The mechanical integrity of composite materials depends primarily on the interface strength and the defect density of the reinforcement which is the provider of enhanced strength and stiffness. In the case of graphene/ polymer nanocomposites which are characterized by an extremely large interface region, any defects in the inclusion (such as folds, cracks, holes etc.) will have a detrimental effect to the internal strain distribution and the resulting mechanical performance. This conventional wisdom, however, can be challenged if the defect size is reduced beyond the critical size for crack formation to the level of atomic vacancies. In that case, there should be no practical effect on crack propagation and depending on the nature of the vacancies the interface strength may be in fact increase. In this work we employed argon ion (Ar+) bombardment and subsequent exposure to hydrogen (H2) to induce (as revealed by X-ray & Ultraviolet photoelectron spectroscopy (XPS/UPS) and Raman spectroscopy) passivated atomic single vacancies to CVD graphene. The modified graphene was subsequently transferred to PMMA bars and the morphology, wettability and the interface adhesion of the CVD graphene/PMMA system were investigated with Atomic Force Microscopy technique and Raman analysis. The results obtained showed clearly an overall improved mechanical behavior of graphene/polymer interface, since an increase as well a more uniform shift distribution with strain is observed. This paves the way for interface engineering in graphene/polymer systems which, in pristine condition, suffer from premature graphene slippage and subsequent failure.
The physics of adhesion of one-dimensional nano structures such as nanotubes, nano wires, and biopolymers on different material substrates is of great interest for the study of biological adhesion and the development of nano electronics and nano mechanics. In this paper, we present force spectroscopy experiments of a single wall carbon nanotube loop using our home-made interferometric atomic force microscope. Characteristic force plateaux during the peeling process allows us to access to quantitative values of the adhesion energy per unit length on various substrates: graphite, mica, platinum,…
The adhesion between a polymer melt and substrate is studied in the presence of chemically attached chains on the substrate surface. Extensive molecular dynamics simulations have been carried out to study the effect of temperature, tethered chain areal density ($Σ$), tethered chain length ($N_{t}$), chain bending energy ($k_θ$) and tensile pull velocity ($v$) on the adhesive failure mechanisms of pullout and/or scission of the tethered chains. We observe a crossover from pure chain pullout to chain scission as $N_{t}$ is increased. Below the glass transition, the value of $N_{t}$ for which thi…
We study the adhesion of poly(3-hexylthiophene) on nanostructured titania surface in vacuo by means of model potential molecular dynamics. We generate large scale atomistic models of nanostructured titania surfaces (consisting of spherical nanocaps on top of a (110) rutile surface) and we study the adhesion of an oligothiophene as a function of their local curvature and roughness. In the limit of a perfect planar surface, the maximum adhesion energy is calculated to be as large as 0:6 eV per monomer, and it corresponds to the oligothiophene oriented along the [$\bar{1}10$] direction of the sur…
The structures and energetics of organic molecules adsorbed onto clean and H-passivated Si(001)-(2$\times$1) surfaces have been calculated using density functional theory. For benzene adsorbed on the clean Si surface the tight-bridge structure was found to be stable and the butterfly structure metastable. Both carbonic acid H$_2$CO$_3$ and propane C$_3$H$_8$ dissociate on contact with the surface. Passivation of the Si surface with H-atoms has a dramatic effect on the surface properties. The passivated surface is very inert and the binding energy of all the molecules is very weak.
