A theory for yield phenomenon of glassy polymers based on the strain non-uniformity under loading conditions

In this work, the yield phenomenon and its related features have been investigated under the concept of strain inhomogeneity, emerged inside the material during deformation processes. This strain non-uniformity in glassy polymers is either a direct consequence of the local microstructural density fluctuations existing in such materials or is the result of the manner by which the free volume is frozen in the glassy state. Assuming a simple strain density distribution function, the rate of plastic deformation can be extracted without any further assumption on a molecular conformational base or any other thermal activated process. The two model parameters required have a physical base related with the magnitude of the free volume and its fluctuation in glassy polymers. Appling this theory on the experimental results for three representative amorphous glassy polymers (PMMA, PS, and PC), all features of yield process, including strain softening effect, are easily described.     

Hydrogel Paint

For a hydrogel coating on a substrate to be stable, covalent bonds polymerize monomer units into polymer chains, crosslink the polymer chains into a polymer network, and interlink the polymer network to the substrate. The three processes—polymerization, crosslinking, and interlinking—usually concur. This concurrency hinders widespread applications of hydrogel coatings. Here a principle is described to create hydrogel paints that decouple polymerization from crosslinking and interlinking. Like a common paint, a hydrogel paint divides the labor between the paint maker and the paint user. The paint maker formulates the hydrogel paint by copolymerizing monomer units and coupling agents into polymer chains, but does not crosslink them. The paint user applies the paint on various materials (elastomer, plastic, glass, ceramic, or metal), and by various operations (brush, cast, dip, spin, or spray). During cure, the coupling agents crosslink the polymer chains into a network and interlink the polymer network to the substrate. As an example, hydrogels with thickness in the range of 2–20 µm are dip coated on medical nitinol wires. The coated wires reduce friction by eightfold, and remain stable over 50 test cycles. Also demonstrated are several proof‐of‐concept applications, including stimuli‐responsive structures and antifouling model boats.     

Polymer Carpets

The fabrication of defined polymer objects of reduced dimensions such as polymer‐coated nanoparticles (zero‐dimensional (0D)), cylindrical brushes (1D), and polymer membranes (2D), is currently the subject of intense research. In particular, ultrathin polymer membranes with high aspect ratios are being discussed as novel materials for miniaturized sensors because they would provide extraordinary sensitivity and dynamic range when sufficient mechanical stability can be combined with flexibility and chemical functionality. Unlike current approaches that rely on crosslinking of polymer layers for stabilization, this report presents the preparation of a new class of polymer material, so‐called “polymer carpets,” a freestanding polymer brush grown by surface‐initiated polymerization on a crosslinked 1‐nm‐thick monolayer. The solid‐supported, as well as freestanding, polymer carpets are found to be mechanically robust and to react instantaneously and reversibly to external stimuli by buckling. The carpet mechanics and the dramatic changes of the film properties (optical, wetting) upon chemical stimuli are investigated in detail as they allow the development of completely new integrated micro‐/nanotechnology devices.     

The Synthesis of Polymer Supports

Conventional polymer supports (polymeric reagents, functional polymers) such as polyacrylamides and polystyrene are based on either strongly polar or nonpolar chemical structures. As a result, these polymers may show low reactivity and poor performance due to their relatively limited ranges of solvent and substrate compatibility. More-recently introduced products are designed on the basis of copolymer structures, which incorporate both polar and nonpolar (hydrophilic and hydrophobic) residues and possess general solvent and substrate compatibility. Due to their ease of production, general solvent and substrate compatibility and improved performance, these new “amphiphilic” copolymers provide new impetus in the study and applications of polymer supports and functional polymers.     

