arXiv subjects

Costantino Creton

Publications and source records attributed to Costantino Creton.

15 recordsLinked to original sources

arXiv2026

Wear in multiple network elastomers arises from the continuous accumulation of molecular damage rather than microcrack growth

Tire wear releases millions of tons of particles annually, bearing immense industrial and environmental impact. However, efforts to mitigate the wear of elastomeric materials remain largely empirical, due to a limited understanding of the underlying damage mechanisms that cause wear. Employing mechanochemical approaches on model multiple network elastomers, we uncover how polymer strand scission events - the elemental damage units in these disordered networks - evolve during frictional wear. Our findings demonstrate that discrete micro-slippage at rough contacting asperities damages the material several micrometers below the surface through stress-activated bond scission events. This steady accumulation of subsurface damage ultimately leads to material erosion through the generation of a degraded viscous layer, painting a new picture of wear as a continuous damage growth process. Our approach further demonstrates an enhanced resilience to wear when tuning material architecture to reduce sensitivity to stress fluctuations, paving the way for knowledge-based strategies to develop more sustainable materials.

cond-mat.soft↗

arXiv2025

Probing the Microscopic Origin of Toughness in Multiple Polymer Networks

Multiple polymer networks, such as double-network elastomers comprising a sacrificial and a matrix network, exhibit exceptional mechanical resilience, commonly attributed to the formation of an extended damage zone before a crack can grow. However, the microscopic mechanisms underlying their toughness remain poorly understood. Here, we combine advanced light scattering methods and molecular dynamics simulations to explore the microscopic relaxation dynamics and stress redistribution at the polymer strand scale of single-network and double-network elastomers under uni-axial loading. Dynamic light scattering experiments show that microscopic rearrangements and bond-breaking events are localized near the crack tip in single networks, readily causing the crack to advance. In contrast, double networks exhibit delocalized microscopic rearrangements well ahead of and not directly correlated with crack propagation, enabling the dissipation of energy over broader regions and timescales. Numerical simulations of the damage zone show that bond breaking in the matrix network of double networks leads to widespread stress redistribution, mitigating catastrophic damage localization. This enhanced ability to redistribute stress in a non-local manner allows a much larger extension before localized macroscopic failure occurs, explaining the superior toughness of double networks. Our findings identify early, delocalized bond-breaking events combined with more efficient dissipation pathways through enhanced microscopic rearrangements as the key microscopic mechanisms responsible for the outstanding toughness and extensibility of multiple elastomer networks.

cond-mat.soft↗

arXiv2022

Multispeckle diffusing wave spectroscopy as a tool to study heterogeneous mechanical behavior in soft solids

Multiple speckle diffusing wave spectroscopy (MSDWS) can be applied to measure spatially heterogeneous mechanical behavior in soft solids, with high sensitivity to deformation and both spatial and temporal resolution. In this paper, we discuss the mathematical approach behind the quantification of the deformation rate from MSDWS data and provide guidelines for optimizing the selection of experimental parameters in measurements. After validating the method in extensional tests on an elastomer, we provide an example of the potentiality of MSDWS by measuring the spatial distribution of the deformation rate during shear debonding of adhesive tapes. We quantitatively characterize the deformation rate distribution related to shearing and peeling under loading. A highly heterogeneous deformation rate distribution is observed, and time-dependent measurements reveal an increase in deformation localization hundreds of seconds before full debonding. This behavior, previously predicted by theory and simulation, is here demonstrated experimentally for the first time.

cond-mat.soft↗

arXiv2021

Strain induced strengthening of soft thermoplastic polyurethanes under cyclic deformation

We investigate the cyclic mechanical behavior in uniaxial tension of three different commercial thermoplastic polyurethane elastomers (TPU) often considered as a sustainable replacement for common filled elastomers. All TPU have similar hard segment contents and linear moduli but sensibly different large strain properties as shown by X-Ray analysis. Despite these differences, we found a stiffening effect after conditioning in step cyclic loading which greatly differs from the common softening (also referred as Mullins effect) observed in chemically crosslinked filled rubbers. We propose that this self-reinforcement is related to the fragmentation of hard domains, naturally present in TPU, in smaller but more numerous sub-units that may act as new physical crosslinking points. The proposed stiffening mechanism is not dissimilar to the strain-induced crystallization observed in stretched natural rubber, but it presents a persistent nature. In particular, it may cause a local reinforcement where an inhomogeneous strain field is present, as is the case of a crack propagating in cyclic fatigue, providing a potential explanation for the well-known toughness and wear resistance of TPU

cond-mat.soft↗

arXiv2021

3D Fluorescent Mapping of Invisible Molecular Damage after Cavi-tation in Hydrogen Exposed Elastomers

