Effects of different ratios of mannitol to sorbitol on the functional properties of sweet potato starch films.

Sorbitol as a plasticizer is easily crystallized from starch film, resulting in the reduction in plasticizing effect. To improve the plasticizing performance of sorbitol in starch films, mannitol, an acyclic hexahydroxy sugar alcohol, was used to cooperate with sorbitol. The effects of different ratios of mannitol (M) to sorbitol (S) as a plasticizer on mechanical properties, thermal properties, water resistance and surface roughness of sweet potato starch films were investigated. The results showed that the surface roughness of starch film with M:S (60:40) was the smallest. The number of hydrogen bonds between plasticizer and starch molecule was proportional to the mannitol content starch film. With the decrease of mannitol contents, the tensile strength of starch films gradually decreased except for M:S (60:40). Moreover, the transverse relaxation time value of starch film with M:S (100:0) was the lowest, indicating that it had the lowest degree of freedom of water molecules. Starch film with M:S (60:40) is the most effective in delaying the retrogradation of starch film. This study offered a new theoretical basis that different ratios of mannitol to sorbitol improve different performances of starch films.

Intermolecular interactions between starch and polyvinyl alcohol for improving mechanical properties of starch-based straws.

Starch/polyvinyl alcohol (PVA) degradable straws with different PVA contents were prepared by the twin-screw extrusion method. The results showed that the starch/PVA straws with 40 % PVA (PS4) had the highest dispersion uniformity of starch and PVA to achieve the best compatibility, and the compatibility size was below the micron level. Molecular interactions between starch and 40 % polyvinyl alcohol reached the highest due to the highest strength of hydrogen bonds, hence resulting in the highest texture densities. Consequently, the largest compatibility and molecular interactions significantly improved the mechanical properties and water resistance of PS4. Compared to the starch/PVA straw with 0 % PVA (PS0), swelling volume of PS4 decreased by 45.5 % (4 °C) and 65.2 % (70 °C), respectively. After soaking, the diameter strength increased by 540.1 % (4 °C, 1 h) and 638.7 % (70 °C, 15 min), respectively. Water absorption decreased by 45.3 % (4 °C, 30 min) and 27.6 % (70 °C, 30 min).

All-Optical Reversible Azo-Based Wrinkling Patterns with High Aspect Ratio and Polarization-Independent Orientation for Light-Responsive Soft Photonics.

Azobenzene-containing polymers (azopolymers) can serve as building blocks for an emerging class of soft photonics. Using their photoresponses for the micro/nanofabrication of smart surface is a key but still a challenging step. Here, we report a simple visible-light-illumination strategy to trigger diverse configurations of surface wrinkling on azopolymer-based film/substrate systems, which can be switched between flat and wrinkled states by controlling the intensity of the incident light. Different photoresponsive characteristics of azobenzene are involved in driving the wrinkling/dewrinkling switch. For the first time, we achieve the controlled wrinkling with an unexpected high aspect ratio and surprisingly polarization-independent ordered orientation by exploiting the unique photosoftening effect of azobenzene. Theoretical analysis reveals that an in situ photoinduced reversible soft/hard-contrast boundary determines the wrinkling orientation, which is used to fabricate diverse on-demand hierarchical wrinkles. These photoresponsive systems find broad photonic applications that are not easily accessible to other systems, e.g., optically reversible smart display, information security, and well-regulated optical devices.

Erratum: 3D Printing Fiber Electrodes for an All-Fiber Integrated Electronic Device via Hybridization of an Asymmetric Supercapacitor and a Temperature Sensor.

[This corrects the article DOI: 10.1002/advs.201801114.].

3D Printing Fiber Electrodes for an All-Fiber Integrated Electronic Device via Hybridization of an Asymmetric Supercapacitor and a Temperature Sensor.

Wearable fiber-shaped electronic devices have drawn abundant attention in scientific research fields, and tremendous efforts are dedicated to the development of various fiber-shaped devices that possess sufficient flexibility. However, most studies suffer from persistent limitations in fabrication cost, efficiency, the preparation procedure, and scalability that impede their practical application in flexible and wearable fields. In this study, a simple, low-cost 3D printing method capable of high manufacturing efficiency, scalability, and complexity capability to fabricate a fiber-shaped integrated device that combines printed fiber-shaped temperature sensors (FTSs) with printed fiber-shaped asymmetric supercapacitors (FASCs) is developed. The FASCs device can provide stable output power to FTSs. Moreover, the temperature responsivity of the integrated device is 1.95% °C-1.

Highly Sensitive Wearable Pressure Sensors Based on Three-Scale Nested Wrinkling Microstructures of Polypyrrole Films.

Pressure sensors have a variety of applications including wearable devices and electronic skins. To satisfy the practical applications, pressure sensors with a high sensitivity, a low detection limit, and a low-cost preparation are extremely needed. Herein, we fabricate highly sensitive pressure sensors based on hierarchically patterned polypyrrole (PPy) films, which are composed of three-scale nested surface wrinkling microstructures through a simple process. Namely, double-scale nested wrinkles are generated via in situ self-wrinkling during oxidative polymerization growth of PPy film on an elastic poly(dimethylsiloxane) substrate in the mixed acidic solution. Subsequent heating/cooling processing induces the third surface wrinkling and thus the controlled formation of three-scale nested wrinkling microstructures. The multiscale nested microstructures combined with stimulus-responsive characteristic and self-adaptive ability of wrinkling morphologies in PPy films offer the as-fabricated piezoresistive pressure sensors with a high sensitivity (19.32 kPa-1), a low detection limit (1 Pa), an ultrafast response (20 ms), and excellent durability and stability (more than 1000 circles), these comprehensive sensing properties being higher than the reported results in literature. Moreover, the pressure sensors have been successfully applied in the wearable electronic fields (e.g., pulse detection and voice recognition) and microcircuit controlling, as demonstrated here.

