Direct Numerical Simulation of Surface Wrinkling for Extraction of Thin Metal Film Material Properties.

This paper presents a direct numerical simulation for the extraction of material properties based on thin-film wrinkling on scotch tape. Conventional FEM-based buckling simulation sometimes requires complex modeling techniques concerning mesh element manipulation or boundary conditions. The direct numerical simulation differs from FEM (finite element method)-based conventional two-step linear-nonlinear buckling simulation in that mechanical imperfections are directly applied into the elements of the simulation model. Hence, it can be performed in one step to find the wrinkling wavelength and amplitude, which are key parameters to extract the material mechanical properties. Moreover, the direct simulation can reduce simulation time and modeling complexity. Using the direct model, the effect of the number of imperfections on wrinkling characteristics was first studied, and then wrinkling wavelengths depending on the elastic moduli of the associated materials were prepared for the extraction of material properties. Thin-film wrinkling test patterns on scotch tape were fabricated using the transfer technique with low adhesion between metal films and the polyimide substrate. The material properties of the thin metal films were determined by comparing the measured wrinkling wavelengths and the proposed direct simulation results. By consequence, the elastic moduli of 300 nm thick gold film and 300 nm thick aluminum were determined as 250 GPa and 300 GPa, respectively.

Surface-Modified Inhaled Microparticle-Encapsulated Celastrol for Enhanced Efficacy in Malignant Pleural Mesothelioma.

Malignant pleural mesothelioma (MPM) is a rare and aggressive cancer affecting the pleural lining of the lungs. Celastrol (Cela), a pentacyclic triterpenoid, has demonstrated promising therapeutic potential as an antioxidant, anti-inflammatory, neuroprotective agent, and anti-cancer agent. In this study, we developed inhaled surface-modified Cela-loaded poly(lactic-co-glycolic) acid (PLGA) microparticles (Cela MPs) for the treatment of MPM using a double emulsion solvent evaporation method. The optimized Cela MPs exhibited high entrapment efficiency (72.8 ± 6.1%) and possessed a wrinkled surface with a mean geometric diameter of ~2 µm and an aerodynamic diameter of 4.5 ± 0.1 µm, suggesting them to be suitable for pulmonary delivery. A subsequent release study showed an initial burst release up to 59.9 ± 2.9%, followed by sustained release. The therapeutic efficacy of Cela MPs was evaluated against four mesothelioma cell lines, where Cela MP exhibited significant reduction in IC50 values, and blank MPs produced no toxicity to normal cells. Additionally, a 3D-spheroid study was performed where a single dose of Cela MP at 1.0 µM significantly inhibited spheroid growth. Cela MP was also able to retain the antioxidant activity of Cela only while mechanistic studies revealed triggered autophagy and an induction of apoptosis. Therefore, these studies highlight the anti-mesothelioma activity of Cela and demonstrate that Cela MPs are a promising inhalable medicine for MPM treatment.

Surface Wrinkling for Flexible and Stretchable Sensors.

Recent advances in nanolithography, miniaturization, and material science, along with developments in wearable electronics, are pushing the frontiers of sensor technology into the large-scale fabrication of highly sensitive, flexible, stretchable, and multimodal detection systems. Various strategies, including surface engineering, have been developed to control the electrical and mechanical characteristics of sensors. In particular, surface wrinkling provides an effective alternative for improving both the sensing performance and mechanical deformability of flexible and stretchable sensors by releasing interfacial stress, preventing electrical failure, and enlarging surface areas. In this study, recent developments in the fabrication strategies of wrinkling structures for sensor applications are discussed. The fundamental mechanics, geometry control strategies, and various fabricating methods for wrinkling patterns are summarized. Furthermore, the current state of wrinkling approaches and their impacts on the development of various types of sensors, including strain, pressure, temperature, chemical, photodetectors, and multimodal sensors, are reviewed. Finally, existing wrinkling approaches, designs, and sensing strategies are extrapolated into future applications.