Elastomers saturated with gas at high pressure suffer from cavity nucleation, inflation, and deflation upon rapid or explosive de-compression. Although this process often results in undetectable changes in appearance, it causes internal damage, hampers func-tionality (e.g., permeability), and shortens lifetime. Here, we tag a model poly(ethyl acrylate) elastomer with π-extended anthracene-maleimide adducts that fluoresce upon polymer chain scission, and map in 3D the internal damage present after a cycle of gas satu-ration and rapid decompression. Interestingly, we observe that each cavity observable during the decompression results in a dam-aged region, the shape of which reveals a fracture locus of randomly oriented penny-shape cracks (i.e., with a flower-like morpholo-gy) that contain crack arrest lines. Thus, cavity growth likely proceeds discontinuously (i.e., non-steadily) through the stable and unstable fracture of numerous 2D crack planes. This non-destructive methodology to visualize in 3D molecular damage in polymer networks is novel and serves to understand how fracture occurs under complex 3D loads, predict mechanical aging of pristine look-ing elastomers, and holds potential to optimize cavitation-resistant materials.

cond-mat.soft↗

arXiv2020

Quantifying and mapping covalent bond scission during elastomer fracture

Many new soft but tough rubbery materials have been recently discovered and new applications such as flexible prosthetics, stretchable electrodes or soft robotics continuously emerge. Yet, a credible multi-scale quantitative picture of damage and fracture of these materials has still not emerged, due to our fundamental inability to disentangle the irreversible scission of chemical bonds along the fracture path from dissipation by internal molecular friction. Here, by coupling new fluorogenic mechanochemistry with quantitative confocal microscopy mapping, we uncover how many and where covalent bonds are broken as an elastomer fractures. Our measurements reveal that bond scission near the crack plane can be delocalized over up to hundreds of micrometers and increase by a factor of 100 depending on temperature and stretch rate, pointing to an intricated coupling between strain rate dependent viscous dissipation and strain dependent irreversible network scission. These findings paint an entirely novel picture of fracture in soft materials, where energy dissipated by covalent bond scission accounts for a much larger fraction of the total fracture energy than previously believed. Our results pioneer the sensitive, quantitative and spatially-resolved detection of bond scission to assess material damage in a variety of soft materials and their applications.

cond-mat.soft↗

arXiv2018

Harnessing entropy to enhance toughness in reversibly crosslinked polymer networks

Reversible crosslinking is a design paradigm for polymeric materials, wherein they are microscopically reinforced with chemical species that form transient crosslinks between the polymer chains. Besides the potential for self-healing, recent experimental work suggests that freely diffusing reversible crosslinks in polymer networks, such as gels, can enhance the toughness of the material without substantial change in elasticity. This presents the opportunity for making highly elastic materials that can be strained to a large extent before rupturing. Here, we employ Gaussian chain theory, molecular simulation, and polymer self-consistent field theory for networks to construct an equilibrium picture for how reversible crosslinks can toughen a polymer network without affecting its linear elasticity. Maximisation of polymer entropy drives the reversible crosslinks to bind preferentially near the permanent crosslinks in the network, leading to local molecular reinforcement without significant alteration of the network topology. In equilibrium conditions, permanent crosslinks share effectively the load with neighbouring reversible crosslinks, forming multi-functional crosslink points. The network is thereby globally toughened, while the linear elasticity is left largely unaltered. Practical guidelines are proposed to optimise this design in experiment, along with a discussion of key kinetic and timescale considerations.

cond-mat.soft↗

arXiv2017

Characterizing Large Strain Elasticity of Brittle Elastomeric Networks by Embedding Them in a Soft Extensible Matrix

