Electrospun nanofibrous interleaves in composite laminate materials

The present work aims for investigate the influence of electrospun Nylon 6,6 nanofibrous mat on the behavior of composite laminates. The main idea is that nanofibrous interleaved into particular ply-to-ply interfaces of a laminate can lead to significant improvements of mechanical properties and delamination/damage resistance. Experimental campaigns were performed to investigate how nanofibers affect both the static and dynamic behavior of the laminate in which they are interleaved. Fracture mechanics tests were initially performed on virgin and 8 different configuration of nanomodified specimens. The purposes of this first step of the work are to understand which geometrical parameters of the nanointerleave influence the behavior of the laminate and, to find the optimal architecture of the nanofibrous mat in order to obtain the best reinforcement. In particular, 3 morphological parameters are investigated: nanofibers diameter, nanofibers orientation and thickness of the reinforce. Two different values for each parameter have been used, and it leads to 8 different configurations of nanoreinforce. Acoustic Emission technique is also used to monitor the tests. Once the optimum configuration has been found, attention is focused on the mechanism of reinforce played by the nanofibers during static and dynamic tests. Low velocity impacts and free decay tests are performed to attest the effect of nanointerlayers and the reinforce mechanism during the dynamic loads. Bump tests are performed before and after the impact on virgin and two different nanomodified laminates configurations. The authors focused their attention on: vibrational behavior, low velocity impact response and post-impact vibration behavior of the nano-interleaved laminates with respect to the response of non-nanomodified ones. Experiments attest that nanofibers significantly strength the delamination resistance of the laminates and increase some mechanical properties. It is demonstrated that the nanofibers are capable to continue to carry on the loads even when the matrix around them is broken.

Active fibre-reinforced composites with embedded shape memory alloys

This dissertation concerns active fibre-reinforced composites with embedded shape memory alloy wires. The structural application of active materials allows to develop adaptive structures which actively respond to changes in the environment, such as morphing structures, self-healing structures and power harvesting devices. In particular, shape memory alloy actuators integrated within a composite actively control the structural shape or stiffness, thus influencing the composite static and dynamic properties. Envisaged applications include, among others, the prevention of thermal buckling of the outer skin of air vehicles, shape changes in panels for improved aerodynamic characteristics and the deployment of large space structures. The study and design of active composites is a complex and multidisciplinary topic, requiring in-depth understanding of both the coupled behaviour of active materials and the interaction between the different composite constituents. Both fibre-reinforced composites and shape memory alloys are extremely active research topics, whose modelling and experimental characterisation still present a number of open problems. Thus, while this dissertation focuses on active composites, some of the research results presented here can be usefully applied to traditional fibre-reinforced composites or other shape memory alloy applications. The dissertation is composed of four chapters. In the first chapter, active fibre-reinforced composites are introduced by giving an overview of the most common choices available for the reinforcement, matrix and production process, together with a brief introduction and classification of active materials. The second chapter presents a number of original contributions regarding the modelling of fibre-reinforced composites. Different two-dimensional laminate theories are derived from a parent three-dimensional theory, introducing a procedure for the a posteriori reconstruction of transverse stresses along the laminate thickness. Accurate through the thickness stresses are crucial for the composite modelling as they are responsible for some common failure mechanisms. A new finite element based on the First-order Shear Deformation Theory and a hybrid stress approach is proposed for the numerical solution of the two-dimensional laminate problem. The element is simple and computationally efficient. The transverse stresses through the laminate thickness are reconstructed starting from a general finite element solution. A two stages procedure is devised, based on Recovery by Compatibility in Patches and three-dimensional equilibrium. Finally, the determination of the elastic parameters of laminated structures via numerical-experimental Bayesian techniques is investigated. Two different estimators are analysed and compared, leading to the definition of an alternative procedure to improve convergence of the estimation process. The third chapter focuses on shape memory alloys, describing their properties and applications. A number of constitutive models proposed in the literature, both one-dimensional and three-dimensional, are critically discussed and compared, underlining their potential and limitations, which are mainly related to the definition of the phase diagram and the choice of internal variables. Some new experimental results on shape memory alloy material characterisation are also presented. These experimental observations display some features of the shape memory alloy behaviour which are generally not included in the current models, thus some ideas are proposed for the development of a new constitutive model. The fourth chapter, finally, focuses on active composite plates with embedded shape memory alloy wires. A number of di®erent approaches can be used to predict the behaviour of such structures, each model presenting different advantages and drawbacks related to complexity and versatility. A simple model able to describe both shape and stiffness control configurations within the same context is proposed and implemented. The model is then validated considering the shape control configuration, which is the most sensitive to model parameters. The experimental work is divided in two parts. In the first part, an active composite is built by gluing prestrained shape memory alloy wires on a carbon fibre laminate strip. This structure is relatively simple to build, however it is useful in order to experimentally demonstrate the feasibility of the concept proposed in the first part of the chapter. In the second part, the making of a fibre-reinforced composite with embedded shape memory alloy wires is investigated, considering different possible choices of materials and manufacturing processes. Although a number of technological issues still need to be faced, the experimental results allow to demonstrate the mechanism of shape control via embedded shape memory alloy wires, while showing a good agreement with the proposed model predictions.