Complex Nanowrinkling in Chiral Liquid Crystal Surfaces: From Shaping Mechanisms to Geometric Statistics.

Surface wrinkling is closely linked to a significant number of surface functionalities such as wetting, structural colour, tribology, frictions, biological growth and more. Given its ubiquity in nature's surfaces and that most material formation processes are driven by self-assembly and self-organization and many are formed by fibrous composites or analogues of liquid crystals, in this work, we extend our previous theory and modeling work on in silico biomimicking nanowrinkling using chiral liquid crystal surface physics by including higher-order anisotropic surface tension nonlinearities. The modeling is based on a compact liquid crystal shape equation containing anisotropic capillary pressures, whose solution predicts a superposition of uniaxial, equibiaxial and biaxial egg carton surfaces with amplitudes dictated by material anchoring energy parameters and by the symmetry of the liquid crystal orientation field. The numerical solutions are validated by analytical solutions. The blending and interaction of egg carton surfaces create surface reliefs whose amplitudes depend on the highest nonlinearity and whose morphology depends on the anchoring coefficient ratio. Targeting specific wrinkling patterns is realized by selecting trajectories on an appropriate parametric space. Finally, given its importance in surface functionalities and applications, the geometric statistics of the patterns up to the fourth order are characterized and connected to the parametric anchoring energy space. We show how to minimize and/or maximize skewness and kurtosis by specific changes in the surface energy anisotropy. Taken together, this paper presents a theory and simulation platform for the design of nano-wrinkled surfaces with targeted surface roughness metrics generated by internal capillary pressures, of interest in the development of biomimetic multifunctional surfaces.

Suspended Palladium/Polymer Bilayer for High-Contrast and Fast Hydrogen Sensors.

Hydrogen sensing is extremely essential for hydrogen-related applications due to the explosibility of hydrogen gas (H2). Here, we first present a high-contrast and fast optical hydrogen sensor, which is a partially suspended Pd/PMMA bilayer on a PDMS substrate with a microgroove array on the surface. The suspended structure reduces constraints from the substrate on the Pd film, leading to a large wrinkling amplitude and fast response rate during hydrogenation. The PMMA film can protect the Pd film from the poisonous impurities in the air and improve the flexibility of the bilayer. When exposed to 4% H2 mixed with air, the reflectance of the sensor drops down from 43 to 4% at 600 nm wavelength, in which the corresponding reflectance contrast, defined as the ratio of the reflectances before and after exposure to hydrogen, is 10.75. Such a high reflectance variation results from the light scattering induced by the wrinkling of the suspended Pd/PMMA bilayer during hydrogenation. Meanwhile, the sensor has a fast response that the reflectance can decrease from 43 to 33% within 0.6 s. Moreover, the sensor shows good recyclability and hydrogen selectivity. These excellent performances suggest that our suspended Pd/PMMA bilayer has great potential for practical hydrogen detection.

Influence of Osmotic Pressure on Nanostructures in Thin Films of a Weakly-Segregated Block Copolymer and Its Blends with a Homopolymer.

We studied the influence of osmotic pressure on nanostructures in thin films of a symmetric weakly-segregated polystyrene-block-poly (methyl methacrylate), P(S-b-MMA), block copolymer and its mixtures with a polystyrene (PS) homopolymer of various compositions. Thin films were deposited on substrates through surface neutralization. The surface neutralization results from the PS mats, which were oxidized and cross-linked by UV-light exposure. Thus, thermal annealing produced perpendicularly oriented lamellae and perforated layers, depending on the content of added PS chains. Nevertheless, a mixed orientation was obtained from cylinders in thin films, where a high content of PS was blended with the P(S-b-MMA). A combination of UV-light exposure and acetic acid rinsing was used to remove the PMMA block. Interestingly, the treatment of PMMA removal inevitably produced osmotic pressure and consequently resulted in surface wrinkling of perpendicular lamellae. As a result, a hierarchical structure with two periodicities was obtained for wrinkled films with perpendicular lamellae. The formation of surface wrinkling is due to the interplay between UV-light exposure and acetic acid rinsing. UV-light exposure resulted in different mechanical properties between the skin and the inner region of a film. Acetic acid rinsing produced osmotic pressure. It was found that surface wrinkling could be suppressed by reducing film thickness, increasing PS content and using high-molecular-weight P(S-b-MMA) BCPs.