Here, the general design and properties of new multiple network elastomers with an exceptional combination of stiffness, toughness, and elasticity are reported. In this paper, it is reported in more detail how the increase in strain at break resulting from the toughening can be used to provide great insight in the large strain properties of otherwise brittle acrylic well crosslinked networks. The networks have been prepared by sequences of polymerization and swelling with monomers. The parameters that have been varied are the nature of the base monomers and the degree of crosslinking of the first network. Here, the small strain properties, equilibrium swelling, and large strain properties in uniaxial tension are characterized. It is shown here that the large strain properties of the multiple networks are quantitatively controlled by the large strain properties of the stretched first network which acts as a percolating filler, while the small and intermediate properties are controlled by the entanglement density which can be largely superior to that of homogeneous networks. Different brittle and prestretched elastomer networks are embedded at a low volume fraction in a soft extensible matrix. The increase in toughness of the final material is directly controlled by the nonlinear elastic properties of the prestretched network and its volume fraction, providing a general design rule for tough soft materials

cond-mat.soft↗

arXiv2017

Mechanics of an Asymmetric Hard--Soft Lamellar Nanomaterial

Nanolayered lamellae are common structures in nanoscience and nanotechnology, but most are nearly symmetric in layer thickness. Here, we report on the structure and mechanics of highly asymmetric and thermodynamically stable soft--hard lamellar structures self-assembled from optimally designed PS1-(PI-b-PS2)3 miktoarm star block copolymers. The remarkable mechanical properties of these strong and ductile PS (polystyrene)-based nanomaterials can be tuned over a broad range by varying the hard layer thickness while maintaining the soft layer thickness constant at 13 nm. Upon deformation, thin PS lamellae (\textless{}100 nm) exhibited kinks and predamaged/damaged grains, as well as cavitation in the soft layers. In contrast, deformation of thick lamellae (\textgreater{}100 nm) manifests cavitation in both soft and hard nanolayers. In situ tensile-SAXS experiments revealed the evolution of cavities during deformation and confirmed that the damage in such systems reflects both plastic deformation by shear and residual cavities. The aspects of the mechanics should point to universal deformation behavior in broader classes of asymmetric hard--soft lamellar materials, whose properties are just being revealed for versatile applications.

cond-mat.soft↗

arXiv2017

Structure of Surfaces and Interfaces of Poly( N,N -dimethylacrylamide) Hydrogels

We investigated the surface structure of hydrogels of poly(N,N-dimethylacrylamide) (PDMA) hydrogels synthesized and cross-linked simultaneously by redox free radical polymerization. We demonstrate the existence of a less cross-linked layer at the surface of the gel at least at two different length scales characterized by shear rheology and by neutron reflectivity, suggesting the existence of a gradient in cross-linking. The composition of the layer is shown to depend on the degree of hydrophobicity of the mold surface and is weaker for more hydrophobic molds. While the macroscopic tests proved the existence of a relatively thick under-cross-linked layer, we also demonstrated by neutron reflectivity that the gel surface at the submicrometric scale (500 nm) was also affected by the surface treatment of the mold. These results should have important implications for the measurement of macroscopic surface properties of these hydrogels such as friction or adhesion.

cond-mat.soft↗

arXiv2016

Fracture of dual crosslink gels with permanent and transient crosslinks

We have carried out systematic fracture experiments in a single edge notch geometry over a range of stretch rates on dual crosslink hydrogels made from polyvinyl alcohol chains chemically crosslinked with glutaraldehyde and physically crosslinked with borate ions. If the energy release rate necessary for crack propagation was calculated conventionally, by using the work done to deform the sample to the critical value of stretch $λ_c$ where the crack propagates, we found that the fracture energy $Γ$ peaks around $λ\sim 0.001 s^{-1}$ before decreasing sharply with increasing stretch rate, in contradiction with the measurements of crack velocity. Combining simulations and experimental observations, we propose therefore here a general method to separate the energy dissipated during loading before crack propagation, from that which is dissipated during crack propagation. For fast loading rates (with a characteristic strain rate only slightly lower than the inverse of the typical breaking time of physical bonds), this improved method to estimate a local energy release rate $g_{local}$ at the onset of crack propagation, gives a value of the local fracture energy $Γ_{local}$ which is constant, consistent with the constant value of the crack propagation velocity measured experimentally. Using this improved method we also obtain the very interesting result that the dual crosslink gels have a much higher value of fracture energy at low loading rates than at high loading rates, contrary to the situation in classical chemically crosslinked elastic networks.

