thin-film-composite-silicon-elastomers-for-cell-culture-skin

Thin Film Composite Silicon Elastomers for Cell Culture and Skin Applications: Manufacturing and Characterization

In this protocol, we present methods to fabricate thin elastomer composite films for advanced cell culture applications and for the development of skin ...

INM - Leibniz Institute for New Materials

Saarland University

The effect of viscoelasticity on adhesion was investigated for micropatterned epoxy surfaces and compared to nonpatterned surfaces. A two-component epoxy system was used to produce epoxy compositions with different viscoelastic properties. Pillar arrays with flat punch tip geometries were fabricated with a two-step soft lithography process. Adhesion properties were measured with a home-built adhesion tester using a spherical sapphire probe as a counter-surface. Compared to flat controls, micropatterned epoxy samples with low viscoelasticity (i.e., low damping factors) showed at least a 20-fold reduction in pull-off force per actual contact area for both low (E' = 2.3 MPa) and high (E' = 2.3 GPa) storage moduli. This antiadhesive behavior may result from poor contact formation and indicates that the adhesion performance of commonly used elastomers for dry adhesives (e.g., polydimethylsiloxane) is governed by the interfacial viscoelasticity. Adhesion significantly increased with increasing viscoelasticity. Micropatterned samples with high viscoelasticity showed a 4-fold reduction in adhesion for aspect ratio (AR) 1.1 patterns but a 2-fold enhancement in adhesion for AR 2.2 patterns. These results indicate that viscoelasticity can enhance the effect of surface patterning on adhesion and should be considered as a significant parameter in the design of artificial patterned adhesives.

Effect of viscoelasticity on adhesion of bioinspired micropatterned epoxy surfaces.

In this work, the adhesion of biomimetic polydimethylsiloxane (PDMS) pillar arrays with mushroom-shaped tips was studied on nano- and micro-rough surfaces and compared to unpatterned controls. The adhesion strength on nano-rough surfaces invariably decreased with increasing roughness, but pillar arrays retained higher adhesion strengths than unpatterned controls in all cases. The results were analyzed with a model that focuses on the effect on adhesion of depressions in a rough surface. The model fits the data very well, suggesting that the pull-off strength for patterned PDMS is controlled by the deepest dimple-like feature on the rough surface. The lower pull-off strength for unpatterned PDMS may be explained by the initiation of the pull-off process at the edge of the probe, where significant stress concentrates. With micro-rough surfaces, pillar arrays showed maximum adhesion with a certain intermediate roughness, while unpatterned controls did not show any measurable adhesion. This effect can be explained by the inability of micropatterned surfaces to conform to very fine and very large surface asperities.

Effect of nano- and micro-roughness on adhesion of bioinspired micropatterned surfaces.

We analyze theoretically the moment of inertia of the desert ant Cataglyphis (C. bicolor and C. fortis) around a vertical axis through its own center of mass when the animal raises its gaster to a vertical position. Compared to the value when the gaster is horizontal, the moment of inertia is reduced to one half; this implies that when increasing its angular acceleration the ant need apply only half the level of torque when the gaster is raised, compared to when the gaster is lowered. As an example, we analyze the cases of an ant running on circular and sinusoidal paths. In both cases, the ant must apply a sideways thrust, anti-roll and anti-pitch torques to avoid toppling, and, on the circular path when accelerating and throughout the sinusoidal trajectory, a torque to enable turning as the path curves. When the ant is accelerating in a very tight circle or running on a very narrow sinusoidal path, in which the amplitude of the sinusoid is less than the length of the ant's body, the forces required for the turning torque can equal and exceed those required for the sideways thrust, and can be reduced significantly by the ant raising the gaster, whereas the foot-thrust for the anti-roll and anti-pitch torques rises only modestly when the gaster is up. This suggests that there may be an evolutionary advantage for employing the gaster-raising mode of locomotion, since this habit will allow desert ants to use lower forces and less energy, and perhaps run faster on more tortuous paths.

Cataglyphis desert ants improve their mobility by raising the gaster.

Hierarchical super-structure identified by polarized light microscopy, electron microscopy and nanoindentation: Implications for the limits of biological control over the growth mode of abalone sea shells.