Observation of General Entropy-Enthalpy Compensation Effect in the Relaxation of Wrinkled Polymer Nanocomposite Films.

Surface-textured polymer nanocomposite (PNC) films are utilized in many device applications, and therefore understanding the relaxation behavior of such films is important. By extending an in situ wrinkle relaxation method, we observed that the thermal stability of wrinkled PNC films, both above and below the glass transition temperature (Tg), is proportional to a film's nanoparticle (polymer grafted and bare) concentration, with a slope that changes sign at a compensation temperature (Tcomp) that is determined to be in the vicinity of the film's Tg. This provides unambiguous confirmation of entropy-enthalpy compensation (EEC) as a general feature of PNC films, implying that the stability of PNC films changes from being enhanced to becoming diminished by simply passing through this characteristic temperature, a phenomenon having evident practical ramifications. We suggest EEC will also arise in films where residual stresses are associated with the film fabrication process, which is relevant to nanotech device applications.

Light-Associated Surface Wrinkling-Based Metrology for the Photosoftening Characterization in Azobenzene-Polymer Supramolecular Complexes.

As an intriguing characteristic of azobenzene-containing materials (azo-materials), photoinduced changes in mechanical properties (e.g., photosoftening) have stimulated many efforts both theoretically and experimentally. Here a simple yet powerful tool (i.e., a light-associated surface wrinkling-based method) to study the photosoftening effect in azobenzene-polymer (azo-polymer) supramolecular complexes is reported. The photo-induced modulus decrease of supramolecular complex films is deduced by analyzing the change of critical wrinkle wavelength of strain-induced surface wrinkling, in the case of varying experiment parameters. In particular, thanks to the facile modular tunability of the supramolecular system, the photosoftening effect has been systematically investigated as a function of azo-moiety content and the molecular weight of the host polymer. Notably, a photosoftening coefficient that is related to the chemical composition/structure of azo-polymers is introduced, and a simple formula that can quantify the connection of the photosoftening with external irradiation conditions and internal chemical factors of azo-polymers is derived for the first time. The obtained results are of great importance not only to enhance understanding of the photosoftening mechanism, but also to thoroughly apply it in diverse smart fields.

Wrinkling instabilities for biologically relevant fiber-reinforced composite materials with a case study of Neo-Hookean/Ogden-Gasser-Holzapfel bilayer.

Wrinkling is a ubiquitous surface phenomenon in many biological tissues and is believed to play an important role in arterial health. As arteries are highly nonlinear, anisotropic, multilayered composite systems, it is necessary to investigate wrinkling incorporating these material characteristics. Several studies have examined surface wrinkling mechanisms with nonlinear isotropic material relationships. Nevertheless, wrinkling associated with anisotropic constitutive models such as Ogden-Gasser-Holzapfel (OGH), which is suitable for soft biological tissues, and in particular arteries, still requires investigation. Here, the effects of OGH parameters such as fibers' orientation, stiffness, and dispersion on the onset of wrinkling, wrinkle wavelength and amplitude are elucidated through analysis of a bilayer system composed of a thin, stiff neo-Hookean membrane and a soft OGH substrate subjected to compression. Critical contractile strain at which wrinkles occur is predicted using both finite element analysis and analytical linear perturbation approach. Results suggest that besides stiffness mismatch, anisotropic features associated with fiber stiffness and distribution might be used in natural layered systems to adjust wrinkling and subsequent folding behaviors. Further analysis of a bilayer system with fibers in the (x-y) plane subjected to compression in the x direction shows a complex dependence of wrinkling strain and wavelength on fiber angle, stiffness, and dispersion. This behavior is captured by an approximation utilizing the linearized anisotropic properties derived from OGH model. Such understanding of wrinkling in this artery wall-like system will help identify the role of wrinkling mechanisms in biological artery in addition to the design of its synthetic counterparts.