Some issues concerning the dynamic response and damage of composite laminates subjected to low velocity impact

Abstract. This thesis presents a discussion on a few specific topics regarding the low velocity impact behaviour of laminated composites. These topics were chosen because of their significance as well as the relatively limited attention received so far by the scientific community. The first issue considered is the comparison between the effects induced by a low velocity impact and by a quasi-static indentation experimental test. An analysis of both test conditions is presented, based on the results of experiments carried out on carbon fibre laminates and on numerical computations by a finite element model. It is shown that both quasi-static and dynamic tests led to qualitatively similar failure patterns; three characteristic contact force thresholds, corresponding to the main steps of damage progression, were identified and found to be equal for impact and indentation. On the other hand, an equal energy absorption resulted in a larger delaminated area in quasi-static than in dynamic tests, while the maximum displacement of the impactor (or indentor) was higher in the case of impact, suggesting a probably more severe fibre damage than in indentation. Secondly, the effect of different specimen dimensions and boundary conditions on its impact response was examined. Experimental testing showed that the relationships of delaminated area with two significant impact parameters, the absorbed energy and the maximum contact force, did not depend on the in-plane dimensions and on the support condition of the coupons. The possibility of predicting, by means of a simplified numerical computation, the occurrence of delaminations during a specific impact event is also discussed. A study about the compressive behaviour of impact damaged laminates is also presented. Unlike most of the contributions available about this subject, the results of compression after impact tests on thin laminates are described in which the global specimen buckling was not prevented. Two different quasi-isotropic stacking sequences, as well as two specimen geometries, were considered. It is shown that in the case of rectangular coupons the lay-up can significantly affect the damage induced by impact. Different buckling shapes were observed in laminates with different stacking sequences, in agreement with the results of numerical analysis. In addition, the experiments showed that impact damage can alter the buckling mode of the laminates in certain situations, whereas it did not affect the compressive strength in every case, depending on the buckling shape. Some considerations about the significance of the test method employed are also proposed. Finally, a comprehensive study is presented regarding the influence of pre-existing in-plane loads on the impact response of laminates. Impact events in several conditions, including both tensile and compressive preloads, both uniaxial and biaxial, were analysed by means of numerical finite element simulations; the case of laminates impacted in postbuckling conditions was also considered. The study focused on how the effect of preload varies with the span-to-thickness ratio of the specimen, which was found to be a key parameter. It is shown that a tensile preload has the strongest effect on the peak stresses at low span-to-thickness ratios, leading to a reduction of the minimum impact energy required to initiate damage, whereas this effect tends to disappear as the span-to-thickness ratio increases. On the other hand, a compression preload exhibits the most detrimental effects at medium span-to-thickness ratios, at which the laminate compressive strength and the critical instability load are close to each other, while the influence of preload can be negligible for thin plates or even beneficial for very thick plates. The possibility to obtain a better explanation of the experimental results described in the literature, in view of the present findings, is highlighted. Throughout the thesis the capabilities and limitations of the finite element model, which was implemented in an in-house program, are discussed. The program did not include any damage model of the material. It is shown that, although this kind of analysis can yield accurate results as long as damage has little effect on the overall mechanical properties of a laminate, it can be helpful in explaining some phenomena and also in distinguishing between what can be modelled without taking into account the material degradation and what requires an appropriate simulation of damage. Sommario. Questa tesi presenta una discussione su alcune tematiche specifiche riguardanti il comportamento dei compositi laminati soggetti ad impatto a bassa velocità. Tali tematiche sono state scelte per la loro importanza, oltre che per l’attenzione relativamente limitata ricevuta finora