Cover Picture: Combinatorial Material Mechanics: High‐Throughput Polymer Synthesis and Nanomechanical Screening (Adv. Mater. 21/2005)

The automated synthesis and nanomechanical characterization of discrete combinatorial arrays of polymers enables high‐throughput discovery and analysis of compliant, functional materials, as shown by Van Vliet and co‐workers on p. 2599. The cover illustrates a triplicate array of 576 polymers automatically printed on a glass microscope slide, where each spot represents a pairwise, systematically varied composition among 24 different monomers. Overlaid on the image of this triplicate array is a differential interference contrast image of a single nanoliter‐scale polymer volume. In less than twenty‐four hours of synthesis and mechanical characterization, the stiffness of each polymer is determined and related to key monomer structures and volume fractions thereof.     

Molding Micropatterns of Elasticity on PEG‐Based Hydrogels to Control Cell Adhesion and Migration

We present an innovative and simple, soft UV lithographic method “FIll‐Molding In Capillaries” (FIMIC) that combines soft lithography with capillary force driven filling of micro‐channels to create smooth hydrogel substrates with a 2D micro‐pattern on the surface. The lithographic procedure involves the molding of a polymer; in our case a bulk PEG‐based hydrogel, via UV‐curing from a microfabricated silicon master. The grooves of the created regular line pattern are consequently filled with a second hydrogel by capillary action. As a result, a smooth surface is obtained with a well‐defined pattern design of the two different polymers on its surface. The FIMIC method is very versatile; the only prerequisite is that the second material is liquid before curing in order to enable the filling process. In this specific case we present the proof of principle of this method by applying two hydrogels which differ in their crosslinking density and therefore in their elasticity. Preliminary cell culture studies on the fabricated elasticity patterned hydrogels indicate the preferred adhesion of the cells to the stiffer regions of the substrates, which implies that the novel substrates are a very useful platform for systematic cell migration studies, e.g. more fundamental investigation of the concept of “durotaxis”.     

Nanodroplet‐Containing Polymers for Efficient Low‐Power Light Upconversion

Sensitized triplet–triplet‐annihilation‐based photon upconversion (TTA‐UC) permits the conversion of light into radiation of higher energy and involves a sequence of photophysical processes between two dyes. In contrast to other upconversion schemes, TTA‐UC allows the frequency shifting of low‐intensity light, which makes it particularly suitable for solar‐energy harvesting technologies. High upconversion yields can be observed for low viscosity solutions of dyes; but, in solid materials, which are better suited for integration in devices, the process is usually less efficient. Here, it is shown that this problem can be solved by using transparent nanodroplet‐containing polymers that consist of a continuous polymer matrix and a dispersed liquid phase containing the upconverting dyes. These materials can be accessed by a simple one‐step procedure that involves the free‐radical polymerization of a microemulsion of hydrophilic monomers, a lipophilic solvent, the upconverting dyes, and a surfactant. Several glassy and rubbery materials are explored and a range of dyes that enable TTA‐UC in different spectral regions are utilized. The materials display upconversion efficiencies of up to ≈15%, approaching the performance of optimized oxygen‐free reference solutions. The data suggest that the matrix not only serves as mechanically coherent carrier for the upconverting liquid phase, but also provides good protection from atmospheric oxygen.     

Self‐Assembly of Shaped Nanoparticles into Free‐Standing 2D and 3D Superlattices

This article describes a novel supramolecular assembly‐mediated strategy for the organization of Au nanoparticles (NPs) with different shapes (e.g., spheres, rods, and cubes) into large‐area, free‐standing 2D and 3D superlattices. This robust approach involves two major steps: (i) the organization of polymer‐tethered NPs within the assemblies of supramolecular comblike block copolymers (CBCPs), and (ii) the disassembly of the assembled CBCP structures to produce free‐standing NP superlattices. It is demonstrated that the crystal structures and lattice constants of the superlattices can be readily tailored by varying the molecular weight of tethered polymers, the volume fraction of NPs, and the matrix of CBCPs. This template‐free approach may open a new avenue for the assembly of NPs into 2D and 3D structures with a wide range of potential applications.     