Wrinkled Hydrogel Surfaces with Modulated Surface Chemistry and Topography: Evaluation As Supports for Cell Growth and Transplant.

We report a straightforward procedure to simultaneously functionalize hydrophobic PC supports with vinylpyrrolidone (VP)-based hydrogels with both variable ionic load as well as surface topography, forming wrinkles. The strategy involves three consecutive steps: first, a contact of the polymeric support (PC) with a photopolymerizable solution comprising vinylic monomers is established. Second, UV-light exposure curing of the solution and finally, the third step involes the swelling of the hydrogel network that finally provokes its surface detachment. Interestingly, a wrinkled hybrid PC/hydrogel interface remains after this detachment. Several experimental parameters permitted us to finely control the wrinkle characteristics such as amplitude and period. The experimental parameters that can be varied, herein we will focus on the variation of the elapsed time (i.e., time of contact between the support and the photosensitive monomer mixture, or the solvent (type and amount) included in the monomer mixture. Equally, the nature of the additional ionic methacrylate monomers (M) employed plays a key role on the final topography. According to confocal raman microscopy results, we evidenced that a monomer diffusion into the PC substrate before the UV irradiation step modifies the interfacial (hydrogel/substrate) chemical composition and leads upon UV irradiation to the formation of a thin hydrogel surface layer. The surface chemical composition and structural characteristics were demonstrated to significantly change the surface interaction with different cell lines, affecting cell adhesion, proliferation, or transplantation.

Writing Wrinkles on Poly(dimethylsiloxane) (PDMS) by Surface Oxidation with a CO2 Laser Engraver.

Surface wrinkles formed by the buckling of a strained stiff layer attached to a soft elastomer foundation have been widely used in a variety of applications. Micropatterning of wrinkled topographies is, however, limited by process/system complexities. In this article, we report an approach to write surface wrinkles with desired pattern geometries on poly(dimethylsiloxane) (PDMS) elastomers using a commercial infrared laser engraver with a spot size of 127 µm. Wrinkled micropatterns with wavelength from <50 to >300 µm were obtained in minutes without using special facilities or atmospheres. The minimal achievable pattern sizes of one-dimensional and two-dimensional patterns and the change of the minimal achievable pattern size with wrinkle orientation were investigated under a given set of operating parameters. Sub-spot size patterning was also demonstrated. To reduce surface cracking, a typical problem in large-area wrinkle patterning, a patterning scheme that separates neighboring laser exposure areas by nonexposure gaps was developed. In addition, micropatterns with gradient wrinkles were created on the surface. This is the first report that patterns microscale surface wrinkles on elastomer surfaces using infrared laser irradiation. The simple and versatile approach is expected to provide a fast yet controllable way to create wrinkled micropatterns at low cost to facilitate a broad array of studies in surface engineering, cellular biomechanics, and optics.

Light-Modulated Surface Micropatterns with Multifunctional Surface Properties on Photodegradable Polymer Films.

Photodegradable polymers constitute an emerging class of materials that are expected to possess advances in the areas of micro/nano- and biotechnology. Herein, we report a green and effective strategy to fabricate light-responsive surface micropatterns by taking advantage of photodegradation chemistry. Thanks to the molecular chain breakage during the photolysis process, the stress field of photodegradable polymer-based wrinkling systems undergoes continuous disturbance, leading to the release/reorganization of the internal stress. Revealed by systematic experiments, the light-induced stress release mechanism enables the dynamic adaption of not only thermal-induced labyrinth wrinkles, but uniaxially oriented wrinkle microstructures induced by mechanical straining. This method paves the way for their diverse applications, for example, in optical information display and storage, and the smart fabrication of multifunctional surfaces as demonstrated here.

Topographical and Electrical Stimulation of Neuronal Cells through Microwrinkled Conducting Polymer Biointerfaces.

