Well-Tailored Norbornene-Based Fluorinated Copolymers toward Modulating Icephobicity and Mechanical Robustness.

Well-tailored construction of icephobic surfaces with mechanical robustness and investigation of the structure-property relationships at the molecular level are highly desirable. Herein, a series of norbornene-based fluorinated polyolefin copolymers (FPOR-x) with varying norbornenyl dodecafluoroheptyl ester (NDFHE) molar fractions (0-100 mol %) were well-designed and fabricated via living ring-opening metathesis polymerization (ROMP) employing NDFHE and norbornenyl pentafluorophenyl ester (NPFPE) as the soft and hard segments, respectively. The mechanical and icephobic properties of the fluorinated copolymers can be regulated by adjusting the soft NDFHE contents. As a result, the well-designed norbornene-based copolymers exhibited a wide range of tunable mechanical properties, including tensile strength ranging from 0.2 to 26.4 MPa, elastic modulus ranging from 0.6 to 593.7 MPa, and breaking elongations ranging from 5718.7% to 3.7%, correlating with the proportion of soft NDFHE content. Furthermore, the synergistic interplay between soft and hard segments, particularly the hardness in the majority and softness in the minority or vice versa, could achieve a significant difference in the local modulus and enhance the propagations of cracks within the three-phase regions (soft regions/hard regions/ice), ultimately leading to a significant reduction in ice shear strength. Notably, FPOR-25% with a tensile strength of 12.0 MPa and an elastic modulus of 227.5 MPa exhibited a remarkably low ice shear strength of 57.7 kPa. This study not only highlights the relationship between the polymer molecular structure and surface icephobic properties but also breaks the limitations of icephobic surfaces with a low modulus.

Flexible Azo-Polyimide-Based Smart Surface with Photoregulatable Surface Micropatterns: Toward Rewritable Information Storage and Wrinkle-Free Device Fabrication.

Stimulus-sensitive materials are of great fascination in surface and interface science owing to their dynamically tunable surface properties and/or morphologies. Herein, we have synthesized an azobenzene-containing polyimide (azo-PI) with enhanced chain flexibility for the fabrication of photosensitive surface patterns on a film/substrate wrinkle system or wrinkle-free devices. The phototriggered cis-trans isomerization kinetics of azobenzene groups in the novel azo-PI with various chain structures were systematically investigated. On the basis of the characteristics of stress relaxation that azobenzene reversible cis-trans isomerization induces in the wrinkled azo-PI film/substrate system, a variety of rewritable visual surface patterns with high resolution and a long legibility time (>30 days) could be easily constructed via visible-light irradiation, enabling the wrinkled azo-PI surfaces to be used as rewritable information storage media. Meanwhile, because of the visible-light irradiation strategy, these photoresponsive surfaces could find potential application in the fabrication of wrinkle-free flexible devices. This study not only sheds light on the influence of the azo-polymer chain structure on its photoresponsive behavior but also provides a versatile strategy for realizing tailor-made smart surface patterns on multilayer functional devices.

Robust Scalable-Manufactured Smart Fabric Surfaces Based on Azobenzene-Containing Maleimide Copolymers for Rewritable Information Storage and Hydrogen Fluoride Visual Sensor.

Functionalized materials with reversible color switching are highly attractive in many application fields, especially as rewritable media for information storage. It is critical yet challenging to develop a cost-effective strategy for the fabrication of stimulus-responsive chromogenic systems. Herein, we present a versatile dip-coating approach to fabricate robust smart textile with acid/base-driven chromotropic capability. Owing to the introduction of novel maleimide-based copolymers bearing azobenzene derivative moieties, smart textiles possess rapid color switching between yellow and orange-red, which is triggered by acid-base stimulations with the resulting reversible protonation/deprotonation of maleimide moieties. As a proof of concept of the application of the smart textile for high-performance rewritable media, various rewritable elaborate patterns can be fast trifluoroacetic acid-printed/triethylamine-erased (within 20 s) with excellent cycling stability and long legible duration (>30 days). Meanwhile, the smart textile can be employed as a visual sensor for the detection of hydrogen fluoride gas leakage. It is highlighted that the as-prepared robust smart textiles with superhydrophobic surfaces have excellent antifouling properties and chemical/mechanical stabilities, which can tolerate harsh environmental conditions and repetitive mechanical deformation. The robust smart textiles with simple low-cost large-scale production may find more advanced potential applications besides information storage and sensors demonstrated.

Preparation and Insights of Smart Foams with Phototunable Foamability Based on Azobenzene-Containing Surfactants.