Over 14% Efficiency in Polymer Solar Cells Enabled by a Chlorinated Polymer Donor

Fluorine‐contained polymers, which have been widely used in highly efficient polymer solar cells (PSCs), are rather costly due to their complicated synthesis and low yields in the preparation of components. Here, the feasibility of replacing the critical fluorine substituents in high‐performance photovoltaic polymer donors with chlorine is demonstrated, and two polymeric donors, PBDB‐T‐2F and PBDB‐T‐2Cl, are synthesized and compared in parallel. The synthesis of PBDB‐T‐2Cl is much simpler than that of PBDB‐T‐2F. The two polymers have very similar optoelectronic and morphological properties, except the chlorinated polymer possess lower molecular energy levels than the fluorinated one. As a result, the PBDB‐T‐2Cl‐based PSCs exhibit higher open circuit voltage (V_oc) than the PBDB‐T‐2F‐based devices, leading to an outstanding power conversion efficiency of over 14%. This work establishes a more economical design paradigm of replacing fluorine with chlorine for preparing highly efficient polymer donors.     

Homopolymer Nanolithography

Future progress in nanoscience and nanotechnology necessitates further development of versatile, labor‐, and cost‐efficient surface patterning strategies. A new approach to nanopatterning is reported, which utilizes surface segregation of a smooth layer of an end‐grafted homopolymer in a poor solvent. The variation in polymer grafting density yields a range of surface nanostructures, including randomly organized pinned spherical micelles, worm‐like structures, networks, and porous films. The capability to use the polymer patterns for site‐specific deposition of small molecules, polymers, or nanoparticles is shown. This versatile strategy enables patterning of curved surfaces with direct access to the substrate and no need in changing polymer composition to realize different surface patterns.     

Influence of Biodopants on PEDOT Biomaterial Polymers: Using QCM‐D to Characterize Polymer Interactions with Proteins and Living Cells

Organic conducting polymers (OCPs) are currently the subject of intense research in the area of biomaterials and bioelectronics. Of the OCPs, poly(3,4‐ethylenedioxythiophene) (PEDOT) has attracted significant interest, however there has been little work on investigating the incorporation of biological compounds as the dopant species in the polymer which are aimed at enhancing the biocompatibility and biofunctionality of the material. Here, we incorporate the biological dopants dextran sulphate, chondroitin sulphate, and alginate, into PEDOT polymers and investigate their influence on a suite of physicochemical and electrochemical properties. We employ QCM‐D to study the mass of adsorption and the viscoelastic properties of the important extracellular matrix proteins fibronectin and collagen. Furthermore, we use QCM‐D to study the adhesion of PC12 neural cells to the PEDOT‐biodopant polymers with and without an adsorbed protein conditioning layer. QCM‐D was found to be an excellent tool with which to study conducting polymer–biological interactions, with this report the first time that QCM‐D has been used to study cell interactions with conducting polymer biomaterials.     

Inorganic–Organic Hybrid Polymers for Information Technology: from Planar Technology to 3D Nanostructures

Sol‐gel synthesis allows inorganic–organic hybrid polymer materials (ORMOCER®s) to be produced, which can be functionalized to tailor their physical and chemical properties such as refractive index or optical loss. A particular material system is discussed here, which is synthesized without addition of water and is applied in optical communications. As examples for 2D and 2.5D technology, planar waveguides, stacked waveguides, and microlenses are shown. Using two‐photon polymerization initiated by femtosecond laser pulses, arbitrary 3D structures can be made in the submicrometer range. In particular, 3D photonic crystal structures are described and discussed.     