Metalization of carbon fiber reinforced polymers (CFRPs) composites by the surface modification method to enhance their electrical conductivity, thermal conductivity, electromagnetic shielding, erosion, and radiation protection, has a significant meaning in the aerospace field. In this study, Sn coating was successfully fabricated on the CFRP composite substrate via low-pressure cold spray under four gas temperatures (473K, 523K, 573K, and 623K). Their bonding mechanism was explored via the surface observation after peel-off adhesion strength, accompanying with surface temperature distribution…
Understanding the adhesion between graphene and other materials is crucial for achieving more reliable graphene-based applications in electronic devices and nanocomposites. The ultra-thin profile of graphene, however, poses significant challenge to direct measurement of its adhesion property using conventional approaches. We show that there is a strong correlation between the morphology of graphene on a compliant substrate with patterned surface and the graphene-substrate adhesion. We establish an analytic model to quantitatively determine such a strong correlation. Results show that, dependin…
Hydrogenated amorphous carbon (a-C:H), deposited by the rf-plasma enhanced chemical vapour deposition (rf-PECVD) technique, is a promising material for large area electronic and interlayer dielectric applications. The structural and electronic properties of rf-PECVD a-C:H, deposited at room temperature from CH4/He and CH4/Ar gas mixtures, are shown to be sensitive to the substrate on which the thin film is deposited. The choice of substrate (c-Si or C7059 glass), and the existence and geometrical dimensions of any metallic pattern on the substrate surface, can result in significant spatial var…
The structural, electronic, and adhesive properties of Cu/SiO$_2$ interfaces are investigated using first-principles density-functional theory within the local density approximation. Interfaces between fcc Cu and $α$-cristobalite(001) surfaces with different surface stoichiometries are considered. Interfacial properties are found to be sensitive to the choice of the termination, and the oxygen density at the substrate surface is the most important factor influencing the strength of adhesion. For oxygen-rich interfaces, the O atoms at the interface substantially rearrange after the deposition o…
Experimental results for adhesive contacts on substrates coated with elastomeric thin films have recently been obtained by C. Tardivat and L. Léger (J. Adhesion Sci. Technol. 15 1055-1078 (2001)) by the so-called JKR test, which provides both adhesion energy and elastic modulus. These data show that on substrates coated with thin films the adhesion and effective elastic modulus of the sphere depend upon the film thickness. In keeping with the experimental conditions, we try to interpret these data using a simple model (E. Barthel and A. Perriot, J. Phys. D 40, 1059-1067 (2007)) in the thin fil…
Two-dimensional (2D) materials assembled into van der Waals (vdW) heterostructures contain unlimited combinations of mechanical, optical, and electrical properties that can be harnessed for potential device applications. Critically, these structures require control over interfacial adhesion in order for them to be constructed and to have enough integrity to survive industrial fabrication processes upon their integration. Here, we promptly determine the quality of adhesion of various exfoliated 2D materials on conventional SiO$_{2}$/Si substrates using ultrasonic delamination threshold testing.…
How friction affects adhesion is addressed. The problem is considered in the context of a very stiff sphere adhering to a compliant, isotropic, linear elastic substrate, and experiencing adhesion and frictional slip relative to each other. The adhesion is considered to be driven by very large attractive tractions between the sphere and the substrate that can act only at very small distances between them. As a consequence, the adhesion behavior can be represented by the Johnson-Kendall-Roberts model, and this is assumed to prevail also when frictional slip is occurring. Frictional slip is consi…
As mechanical structures enter the nanoscale regime, the influence of van der Waals forces increases. Graphene is attractive for nanomechanical systems because its Young's modulus and strength are both intrinsically high, but the mechanical behavior of graphene is also strongly influenced by the van der Waals force. For example, this force clamps graphene samples to substrates, and also holds together the individual graphene sheets in multilayer samples. Here we use a pressurized blister test to directly measure the adhesion energy of graphene sheets with a silicon oxide substrate. We find an …
Tunable dry adhesion is a crucial mechanism in compliant manipulation. The gripping force, mainly originated from the van der Waals force between the adhesive composite and the object to be gripped, can be controlled by reversibly varying the physical properties (e.g., stiffness) of the composite via external stimuli. The maximal gripping force Fmax and its tunability depend on, among other factors, the stress distribution on the gripping interface and its fracture dynamics (during detaching), which in turn are determined by the composite microstructure. Here, we present a computational framew…
