation along the adhesive bond line showed a similar trend as observed with the experimental stress distribution (DIC) but with a lesser magnitude. A parametric study using finite element based Monte-Carlo simulation was carried out to assess the effect of variation in various joint parameters like adhesive modulus, bondline thickness, adherend geometrical and material properties on peel and shear stress in the joint. It was found that the adhesive modulus and bond line thickness had a significant influence on the magnitude of stresses developed in the bond line. Thus, to summarize, an attempt has been made to study the bond line integrity of a composite epoxy adhesive lap joint using experimental, analytical and numerical approaches. Advanced NDE tools like oblique incidence ultrasound, non linear ultrasound, Lamb wave inspection and digital image correlation have been used to extract parameters which can be used to evaluate composite bonded joints. The results obtained and reported in the thesis have been encouraging and indicate that in specific cases where the bond line thickness and other relevant parameters if can be maintained or presumed reasonably non variant, it is possible to effectively evaluate the integrity of a composite bonded joint.