Determinative Surface-Wrinkling Microstructures on Polypyrrole Films by Laser Writing.

We report a simple and efficient laser-writing strategy to fabricate hierarchical nested wrinkling microstructures on conductive polypyrrole (PPy) films, which enables us to develop advanced functional surfaces with diverse applications. The present strategy adopts the photothermal effect of PPy films to mimick the formation of hierarchical nested wrinkles observed in nature and design controlled microscale wrinkling patterns. Here, the PPy film is grown on a poly(dimethylsiloxane) (PDMS) substrate via oxidation polymerization of pyrrole in an acidic solution, accompanied by in situ self-wrinkling with wavelengths of two different scales (i.e., λ1 and λ2). Subsequent laser exposure of the PPy/PDMS bilayer induces a new surface wrinkling with a larger wavelength (i.e., λ3). Owing to the retention of the initial λ1 wrinkles, we obtain hierarchical nested wrinkles with the smaller λ1 wrinkles nested in the larger λ3 ones. Importantly, we realize the large-scale path-determinative fabrication of complex oriented wrinkling microstructures by controlling the relative motion between the bilayer and the laser. Combined with the induced changes in surface color, surface-wrinkling microstructures, and conductivity in the PPy films, the laser-writing strategy can find broad applications, for example, in modulation of surface wetting properties and fabrication of microcircuits, as demonstrated in this work.

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.

Self-Supported Crack-Free Conducting Polymer Films with Stabilized Wrinkling Patterns and Their Applications.

Self-supported conducting polymer films with controlled microarchitectures are highly attractive from fundamental and applied points of view. Here a versatile strategy is demonstrated to fabricate thin free-standing crack-free polyaniline (PANI)-based films with stable wrinkling patterns. It is based on oxidization polymerization of pyrrole inside a pre-wrinkled PANI film, in which the wrinkled PANI film is used both as a template and oxidizing agent for the first time. The subsequently grown polypyrrole (PPy) and the formation of interpenetrated PANI/PPy networks play a decisive role in enhancing the film integrity and the stability of wrinkles. This enhancing effect is attributed to the modification of internal stresses by the interpenetrated PANI/PPy microstructures. Consequently, a crack-free film with stable controlled wrinkles such as the wavelength, orientation and spatial location has been achieved. Moreover, the wrinkling PANI/PPy film can be removed from the initially deposited substrate to become free-standing. It can be further transferred onto target substrates to fabricate hierarchical patterns and functional devices such as flexible electrodes, gas sensors, and surface-enhanced Raman scattering substrates. This simple universal enhancing strategy has been extended to fabrication of other PANI-based composite systems with crack-free film integrity and stabilized surface patterns, irrespective of pattern types and film geometries.

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.

Patterning Surfaces on Azo-Based Multilayer Films via Surface Wrinkling Combined with Visible Light Irradiation.

Here, a simple combined strategy of surface wrinkling with visible light irradiation to fabricate well tunable hierarchical surface patterns on azo-containing multilayer films is reported. The key to tailor surface patterns is to introduce a photosensitive poly(disperse orange 3) intermediate layer into the film/substrate wrinkling system, in which the modulus decrease is induced by the reversible photoisomerization. The existence of a photoinert top layer prevents the photoisomerization-induced stress release in the intermediate layer to some extent. Consequently, the as-formed wrinkling patterns can be modulated over a large area by light irradiation. Interestingly, in the case of selective exposure, the wrinkle wavelength in the exposed region decreases, while the wrinkles in the unexposed region are evolved into highly oriented wrinkles with the orientation perpendicular to the exposed/unexposed boundary. Compared with traditional single layer-based film/substrate systems, the multilayer system consisting of the photosensitive intermediate layer offers unprecedented advantages in the patterning controllability/universality. As demonstrated here, this simple and versatile strategy can be conveniently extended to functional multilayer systems for the creation of prescribed hierarchical surface patterns with optically tailored microstructures.

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.

Tuning and Erasing Surface Wrinkles by Reversible Visible-Light-Induced Photoisomerization.

Periodic wrinkling across different scales has received considerable attention because it not only represents structure failure but also finds wide applications. How to prevent wrinkling or create desired wrinkling patterns is non-trivial because the dynamic evolution of wrinkles is a highly nonlinear problem. Herein, we report a simple yet powerful method to dynamically tune and/or erase wrinkling patterns with visible light. The light-induced photoisomerization of azobenzene units in azopolymer films leads to stress release and consequently to the erasure of the wrinkles. The wrinkles in unexposed regions are also affected and oriented perpendicular to the exposed boundary during the stress reorganization. Theoretical models were developed to understand the dynamics of the reversible photoisomerization-induced wrinkle evolution. This method can be applied for designing functional materials/devices, for example, for the reversible optical writing/erasure of information as demonstrated here.