A powerful principle in nature is the presence of surface patterns to improve specific characteristics or to enable completely new functions. Here, we present two case studies where bioinspired surface patterns based on the adhesive system of geckos may be applied for biomedical applications: residue-free adhesion to skin and gecko-inspired suture threads for knot-free wound closure.

Bioinspired polymeric surface patterns for medical applications.

We tested the adhesive response of polymer surfaces structured with arrays of cylindrical fibrils having diameters of 10-20 µm and aspect ratios 1-2.4. Fibrils had two different tip shapes of end-flaps and round edges. A preload-induced mechanical buckling instability of the fibrils was used to switch between the states of adhesion and non-adhesion. Non-adhesion in fibrils with round edges was reached at preloads that caused fibril buckling, whereas fibrils with end-flaps showed adhesion loss only at very high preloads. The round edge acted as a circumferential flaw prohibiting smooth tip contact recovery leading to an adhesion loss. In situ observations showed that, after reversal of buckling, the end-flaps unfold and re-form contact under prevailing compressive stress, retaining adhesion in spite of buckling. At very high preloads, however, end-flaps are unable to re-form contact resulting in adhesion loss. Additionally, the end-flaps showed varying contact adaptability as a function of the fibril-probe alignment, which further affects the preload for adhesion loss. The combined influence of preload, tip shape and alignment on adhesion can be used to switch adhesion in bioinspired fibrillar arrays.

Preload-responsive adhesion: effects of aspect ratio, tip shape and alignment.

Copper kills bacteria rapidly by a mechanism that is not yet fully resolved. The antibacterial property of copper has raised interest in its use in hospitals, in place of plastic or stainless steel. On the latter surfaces, bacteria can survive for days or even weeks. Copper surfaces could thus provide a powerful accessory measure to curb nosocomial infections. We here investigated the effect of the copper surface structure on the efficiency of contact killing of Escherichia coli, an aspect which so far has received very little attention. It was shown that electroplated copper surfaces killed bacteria more rapidly than either polished copper or native rolled copper. The release of ionic copper was also more rapid from electroplated copper compared to the other materials. Scanning electron microscopy revealed that the bacteria nudged into the grooves between the copper grains of deposited copper. The findings suggest that, in terms of contact killing, more efficient copper surfaces can be engineered. 

Surface structure influences contact killing of bacteria by copper.

The goal of our study is to better understand the design parameters of bioinspired dry adhesives inspired by geckos. For this, we fabricated single macroscopic pillars of 400 μm diameter with different aspect ratios and different tip shapes (i.e., flat tips, spherical tips with different radii, and mushroom tips with different diameters). Tilt-angle-dependent adhesion measurements showed that although the tip shape of the pillars strongly influences the pull-off force, the pull-off strength is similar for flat and mushroom-shaped tips. We found no tilt-angle dependency of adhesion for spherical tip structures and, except for high tilt angle and low preload experiments, no tilt-angle effect for mushroom-tip pillars. For flat-tip pillars, we found a strong influence of tilt angle on adhesion, which decreased linearly with increasing aspect ratio. The experiments show that for the tested aspect ratios between 1 and 5, a linear decrease of tilt-angle dependency is found. The results of our studies will help to design bioinspired adhesives for application on smooth and rough surfaces. 

Single macroscopic pillars as model system for bioinspired adhesives: influence of tip dimension, aspect ratio, and tilt angle.

Bacterial repellence in suture materials is a desirable property that can potentially improve the healing process by preventing infection. We describe a method for generating nanostructures at the surface of commercial sutures of different composition, and their potential for preventing biofilm formation. We show how bacteria attachment is altered in the presence of nanosized topographies and identify optimum designs for preventing it without compromising biocompatibility and applicability in terms of nanostructure robustness or tissue friction. These studies open new possibilities for flexible and cost-effective realization of topography-based antibacterial coatings for absorbable biomedical textiles. 

Nanostructured medical sutures with antibacterial properties.