cond-mat.soft↗

arXiv2015

Rate-dependent elastic hysteresis during the peeling of Pressure Sensitive Adhesives

The modelling of the adherence energy during peeling of Pressure Sensitive Adhesives (PSA) has received much attention since the 1950's, uncovering several factors that aim at explaining their high adherence on most substrates, such as the softness and strong viscoelastic behaviour of the adhesive, the low thickness of the adhesive layer and its confinement by a rigid backing. The more recent investigation of adhesives by probe-tack methods also revealed the importance of cavitation and stringing mechanisms during debonding, underlining the influence of large deformations and of the related non-linear response of the material, which also intervenes during peeling. Although a global modelling of the complex coupling of all these ingredients remains a formidable issue, we report here some key experiments and modelling arguments that should constitute an important step forward. We first measure a non-trivial dependence of the adherence energy on the loading geometry, namely through the influence of the peeling angle, which is found to be separable from the peeling velocity dependence. This is the first time to our knowledge that such adherence energy dependence on the peeling angle is systematically investigated and unambiguously demonstrated. Secondly, we reveal an independent strong influence of the large strain rheology of the adhesives on the adherence energy. We complete both measurements with a microscopic investigation of the debonding region. We discuss existing modellings in light of these measurements and of recent soft material mechanics arguments, to show that the adherence energy during peeling of PSA should not be associated to the propagation of an interfacial stress singularity. The relevant deformation mechanisms are actually located over the whole adhesive thickness, and the adherence energy during peeling of PSA should rather be associated to the energy loss by viscous friction and by rate-dependent elastic hysteresis.

cond-mat.soft↗

arXiv2013

Quantitative analysis of the debonding structure of soft adhesives

We experimentally investigate the growth dynamics of cavities nucleating during the first stages of debonding of three different model adhesives. The material properties of these adhesives range from a more liquid-like material to a soft viscoelastic solid and are carefully characterized by small strain oscillatory shear rheology as well as large strain uniaxial extension. The debonding experiments are performed on a probe tack set-up. Using high contrast images of the debonding process and precise image analysis tools we quantify the total projected area of the cavities, the average cavity shape and growth rate and link these observations to the material properties. These measurements are then used to access corrected effective stress and strain curves that can be directly compared to the results from the uniaxial extension.

cond-mat.soft↗

arXiv2010

Self-assembly in solution of a reversible comb-shaped supramolecular polymer

We report a single step synthesis of a polyisobutene with a bis-urea moiety in the middle of the chain. In low polarity solvents, this polymer self-assembles by hydrogen bonding to form a combshaped polymer with a central hydrogen bonded backbone and polyisobutene arms. The comb backbone can be reversibly broken, and consequently, its length can be tuned by changing the solvent, the concentration or the temperature. Moreover, we have proved that the bulkiness of the side-chains have a strong influence on both the self-assembly pattern and the length of the backbone. Finally, the density of arms can be reduced, by simply mixing with a low molar mass bis-urea.

cond-mat.soft↗

arXiv2004

Cavity Growth in Soft Solids

Soft polymer-based solid materials can be defined as solid materials with elastic moduli below 1 MPa. In order to obtain such a low modulus while retaining a solid character, all these materials are based on a network of fixed points (crosslinks, physical interactions) keeping together a liquid-like matrix. Since they are not able to flow, very large deformations will lead to failure by fracture or cavitation. We discuss in this paper new experimental data suggesting that the growth of a cavity in a soft nearly elastic solid undergoes a transition from a stress-controlled growth, when the initial cavity size is larger than Gc/E, to an energy-activated growth, when the initial cavity size is smaller than Gc/E. The important material length scale Gc/E represents the ratio between the surface energy necessary to expand the cavity and the elastic modulus. This energy activated growth regime is due to the existence of a metastable solution and significantly increases the apparent cavitation stress for layers thinner than 1000 Gc/E.

cond-mat.soft↗