Direct Fabrication of Freestanding and Patterned Nanoporous Junctions in a 3D Micro‐Nanofluidic Device for Ion‐Selective Transport

In the field of micro‐nanofluidics, a freestanding configuration of a nanoporous junction is highly demanded to increase the design flexibility of the microscale device and the interfacial area between the nanoporous junction and microchannels, thereby improving the functionality and performance. This work first reports direct fabrication and incorporation of a freestanding nanoporous junction in a microfluidic device by performing an electrolyte‐assisted electrospinning process to fabricate a freestanding nanofiber membrane and subsequently impregnating the nanofiber membrane with a nanoporous precursor material followed by a solidification process. This process also enables to readily control the geometry of the nanoporous junction depending on its application. By these advantages, vertically stacked 3D micro‐nanofluidic devices with complex configurations are easily achieved. To demonstrate the broad applicability of this process in various research fields, a reverse electrodialysis‐based energy harvester and an ion concentration polarization‐based preconcentrator are produced. The freestanding Nafion‐polyvinylidene fluoride nanofiber membrane (F‐NPNM) energy harvester generates a high power (59.87 nW) owing to the enlarged interfacial area. Besides, 3D multiplexed and multi‐stacked F‐NPNM preconcentrators accumulate multiple preconcentrated plugs that can increase the operating sample volume and the degree of freedom of handling. Hence, the proposed process is expected to contribute to numerous research fields related to micro‐nanofluidics in the future.     

Tough Self‐Healing Elastomers by Molecular Enforced Integration of Covalent and Reversible Networks

Self‐healing polymers crosslinked by solely reversible bonds are intrinsically weaker than common covalently crosslinked networks. Introducing covalent crosslinks into a reversible network would improve mechanical strength. It is challenging, however, to apply this concept to “dry” elastomers, largely because reversible crosslinks such as hydrogen bonds are often polar motifs, whereas covalent crosslinks are nonpolar motifs. These two types of bonds are intrinsically immiscible without cosolvents. Here, we design and fabricate a hybrid polymer network by crosslinking randomly branched polymers carrying motifs that can form both reversible hydrogen bonds and permanent covalent crosslinks. The randomly branched polymer links such two types of bonds and forces them to mix on the molecular level without cosolvents. This enables a hybrid “dry” elastomer that is very tough with fracture energy 13500 Jm^?2 comparable to that of natural rubber. Moreover, the elastomer can self‐heal at room temperature with a recovered tensile strength 4 MPa, which is 30% of its original value, yet comparable to the pristine strength of existing self‐healing polymers. The concept of forcing covalent and reversible bonds to mix at molecular scale to create a homogenous network is quite general and should enable development of tough, self‐healing polymers of practical usage.     

Nanostructured Organic–Inorganic Composite Materials by Twin Polymerization of Hybrid Monomers

Forming two structurally different but associated polymer structures in a single step is a possible route for the production of nanostructured materials. By means of twin polymerization of specially constructed monomers consisting of two different covalently bonded building blocks (hybrid monomers), this route is realized. What is important is that two different macromolecular structures are formed from one monomer in a single process. The two polymers formed can be linear, branched, or cross‐linked structures. The molecular composition of the hybrid monomer defines the degree of cross‐linking of the corresponding macromolecular structures that is theoretically possible.     

Mechano‐Plastic Pyrolysis of Dynamic Covalent Polymer Network toward Hierarchical 3D Ceramics

Shaping ceramics into complex 3D geometries is desirable yet challenging, particularly those with structural hierarchy spanning different length scales. A mechano‐plastic pyrolysis process that overcomes this limitation is reported. In addition to taking advantage of the moldability of organic polymers, the process uniquely incorporates mechano‐plasticity via dynamic covalent bond exchange for reconfiguring the shape of a preceramic polymer. The combined steps result in simultaneous shape control at both micro‐ and macro‐scales. Further pyrolysis leads to complex ceramic structures that are otherwise difficult to produce. To enable this process, rational design of the polymer network is required to satisfy an unusual combination of mechano‐plasticity and pyrolysis. Overall, the process offers an avenue for efficient fabrication of hierarchical 3D ceramic structures suitable for engineering applications.     