A switchable dry adhesive based on a nickel-titanium (NiTi) shape-memory alloy with an adhesive silicone rubber surface has been developed. Although several studies investigate micropatterned, bioinspired adhesive surfaces, very few focus on reversible adhesion. The system here is based on the indentation-induced two-way shape-memory effect in NiTi alloys. NiTi is trained by mechanical deformation through indentation and grinding to elicit a temperature-induced switchable topography with protrusions at high temperature and a flat surface at low temperature. The trained surfaces are coated with either a smooth or a patterned adhesive polydimethylsiloxane (PDMS) layer, resulting in a temperature-induced switchable surface, used for dry adhesion. Adhesion tests show that the temperature-induced topographical change of the NiTi influences the adhesive performance of the hybrid system. For samples with a smooth PDMS layer the transition from flat to structured state reduces adhesion by 56%, and for samples with a micropatterned PDMS layer adhesion is switchable by nearly 100%. Both hybrid systems reveal strong reversibility related to the NiTi martensitic phase transformation, allowing repeated switching between an adhesive and a nonadhesive state. These effects have been discussed in terms of reversible changes in contact area and varying tilt angles of the pillars with respect to the substrate surface.

Temperature-Induced Switchable Adhesion using Nickel-Titanium-Polydimethylsiloxane Hybrid Surfaces.

Nature uses hierarchical fibrillar structures to mediate temporary adhesion to arbitrary substrates. Such structures provide high compliance such that the flat fibril tips can be better positioned with respect to asperities of a wavy rough substrate. We investigated the buckling and adhesion of hierarchically structured adhesives in contact with flat smooth, flat rough and wavy rough substrates. A macroscopic model for the structural adhesive was fabricated by molding polydimethylsiloxane into pillars of diameter in the range of 0.3-4.8 mm, with up to three different hierarchy levels. Both flat-ended and mushroom-shaped hierarchical samples buckled at preloads one quarter that of the single level structures. We explain this behavior by a change in the buckling mode; buckling leads to a loss of contact and diminishes adhesion. Our results indicate that hierarchical structures can have a strong influence on the degree of adhesion on both flat and wavy substrates. Strategies are discussed that achieve highly compliant substrates which adhere to rough substrates. 

Hierarchical macroscopic fibrillar adhesives: in situ study of buckling and adhesion mechanisms on wavy substrates.

Patterned microstructures represent a potential approach for improving current wound closure strategies. Microstructures can be fabricated by multiple techniques including replica molding of soft polymer-based materials. However, polymeric microstructures often lack the required shear resistance with tissue needed for wound closure. In this work, scalable microstructures made from composites based on polydimethylsiloxane (PDMS) were explored to enhance the shear resistance with wet tissue. To achieve suitable mechanical properties, PDMS was reinforced by incorporation of polyethylene (PE) particles into the pre-polymer and by coating PE particle reinforced substrates with parylene. The reinforced microstructures showed a 6-fold enhancement, the coated structures even a 13-fold enhancement in Young׳s modulus over pure PDMS. Shear tests of mushroom-shaped microstructures (diameter 450µm, length 1mm) against chicken muscle tissue demonstrate first correlations that will be useful for future design of wound closure or stabilization implants.

Bioinspired polydimethylsiloxane-based composites with high shear resistance against wet tissue.

The benefits of synthetic fibrillar dry adhesives for temporary and reversible attachment to hard objects with smooth surfaces have been successfully demonstrated in previous studies. However, surface roughness induces a dramatic reduction in pull-off stresses and necessarily requires revised design concepts. Toward this aim, we introduce cylindrical two-phase single pillars, which are composed of a mechanically stiff stalk and a soft tip layer. Adhesion to smooth and rough substrates is shown to exceed that of conventional pillar structures. The adhesion characteristics can be tuned by varying the thickness of the soft tip layer, the ratio of the Young's moduli and the curvature of the interface between the two phases. For rough substrates, adhesion values similar to those obtained on smooth substrates were achieved. Our concept of composite pillars overcomes current practical limitations caused by surface roughness and opens up fields of application where roughness is omnipresent.

Composite Pillars with a Tunable Interface for Adhesion to Rough Substrates.