dalla comunità scientifica. La prima delle problematiche considerate è il confronto fra gli effetti prodotti da una prova sperimentale di impatto a bassa velocità e da una prova di indentazione quasi statica. Viene presentata un’analisi di entrambe le condizioni di prova, basata sui risultati di esperimenti condotti su laminati in fibra di carbonio e su calcoli numerici svolti con un modello ad elementi finiti. È mostrato che sia le prove quasi statiche sia quelle dinamiche portano a un danneggiamento con caratteristiche qualitativamente simili; tre valori di soglia caratteristici della forza di contatto, corrispondenti alle fasi principali di progressione del danno, sono stati individuati e stimati uguali per impatto e indentazione. D’altro canto lo stesso assorbimento di energia ha portato ad un’area delaminata maggiore nelle prove statiche rispetto a quelle dinamiche, mentre il massimo spostamento dell’impattatore (o indentatore) è risultato maggiore nel caso dell’impatto, indicando la probabilità di un danneggiamento delle fibre più severo rispetto al caso dell’indentazione. In secondo luogo è stato esaminato l’effetto di diverse dimensioni del provino e diverse condizioni al contorno sulla sua risposta all’impatto. Le prove sperimentali hanno mostrato che le relazioni fra l’area delaminata e due parametri di impatto significativi, l’energia assorbita e la massima forza di contatto, non dipendono dalle dimensioni nel piano dei provini e dalle loro condizioni di supporto. Viene anche discussa la possibilità di prevedere, per mezzo di un calcolo numerico semplificato, il verificarsi di delaminazioni durante un determinato caso di impatto. È presentato anche uno studio sul comportamento a compressione di laminati danneggiati da impatto. Diversamente della maggior parte della letteratura disponibile su questo argomento, vengono qui descritti i risultati di prove di compressione dopo impatto su laminati sottili durante le quali l’instabilità elastica globale dei provini non è stata impedita. Sono state considerate due differenti sequenze di laminazione quasi isotrope, oltre a due geometrie per i provini. Viene mostrato come nel caso di provini rettangolari la sequenza di laminazione possa influenzare sensibilmente il danno prodotto dall’impatto. Due diversi tipi di deformate in condizioni di instabilità sono stati osservati per laminati con diversa laminazione, in accordo con i risultati dell’analisi numerica. Gli esperimenti hanno mostrato inoltre che in certe situazioni il danno da impatto può alterare la deformata che il laminato assume in seguito ad instabilità; d’altra parte tale danno non ha sempre influenzato la resistenza a compressione, a seconda della deformata. Vengono proposte anche alcune considerazioni sulla significatività del metodo di prova utilizzato. Infine viene presentato uno studio esaustivo riguardo all’influenza di carichi membranali preesistenti sulla risposta all’impatto dei laminati. Sono stati analizzati con simulazioni numeriche ad elementi finiti casi di impatto in diverse condizioni di precarico, sia di trazione sia di compressione, sia monoassiali sia biassiali; è stato preso in considerazione anche il caso di laminati impattati in condizioni di postbuckling. Lo studio si è concentrato in particolare sulla dipendenza degli effetti del precarico dal rapporto larghezza-spessore del provino, che si è rivelato un parametro fondamentale. Viene illustrato che un precarico di trazione ha l’effetto più marcato sulle massime tensioni per bassi rapporti larghezza-spessore, portando ad una riduzione della minima energia di impatto necessaria per innescare il danneggiamento, mentre questo effetto tende a scomparire all’aumentare di tale rapporto. Il precarico di compressione evidenzia invece gli effetti più deleteri a rapporti larghezza-spessore intermedi, ai quali la resistenza a compressione del laminato e il suo carico critico di instabilità sono paragonabili, mentre l’influenza del precarico può essere trascurabile per piastre sottili o addirittura benefica per piastre molto spesse. Viene evidenziata la possibilità di trovare una spiegazione più soddisfacente dei risultati sperimentali riportati in letteratura, alla luce del presente contributo. Nel corso della tesi vengono anche discussi le potenzialità ed i limiti del modello ad elementi finiti utilizzato, che è stato implementato in un programma scritto in proprio. Il programma non comprende alcuna modellazione del danneggiamento del materiale. Viene però spiegato come, nonostante questo tipo di analisi possa portare a risultati accurati soltanto finché il danno ha scarsi effetti sulle proprietà meccaniche d’insieme del laminato, esso possa essere utile per spiegare alcuni fenomeni, oltre che per distinguere fra ciò che si può riprodurre senza tenere conto del degrado del materiale e ciò che invece richiede una simulazione adeguata del danneggiamento.