The development of smart biointerfaces combining multiple functions is crucial for triggering a variety of cellular responses. In this work, wrinkled organic interfaces based on the conducting polymer poly(3,4-ethylene dioxythiophene) doped with poly(styrene sulfonate) are developed with the aim to simultaneously convey electrical and topographical stimuli to cultured cells. The surface wrinkling of thin films on heat-shrink polymer sheets allows for rapid patterning of self-assembled anisotropic topographies characterized by micro/sub-microscale aligned wrinkles. The developed interfaces prove to support the growth and differentiation of neural cells (SH-SY5Y, human neuroblastoma) and are remarkably effective in promoting axonal guidance, by guiding and stimulating the neurite growth in differentiating cells. Electrical stimulation with biphasic pulses delivered through the conductive wrinkled interface is found to further promote the neurite growth, demonstrating the suitability of such interfaces as platforms for conveying multiple stimuli to cells and tissues.

Wood-mimetic skins prepared using horseradish peroxidase catalysis to induce surface wrinkling of chitosan film upon drying.

We previously developed bio-based wrinkled surfaces induced by wood-mimetic skins upon drying in which microscopic wrinkles were fabricated on a chitosan (CS) film by immersing it in a phenolic acid solution, followed by horseradish peroxidase (HRP)-catalyzed surface reaction and drying. However, the detailed structure of the resulting wood-mimetic skins, including crosslinking mode and thickness, has not been clarified due to the difficulty of the analysis. Here, we prepare wrinkled films using ferulic acid (FE), vanillic acid (VA), and homovanillic acid (HO) and characterize their structures to clarify the unknown characteristics of wood-mimetic skin. Chemical and structural analyses of wood-mimetic skins prepared using VA and HO indicate that the crosslinking structure in the skin is composed of ionic bonds between CS and an oligophenolic residue generated by the HRP-catalyzed reaction on the CS surface. Moreover, the quantity of these ionic bonds is related to the skin hardness and wrinkle size. Finally, SEM and TOF-SIMS analyses indicate that the skin thickness is on the submicron order (<200nm).

Simple and Versatile Strategy to Prevent Surface Wrinkling by Visible Light Irradiation.

A stiff film bonded to a compliant substrate is susceptible to surface wrinkling when it is subjected to in-plane compression. Prevention of surface wrinkling is essential in many cases to maintain the integrity and functionality of this kind of system. Here we report a simple versatile technique to restrain surface wrinkling of an amorphous poly(p-aminoazobenzene) (PAAB) film by visible light irradiation. The key idea is to use the combined effects of photosoftening of the PAAB film and the stress release induced by the reversible photoisomerization. The main finding given by experiments and dimensional analysis is that the elastic modulus Ef of the film is well modulated by the ratio of light intensity and the release rate, i.e., I/V. Furthermore, the explicit solution describing the correlation of I/V with Ef is derived for the first time. The difference between the calculated critical wrinkling strain εc,t based on Ef and the experimentally measured value εc enables us to quantitatively evaluate the release amount of the compressive stress in the film. These key solutions provide a simple strategy to prevent the undesired surface wrinkling. Additionally, they allow us to propose a wrinkling-based technique to investigate photoinduced changes in the mechanical properties of azo-containing materials.

Synergism of Dewetting and Self-Wrinkling To Create Two-Dimensional Ordered Arrays of Functional Microspheres.

Here we report a simple, novel, yet robust nonlithographic method for the controlled fabrication of two-dimensional (2-D) ordered arrays of polyethylene glycol (PEG) microspheres. It is based on the synergistic combination of two bottom-up processes enabling periodic structure formation for the first time: dewetting and the mechanical wrinkle formation. The deterministic dewetting results from the hydrophilic polymer PEG on an incompatible polystyrene (PS) film bound to a polydimethylsiloxane (PDMS) substrate, which is directed both by a wrinkled template and by the template-directed in-situ self-wrinkling PS/PDMS substrate. Two strategies have been introduced to achieve synergism to enhance the 2-D ordering, i.e., employing 2-D in-situ self-wrinkling substrates and boundary conditions. As a result, we achieve highly ordered 2-D arrays of PEG microspheres with desired self-organized microstructures, such as the array location (e.g., selectively on the crest/in the valley of the wrinkles), diameter, spacing of the microspheres, and array direction. Additionally, the coordination of PEG with HAuCl4 is utilized to fabricate 2-D ordered arrays of functional PEG-HAuCl4 composite microspheres, which are further converted into different Au nanoparticle arrays. This simple versatile combined strategy could be extended to fabricate highly ordered 2-D arrays of other functional materials and achieve desirable properties and functionalities.