Micropatterned polymer surfaces that operate at various temperatures are required for emerging technical applications such as handling of objects or space debris. As the mechanical properties of polymers can vary significantly with temperature, adhesion performance can exhibit large variability. In the present paper, we experimentally study temperature effects on the adhesion of micropatterned adhesives (pillar length 20µm, aspect ratios 0.4 and 2) made from three different polymers, i.e., polydimethylsiloxane (PDMS), perfluoropolyether dimethacrylate (PFPEdma), and polyurethane (PU-ht). PU specimens showed the highest pull-off stresses of about 57kPa at 60°C, i.e., more than twice the value of unpatterned control samples. The work of separation similarly showed a maximum at that temperature, which was identified as the glass transition temperature, Tg. PDMS and PFPEdma specimens were tested above their Tg. As a result, the adhesion properties decreased monotonically (about 50% for both materials) for temperature elevation from 20 to 120°C. Overall, the results obtained in our study indicate that the operating temperature related to the glass transition temperature should be considered as a significant parameter for assessing the adhesion performance of micropatterned adhesives and in the technical design of adhesion devices.

Elevated temperature adhesion of bioinspired polymeric micropatterns to glass.

For designing new skin adhesives, the complex mechanical interaction of soft elastomers with surfaces of various roughnesses needs to be better understood. We systematically studied the effects of a wide set of roughness characteristics, film thickness, hold time and material relaxation on the adhesive behaviour of the silicone elastomer SSA 7-9800 (Dow Corning). As model surfaces, we used epoxy replicas obtained from substrates with roughness ranging from very smooth to skin-like. Our results demonstrate that films of thin and intermediate thickness (60 and 160 µm) adhered best to a sub-micron rough surface, with a pull-off stress of about 50 kPa. Significant variations in pull-off stress and detachment mechanism with roughness and hold time were found. In contrast, 320 µm thick films adhered with lower pull-off stress of about 17 kPa, but were less sensitive to roughness and hold time. It is demonstrated that the adhesion performance of the silicone films to rough surfaces can be tuned by tailoring the film thickness and contact time.

Article	Year
Effect of viscoelasticity on adhesion of bioinspired micropatterned epoxy surfaces. Langmuir : the ACS journal of surfaces and colloids\| PubMed ID: 21604777	2011
Effect of nano- and micro-roughness on adhesion of bioinspired micropatterned surfaces. Acta biomaterialia\| PubMed ID: 21925624	2012
Cataglyphis desert ants improve their mobility by raising the gaster. Journal of theoretical biology\| PubMed ID: 22178639	2012
Hierarchical super-structure identified by polarized light microscopy, electron microscopy and nanoindentation: Implications for the limits of biological control over the growth mode of abal... BMC biophysics\| PubMed ID: 22967319	2012
Bioinspired polymeric surface patterns for medical applications. Journal of applied biomaterials & functional materials\| PubMed ID: 23242878	2012
Preload-responsive adhesion: effects of aspect ratio, tip shape and alignment. Journal of the Royal Society, Interface\| PubMed ID: 23554348	2013
Surface structure influences contact killing of bacteria by copper. MicrobiologyOpen\| PubMed ID: 24740976	2014
Single macroscopic pillars as model system for bioinspired adhesives: influence of tip dimension, aspect ratio, and tilt angle. ACS applied materials & interfaces\| PubMed ID: 24779439	2014
Nanostructured medical sutures with antibacterial properties. Biomaterials\| PubMed ID: 25818435	2015
Temperature-Induced Switchable Adhesion using Nickel-Titanium-Polydimethylsiloxane Hybrid Surfaces. Advanced functional materials\| PubMed ID: 26120295	2015
Hierarchical macroscopic fibrillar adhesives: in situ study of buckling and adhesion mechanisms on wavy substrates. Bioinspiration & biomimetics\| PubMed ID: 26496128	2015
Bioinspired polydimethylsiloxane-based composites with high shear resistance against wet tissue. Journal of the mechanical behavior of biomedical materials\| PubMed ID: 26849031	2016
Composite Pillars with a Tunable Interface for Adhesion to Rough Substrates. ACS applied materials & interfaces\| PubMed ID: 27997118	2017
Elevated temperature adhesion of bioinspired polymeric micropatterns to glass. Journal of the mechanical behavior of biomedical materials\| PubMed ID: 28411957	2017
Adhesion and relaxation of a soft elastomer on surfaces with skin like roughness. Journal of the mechanical behavior of biomedical materials\| PubMed ID: 29459289	2018

Eduard Arzt

Biography

JoVE Journal Publications

Other Publications