Delocalizing strain in a thin metal film on a polymer substrate

Under tension, a freestanding thin metal film usually ruptures at a smaller strain than its bulk counterpart. Often this apparent brittleness does not result from cleavage, but from strain localization, such as necking. By volume conservation, necking causes local elongation. This elongation is much smaller than the film length, and adds little to the overall strain. The film ruptures when the overall strain just exceeds the necking initiation strain, ε_N, which for a weakly hardening film is not far beyond its elastic limit. Now consider a weakly hardening metal film on a steeply hardening polymer substrate. If the metal film is fully bonded to the polymer substrate, the substrate suppresses large local elongation in the film, so that the metal film may deform uniformly far beyond ε_N. If the metal film debonds from the substrate, however, the film becomes freestanding and ruptures at a smaller strain than the fully bonded film; the polymer substrate remains intact. We study strain delocalization in the metal film on the polymer substrate by analyzing incipient and large-amplitude nonuniform deformation, as well as debond-assisted necking. The theoretical considerations call for further experiments to clarify the rupture behavior of the metal-on-polymer laminates.     

Processes and states during polymer film formation by simultaneous crosslinking and solvent evaporation

Coating film formation with simultaneous crosslinking and solvent evaporation, accompanied by passage of the polymer film through glass transition region, is a complex process by which temporary or permanent anisotropic and gradient network structures can be formed. Evaporation and crosslinking are processes that are interdependent. The changes in structure (growth of branched molecules and network evolution) are a function of reaction kinetics, which gets diffusion controlled when the system passes through the glass transition region. Structural changes are determined by branching, gelation, and network build-up and depend on the architecture of network precursors. Thermodynamic interactions of polymer with solvents affect the solvent activity which determines the vapor pressure of the solvent over the film and thus the evaporation rate. The glass transition temperature increases as a result of both the decreasing solvent content and conversion of functional groups into bonds. By interplay of these two factors more or less solvent can be locked in by vitrification. The roles and intensity of these basic processes and interrelations are discussed. Some older results are reviewed and new experimental evidence is added. The interrelations are illustrated by time dependences of solvent evaporation and conversion of functional groups for solvent-based high-solids polyurethane systems composed of a hydroxyfunctional star oligomer and triisocyanate and by the role of the ratio of evaporation to crosslinking rates. Evidence was obtained of gradient formation in which appearance of a glassy surface layer is an important event in the history of film formation that determines solvent retention and other film characteristics.     

Elektrospray‐Ionisation (ESI)

EElectrospray‐ionization (ESI) – pinhole‐free electrophoretic deposition of ultra thin polymer layers Electrospray ionization (ESI) of polymer solutions is used in mass spectroscopy to analyze the molar mass of macromolecules. The singularized polymer molecules are transferred into the mass spectrometer after separating through a special mechanism under high voltage and normal pressure conditions. This process can be adapted for plane deposition of single polymer molecules. Structure, composition and molar mass distribution of polymers are retained. Layers of polar or ionic polymers can be deposited in a thickness of monolayers up to hundreds of nanometers. It is interesting to mention that the ESI‐process belongs to the electrophoretic techniques. Therefore, deposition of pinhole‐free layers on electrical conductive substrates is not only possible on the nozzle facing side of the substrate but although on the back side. This behavior was used to enwrap closely packed carbon fiber bundles with adhesive polymer layers.     

DNA‐SMART: Biopatterned Polymer Film Microchannels for Selective Immobilization of Proteins and Cells

A novel SMART module, dubbed “DNA‐SMART” (DNA substrate modification and replication by thermoforming) is reported, where polymer films are premodified with single‐stranded DNA capture strands, microthermoformed into 3D structures, and postmodified with complementary DNA‐protein conjugates to realize complex biologically active surfaces within microfluidic devices. As a proof of feasibility, it is demonstrated that microchannels presenting three different proteins on their inner curvilinear surface can be used for selective capture of cells under flow conditions.