Smart foams with tunable foamability exhibit superb applications in many fields such as colloidal and interface science. Herein, we have synthesized an azobenzene-containing surfactant with excellent photoresponsiveness by a simple thiol-maleimide click reaction between thioglycolic acid and 4-(N-maleimide) azobenzene (MAB). The structure and the photoresponsive behavior of the novel surfactant are characterized. Depending on the solution concentration, the synthesized surfactant demonstrated various speeds for the trans/cis photoisomerization varying from 9 to 24 s for the given concentration range and excellent reversible photoisomerization cycling stability (more than 20 cycles) upon light irradiation. Based on these conformational switches, a series of phototriggered obvious surface properties (e.g., critical micelle concentration (CMC), surface tension (γ), and surface excess concentration (Γ)) changes of the surfactant are achieved. More specifically, the smart foam system with tunable foamability is realized. As-formed smart foams with rapid photocontrolled reversible foaming/defoaming transition and excellent cycling stability make them very attractive candidates for applications in wastewater treatment, green textile, oil extraction, and emulsification.

Cytocompatible and non-fouling zwitterionic hyaluronic acid-based hydrogels using thiol-ene "click" chemistry for cell encapsulation.

In this work, a facile click reaction strategy is employed to form hydrogels in situ with cytocompatibility, biodegradability, self-healing property and resistance to protein. The thiol-functionalized zwitterionic carboxybetaine methacrylate copolymer, which take part as a cross-linker in the "thiol-ene" click reaction with the methacrylated hyaluronic acid. The hydrogels are obtained under the physiological condition without the presence of any copper catalyst and UV light. The hydrogel consisting of zwitterionic component shows an obvious reduction in protein adsorption and cell adhesion and avoid non-targeted factor interference in the biological experiments. The hydrogels also demonstrate adjustable degradation behavior. Human mesenchymal stem cells (hMSCs) are easily encapsulated into the hydrogels and remains metabolically active, indicating the excellent biocompatibility of the hydrogels. Additionally, the result of the cytokine secretion assays (IL-6 and TNF-α) has shown that this clickable hydrogel can serve to suppress inflammatory reactions and is beneficial for in vivo applications. Based on the above results, this clickable hydrogel with excellent performance can be an amenable platform for 3D cell encapsulation.

Enhanced breakdown strength and suppressed dielectric loss of polymer nanocomposites with BaTiO3 fillers modified by fluoropolymer.

The introduction of ceramic fillers into a polymer matrix is an effective way to obtain dielectric nanocomposites with high energy storage density. However, the inorganic fillers are difficult to disperse evenly into the polymer matrix because of the poor compatibility, which stems from the large surface energy difference and the mismatch in dielectric constant between the fillers and polymer matrix. Polymer nanocomposites with high dielectric constant while maintaining high breakdown strength have great potential to achieve high energy storage density. In this work, poly(dodecafluoroheptyl methacrylate) terminated with a thiol end group (PDFMA-SH) was synthesized via a two-step process including Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization and subsequent aminolysis reaction. The polymer was then grafted into the surface of BaTiO3 (BT) nanoparticles by a "thiol-ene" click reaction to reduce the surface energy of BT nanoparticles. A novel nanocomposite consisted of the core-shell structured PDFMA@BT hybrid nanoparticles and poly(vinylidene fluoride-chlorotrifluoroethylene) (P(VDF-CTFE)) matrix was prepared. The influence of the fluoropolymer shell on the dispersion of fillers, the compatibility between the fillers and polymer matrix, dielectric properties and breakdown strength were investigated systematically. The results indicate that the strong interfacial adhesion between the hybrid nanoparticles and P(VDF-CTFE) matrix makes the fillers uniformly dispersed in the polymer matrix. Meanwhile, the excellent compatibility between the two components is favorable for enhancing the breakdown strength and suppressing dielectric loss, providing a condition to prepare dielectric materials with high energy storage density.

Light-printable epoxy oligomer wrinkle-forming surface for rewritable information storage.

Smart surfaces with controlled topography show broad and fantastic applications in optics, biology and information science. Herein, we report a simple visible-light-illumination approach to fabricate a smart wrinkle-forming surface with photo-controllable hierarchical surface patterns as well as rewritable high-resolution patterns of information by using an azobenzene-containing epoxy-based oligomer. The epoxy oligomer was synthesized via the ring-opening polymerization of bisphenol AF diglycidyl ether (BADFGE) with p-aminoazobenzene (AAB) and characterized using FTIR, 1H NMR and 19F NMR spectroscopies. When the epoxy oligomer film was deposited on an elastic substrate, the formation of surface wrinkles was triggered via a circulation of heating/cooling and photo-tailored due to photo-softening together with the release of stress induced by cycles of photoisomerization of azobenzene in the oligomer. The wrinkles in selectively light-exposed regions could be photo-erased within tens of seconds, yielding a different pattern of information. The high-resolution photo-printed images were shown to be rewritable for multiple cycles and legible for over 3 months in dark ambient conditions. The as-formed epoxy oligomer wrinkle-forming surface was found to be inexpensive and its fabrication was easily amenable to scale up, indicating its great potential as ink-free light printable media for rewritable information storage.