We investigate the adsorption of graphene sheets on h-BN substrates by means of first-principles calculations in the framework of adiabatic connection fluctuation-dissipation theory in the random phase approximation. We obtain adhesion energies for different crystallographic stacking configurations and show that the interlayer bonding is due to long-range van der Waals forces. The interplay of elastic and adhesion energies is shown to lead to stacking disorder and moiré structures. Band structure calculations reveal substrate induced mass terms in graphene which change their sign with the stac…
Indirect magnetoelectric effect has been studied in magnetostrictive-film/substrate/piezoelectric-actuator heterostructures. Two different substrates have been employed: a flexible substrate (Young's modulus of 4 GPa) and a rigid one (Young's modulus of 180 GPa). A clear optimization of the indirect magnetoelectric coupling, studied by micro-strip ferromagnetic resonance, has been highlighted when using the polymer substrate. However, in contrast to the rigid substrate, the flexible substrate also leads to an a priori undesirable and huge uniaxial anisotropy which seems to be related to a non …
We demonstrate the direct dry transfer of large area Chemical Vapor Deposition graphene to several polymers (low density polyethylene, high density polyethylene, polystyrene, polylactide acid and poly(vinylidenefluoride-co-trifluoroethylene) by means of only moderate heat and pressure, and the later mechanical peeling of the original graphene substrate. Simulations of the graphene-polymer interactions, rheological tests and graphene transfer at various experimental conditions show that controlling the graphene-polymer interface is the key to controlling graphene transfer. Raman spectroscopy an…
Interfacial adhesion between graphene and a SiO2 substrate is studied by density functional theory (DFT) with dispersion corrections. The results demonstrate the van der Waals (vdW) interaction as the predominate mechanism for the graphene/SiO2 interface. It is found that the interaction strength is strongly influenced by changes of the SiO2 surface structures due to surface reactions with water. The adhesion energy is reduced when the reconstructed SiO2 surface is hydroxylated, and further reduced when covered by a monolayer of adsorbed water molecules. Thus, the effect of humidity may help e…
Understanding material behavior under high velocity impact is the key to addressing a variety of fundamental questions in areas ranging from asteroid strikes and geological cratering to impact-induced phase transformations, spallation, wear, and ballistic penetration. Recently, adhesion has emerged in this spectrum since it has been found that micrometer-sized metallic particles can bond to metallic substrates under supersonic-impact conditions. However, the mechanistic aspects of impact-induced adhesion are still unresolved. Here we study supersonic impact of individual metallic microparticle…
With the aim of understanding failure modes in the peeling of silicone-based adhesive joints and, in particular, the occurrence of adhesive or cohesive failure, an experimental campaign has been conducted by considering plastic substrates with different surface roughness. A flexible strip has been bonded onto such substrates using a silicone adhesive, by controlling its thickness. Peeling tests with 90° and 180° peeling angle configurations have been performed and the effect of joint parameters, such as surface roughness and adhesive thickness, onto the adhesion energy and the failure mode are…
The surface tension of compliant materials such as gels provides resistance to deformation in addition to and sometimes surpassing that due to elasticity. This article studies how surface tension changes the contact mechanics of a small hard sphere indenting a soft elastic substrate. Previous studies have examined the special case where the external load is zero, so contact is driven by adhesion alone. Here, we tackle the much more complicated problem where, in addition to adhesion, deformation is driven by an indentation force. We present an exact solution based on small strain theory. The re…
Breast cancer is the most common type of cancer observed in women. Communication with the tumor microenvironment allows invading breast cancer cells, such as triple negative breast cancer cells, to adapt to specific substrates. The substrate topography modulates the cellular behavior, among other factors. A number of different materials and micro/nanofabrication techniques have been employed to develop substrates for cell culturing. Silicon-based substrates present a lot of advantages as they are amenable to a wide range of processing techniques and they permit rigorous control over the surfac…
Pairs of electrodes with nanometer separation (nano-gap) are achieved through an electromigration-induced break-junction (EIBJ) technique at room temperature. Lithographically defined gold (Au) wires are formed by e-beam evaporation over oxide coated silicon substrates silanized with (3-Mercaptopropyl)trimethoxysilane (MPTMS) and then subjected to electromigration at room temperature to create a nanometer scale gap between the two newly formed Au electrodes. The Si-O-Si covalent bond at the SiO$_2$ surface and the Au-sulphur (Au-S) bond at the top evaporated Au side, makes MPTMS as an efficien…
The interaction of graphene with neighboring materials and structures plays an important role in its behavior, both scientifically and technologically. The interactions are complicated due to the interplay between surface forces and possibly nonlinear elastic behavior. Here we review recent experimental and theoretical advances in the understanding of graphene adhesion. We organize our discussion into experimental and theoretical efforts directed toward: graphene conformation to a substrate, determination of adhesion energy, and applications where graphene adhesion plays an important role. We …