Mass transport in polymers

The study of mass transport in polymeric membranes has grown in importance due to its potential application in many processes such as separation of gases and vapors, packaging, controlled drug release. The diffusion of a low molecular weight species in a polymer is often accompanied by other phenomena like swelling, reactions, stresses, that have not been investigated in all their aspects yet. Furthermore, novel materials have been developed that include inorganic fillers, reactive functional groups or ions, that make the scenery even more complicated. The present work focused on the experimental study of systems where the diffusion is accompanied by other processes; suitable models were also developed to describe the particular circumstances in order to understand the underlying concepts and be able to design the performances of the material. The effect of solvent-induced deformation in polymeric films during sorption processes was studied since the dilation, especially in constrained membranes, can cause the development of stresses and therefore early failures of the material. The bending beam technique was used to test the effects of the dilation and the stress induced in the polymer by penetrant diffusion. A model based on the laminate theory was developed that accounts for the swelling and is able to predict the stress that raise in the material. The addition of inorganic fillers affects the transport properties of polymeric films. Mixed matrix membranes based on fluorinated, high free volume matrices show attractive performances for separation purposes but there is a need for deeper investigation of the selectivity properties towards gases and vapors. A new procedure based on the NELF model was tested on the experimental data; it allows to predict solubility of every penetrant on the basis of data for one vapor. The method has proved to be useful also for the determination of the diffusion coefficient and for an estimation of the permeability in the composite materials. Oxygen scavenging systems can overcome lack of barrier properties in common polymers that forbids their application in sensitive applications as food packaging. The final goal of obtaining a membrane almost impermeable to oxygen leads to experimental times out of reach. Hence, a simple model was developed in order to describe the transport of oxygen in a membrane with also reactive groups and analyze the experimental data collected on SBS copolymers that show attractive scavenging capacity. Furthermore, a model for predicting the oxygen barrier behavior of a film formed as a blend of OSP in a common packaging material was built, considering particles capable of reactions with oxygen embedded in a non-reactive matrix. Perfluorosulphonic acid ionomers (PFSI) are capturing attention due to a high thermal and chemical resistance coupled with very peculiar transport properties, that make them appropriate to be used in fuel cells. The possible effect of different formation procedure was studied together with the swelling due to water sorption since both water uptake and dilation can dramatically affect the fuel cells performances. The water diffusion and sorption was studied with a FTIR-ATR spectrometer that can give deeper information on the bonds between water molecules and the sulphonic hydrophilic groups and, therefore, on the microstructure of the hydrated ionomer.