Smart Copolymer-Functionalized Flexible Surfaces with Photoswitchable Wettability: From Superhydrophobicity with "Rose Petal" Effect to Superhydrophilicity.

Realizing smart surfaces with switchable wettability inspired by nature continues to be fascinating as well as challenging. Herein, we present a versatile dip-coating approach to fabricate smart polymer-functionalized flexible surfaces with photoswitchable superwettability. Decorated with novel acrylate copolymers bearing a trifluoromethyl side chain and fluorine-containing azobenzene derivative moieties, the modified cotton fabric possesses a rose petal-like superhydrophobicity with contact angles larger than 150° and high water adhesion. This smart surface exhibits rapid phototriggered wettability transformation between superhydrophobicity and superhydrophilicity via alternate irradiation with ultraviolet and visible light, respectively. Meanwhile, the as-prepared flexible smart surfaces have excellent chemical and physical stabilities, which could tolerate harsh environmental conditions and repetitive mechanical deformation (e.g., stretching, curling, folding, and twisting) as well as multiple washing. More importantly, based on the excellent photocontrollability, various erasable and rewritable patterns with distinct wetting properties upon selective photoirradiation can be obtained. This simple strategy and the developed smart surface may find more advanced potential applications in controllable liquid transport, patterning droplet microarrays, and microfluidic devices.

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.

Photocontrollable Wrinkle Morphology Evolution on Azo-Based Multilayers for Hierarchical Surface Micropatterns Fabrication.

Inspired by nature, comprehensive understanding and ingenious utilization of the self-organized wrinkling behaviors of the sandwiched multilayer bonded on substrates are important for engineering and/or functional laminated devices design. Herein, we report a facile and effective strategy to regulate the wrinkles morphology evolution and the resultant hierarchical surface micropatterns on azobenzene-based laminated multilayers by visible-light irradiation. Revealed by systematic experiments, the photocontrolled dynamic wrinkle evolutions are triggered by the reversible photoisomerization of azobenzene in the top azopolymer film and are strongly dependent on the intermediate photoinert layers (e.g., polystyrene and oxygen plasma-induced SiO x layer) with the wrinkle-reinforcing effect or the stress relaxation acceleration effect. Interestingly, large-area well-defined hierarchical surface wrinkle patterns could be fabricated on the multilayers upon selective exposure. In the unexposed region, the wrinkles evolved into highly oriented patterns, whereas in the exposed region, they were fully erased or evolved into smaller-wavelength wrinkles. This study not only sheds light on the morphological evolution of the wrinkling laminated composites in engineering and nature but also paves a new avenue to conveniently and controllably realize the hierarchical stimulus-responsive surface patterns.

Methyl Methacrylate HIPE Solely Stabilized by Fluorinated Di-block Copolymer for Fabrication of Highly Porous and Interconnected Polymer Monoliths.

Preparation of stable water-in-oil (W/O) high internal phase emulsion (HIPE) containing methyl methacrylate (MMA) monomer as oil phase is a difficult task due to the significant solubility of MMA in water. Here, for the first time a fluorinated di-block copolymer (FDBC) poly (2-dimethylamino)ethylmethacrylate-b-poly (trifluoroethyl methacrylate) (PDMAEMA-b-PTFEMA) is proposed to stabilize HIPEs of MMA without the use of any co-stabilizer or thickening agent. Fluorinated segments in FDBC anchored well at oil/water interface of HIPE, offering high hydrophobicity to the partially hydrophilic MMA monomer and in turn stabilization to MMA-HIPE. By using fluorinated di-block copolymer as stabilizer, highly stable HIPEs can be obtained. In addition, highly interconnected porous monoliths were obtained after free radical polymerization, which are highly desirable materials in various practical applications including tissue engineering scaffolds, separation science, bio-engineering and so on. The as-prepared MMA-HIPEs possess high thermal stability without phase separation. The textural characteristics of as-prepared composites, such as pore size and distribution, can be easily controlled by simply varying the amount of FDBC and/or dispersed phase fraction. Moreover, the influence of di-block concentration on water uptake (WU) capability of the prepared porous monoliths is explored.

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.

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.

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.

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.

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.