We study the mechanics of pressurized graphene membranes using an experimental configuration that allows the determination of the elasticity of graphene and the adhesion energy between a substrate and a graphene (or other two-dimensional solid) membrane. The test consists of a monolayer graphene membrane adhered to a substrate by surface forces. The substrate is patterned with etched microcavities of a prescribed volume and when they are covered with the graphene monolayer it traps a fixed number (N) of gas molecules in the microchamber. By lowering the ambient pressure, and thus changing the …
The effect of annealing on the dynamical behavior of swelling for ultrathin polyacrylamide films deposited on silicon substrates have been studied using X-ray reflectivity technique. The spin coated polyacrylamide films of similar thicknesses were annealed at various temperatures below and above the glass transition temperature of the polymer. The electron density of the films was found to increase systematically on annealing. The swelling dynamics of the annealed films were found to have systematic dependence on the temperature of annealing. The interaction between the substrate and the polym…
Soft supramolecular materials are promising for the design of innovative and highly tunable adhesives. These materials are composed of polymer chains functionalized by strongly interacting moieties, sometimes called "stickers". In order to systematically investigate the effect of the presence of associative groups on the debonding properties of a supramolecular adhesive, a series of supramolecular model systems has been characterized by probe-tack tests. These model materials, composed of linear and low dispersity poly(butylacrylate) chains functionalized in the middle by a single tri-urea sti…
Characteristics of relaxed density profile and conformation of polymer chains are studied by a Monte Carlo simulation on a discrete lattice in three dimensions using different segmental (kink-jump $K$, crank-shaft $C$, reptation $R$) dynamics. Three distinct density regimes, substrate, bulk, and interface, are identified. With the $KC$ segmental dynamics we find that the substrate coverage grows with a power-law, $d_s \propto t^γ$ with a field dependent nonuniversal exponent $γ= 0.23 + 0.7 E$. The bulk volume fraction $d_b$ and the substrate polymer density ($d_s$) increases exponentially with…
Membranes derived from ultrathin polymeric films are promising to meet fast separations, but currently available approaches to produce polymer films with greatly reduced thicknesses on porous supports still faces challenges. Here, defect-free ultrathin polymer covering films (UPCFs) are realized by a facile general approach of rapid solvent evaporation. By fast evaporating dilute polymer solutions, we realize ultrathin coating (~30 nm) of porous substrates exclusively on the top surface, forming UPCFs with a block copolymer of polystyrene-block-poly(2-vinyl pyridine) at room temperature or a h…
Polystyrene and polyvinyl chloride thin films are explored as sample supports for extreme ultraviolet (XUV) spectroscopy of molecular transition metal complexes. Thin polymer films prepared by slip-coating are flat, smooth, and transmit much more XUV light than silicon nitride windows. Analytes can be directly cast onto the polymer surface, or codeposited within it. The M-edge x-ray absorption near-edge (XANES) spectra (40-90 eV) of eight archetypal transition metal complexes (M=Mn, Fe, Co, Ni) are presented to demonstrate the versatility of this method. The films are suitable for pump/probe t…
Graphene wetting by polymers is a critical issue to both the success of polymer-aided transfer of large size sheets onto specific substrates and to the development of well performing nanocomposites. Here we show for the first time that high temperature contact angle measurements can be performed to investigate the wettability of CVD graphene by molten polymers. In particular, poly(methyl methacrylate), a widely used polymer support for CVD graphene transfer, has been adopted herein for this proof-of-concept study and the values of contact angle and work of adhesion have been provided in the te…
We present an investigation of the role of micropatterning on adhesion properties at soft deformable polydimethylsiloxane (PDMS)/ acrylic adhesive interfaces. Contrary to what has been observed for low aspect ratio rigid patterns, where the adhesion enhancement was found to only result from the increase of interfacial area due to patterning, we show that for soft elastic arrays of cylindrical pillars, the elastic deformation of the patterns can lead to noticeable extra adhesion increase. The effect of the geometrical characteristics of the patterning for hexagonal arrays of PDMS micropillars o…
Vertically aligned carbon nanotube (CNT) forests are a particularly interesting class of nanomaterials, because they combine multifunctional properties, such as high energy absorption, compressive strength, recoverability and super-hydrophobicity with light weight. These characteristics make them suitable for application as coating, protective layers and antifouling substrates for metallic pipelines and blades. Direct growth of CNT forests on metals offers the possibility to transfer the tunable CNT functionalities directly onto the desired substrates. Here, we focus on characterizing the stru…