Bonded structures for enhanced damage tolerant pressurized fuselages

Adhesive bonding provides solutions to realize cost effective and low weight aircraft fuselage structures, in particular where the Damage Tolerance (DT) is the design criterion. Bonded structures that combine Metal Laminates (MLs) and eventually Selective Reinforcements can guarantee slow crack propagation, crack arrest and large damage capability. To optimize the design exploiting the benefit of bonded structures incorporating selective reinforcement requires reliable analysis tools. The effect of bonded doublers / selective reinforcements is very difficult to be predicted numerically or analytically due to the complexity of the underlying mechanisms and failures modes acting. Reliable predictions of crack growth and residual strength can only be based on sound empirical and phenomenological considerations strictly related to the specific structural concept. Large flat stiffened panels that combine MLs and selective reinforcements have been tested with the purpose of investigating solutions applicable to pressurized fuselages. The large test campaign (for a total of 35 stiffened panels) has quantitatively investigated the role of the different metallic skin concepts (monolithic vs. MLs) of the aluminum, titanium and glass-fiber reinforcements, of the stringers material and cross sections and of the geometry and location of doublers / selective reinforcements. Bonded doublers and selective reinforcements confirmed to be outstanding tools to improve the DT properties of structural elements with a minor weight increase. However the choice of proper materials for the skin and the stringers must be not underestimated since they play an important role as well. A fuselage structural concept has been developed to exploit the benefit of a metal laminate design concept in terms of high Fatigue and Damage Tolerance (F&DT) performances. The structure used laminated skin (0.8mm thick), bonded stringers, two different splicing solutions and selective reinforcements (glass prepreg embedded in the laminate) under the circumferential frames. To validate the design concept a curved panel was manufactured and tested under loading conditions representative of a single aisle fuselage: cyclic internal pressurization plus longitudinal loads. The geometry of the panel, design and loading conditions were tailored for the requirements of the upper front fuselage. The curved panel has been fatigue tested for 60 000 cycles before the introduction of artificial damages (cracks in longitudinal and circumferential directions). The crack growth of the artificial damages has been investigated for about 85 000 cycles. At the end a residual strength test has been performed with a “2 bay over broken frame” longitudinal crack. The reparability of this innovative concept has been taken into account during design and demonstrated with the use of an external riveted repair. The F&DT curved panel test has confirmed that a long fatigue life and high damage tolerance can be achieved with a hybrid metal laminate low weight configuration. The superior fatigue life from metal laminates and the high damage tolerance characteristics provided by integrated selective reinforcements are the key concepts that provided the excellent performances. The weight comparison between the innovative bonded concept and a conventional monolithic riveted design solution showed a significant potential weight saving but the weight advantages shall be traded off with the additional costs.

Mechanical behavior of flat and curved laminates interleaved by electrospun nanofibers

A major weakness of composite materials is that low-velocity impact, introduced accidentally during manufacture, operation or maintenance of the aircraft, may result in delaminations between the plies. Therefore, the first part of this study is focused on mechanics of curved laminates under impact. For this aim, the effect of preloading on impact response of curved composite laminates is considered. By applying the preload, the stress through the thickness and curvature of the laminates increased. The results showed that all impact parameters are varied significantly. For understanding the contribution rate of preloading and pre-stress on the obtained results another test is designed. The interesting phenomenon is that the preloading can decrease the damaged area when the curvature of the both specimens is the same. Finally the effect of curvature type, concave and convex, is investigated under impact loading. In the second part, a new composition of nanofibrous mats are developed to improve the efficiency of curved laminates under impact loading. Therefore, at first some fracture tests are conducted to consider the effect of Nylon 6,6, PCL, and their mixture on mode I and mode II fracture toughness. For this goal, nanofibers are electrospun and interleaved between mid-plane of laminate composite to conduct mode I and mode II tests. The results shows that efficiency of Nylon 6,6 is better than PCL in mode II, while the effect of PCL on fracture toughness of mode I is more. By mixing these nanofibers the shortage of the individual nanofibers is compensated and so the Nylon 6,6/PCL nanofibers could increased mode I and II fracture toughness. Then all these nanofibers are used between all layers of composite layers to investigate their effect on damaged area. The results showed that PCL could decrease the damaged area about 25% and Nylon 6,6 and mixed nanofibers about 50%.