Bioinspired Fabrication of Free-Standing Conducting Films with Hierarchical Surface Wrinkling Patterns.

Mechanical instability has been shown to play an important role in the formation of wrinkle structures in biofilms, which not only can adopt instability modes as templates to regulate their 3D architectures but also can tune internal stresses to achieve stable patterns. Inspired by nature, we report a mechanical-chemical coupling method to fabricate free-standing conducting films with instability-driven hierarchical micro/nanostructured patterns. When polypyrrole (PPy) film is grown on an elastic substrate via chemical oxidation polymerization, differential growth along with in situ self-reinforcing effect induces stable wrinkle patterns with different scales of wavelengths. The self-reinforcing effect modifies the internal stresses, hence PPy films with intact wrinkles can be removed from substrates and further transferred onto target substrates for functional device fabrication. To understand the buckling mechanics, we construct a model which reveals the formation of hierarchical wrinkle patterns.

Redox-Switchable Surface Wrinkling on Polyaniline Film.

Here the redox-driven switch between the wrinkled and dewrinkled states on poly-aniline (PANI) film is reported. This switch is derived from the reversible transition in different intrinsic redox states of polyaniline (e.g., between emeraldine salt (ES) and leucoemeraldine base (LEB) or between ES and pernigraniline base (PB)) that are involved in the redox reaction, coupled with the corresponding volume expansion/shrinkage. Interestingly, the as-wrinkled ES film becomes deswollen and dewrinkled when reduced to the LEB state or oxidized to the PB state. Conversely, oxidation of the LEB film or reduction of the PB film into the swollen ES film leads to the reoccurrence of surface wrinkling. Furthermore, the reducibility of the dewrinkled LEB film and the oxidizability of the dewrinkled PB film are well utilized respectively to yield various wrinkled PANI-based composite films.

Bio-based Wrinkled Surfaces Harnessed from Biological Design Principles of Wood and Peroxidase Activity.

A new and simple approach for surface wrinkling inspired by polymer assemblies in wood fibers is introduced. A hard skin is synthesized on a linear polysaccharide support that resembles the structural units of the cell wall. This skin, a wood mimetic layer, is produced through immersion in a solution containing phenolic precursor and subsequent surface reaction by horseradish peroxidase. A patterned surface with micron-scale wrinkles is formed upon drying and as a result of inhomogeneous shrinkage. We demonstrate that the design of the wrinkled surfaces can be controlled by the molecular structure of the phenolic precursor, temperature, and drying stress. It is noteworthy that this is a totally bio-based system involving green materials and processes.

Conducting shrinkable nanocomposite based on au-nanoparticle implanted plastic sheet: tunable thermally induced surface wrinkling.

A thermally shrinkable and conductive nanocomposite material is prepared by supersonic cluster beam implantation (SCBI) of neutral Au nanoparticles (Au NPs) into a commercially available thermo-retractable polystyrene (PS) sheet. Micronanowrinkling is obtained during shrinking, which is studied by means of SEM, TEM and AFM imaging. Characteristic periodicity is determined and correlated with nanoparticle implantation dose, which permits us to tune the topographic pattern. Remarkable differences emerged with respect to the well-known case of wrinkling of bilayer metal-polymer. Wrinkled composite surfaces are characterized by a peculiar multiscale structuring that promises potential technological applications in the field of catalytic surfaces, sensors, biointerfaces, and optics, among others.