A PFS/PLA block copolymer was studied to probe the effect of strong surface interactions on pattern formation in PFS block copolymer thin films. Successful synthesis of PFS‐b‐PLA was demonstrated. Thin films of these polymers show phase separation to form PFS microdomains in a PLA matrix, and ultrathin films (<5 nm) formed SINPATs on silicon and mica. The SINPATs consisted of strongly surface‐adsorbed PLA blocks on top of which the PFS blocks dewetted into sphere‐like features. The lateral spacing between these features was regular, and was typically much larger than the length scale associated with regular block copolymer phase separation.
Summary: The impact of a droplet on a solid surface, pre‐patterned with a barrier, was studied using a diffuse interface model. The effect of the wettability of the barrier material and the width of the barrier on droplet spreading was investigated. The results show that depending on the barrier wettability and width, the flow of the spreading droplet can be controlled and that the droplet may or may not overflow the barrier.
Droplet shapes with the corresponding velocity field for different barrier contact angles at ± = 1.5. 相似文献
This paper aims to report the fabrication of biodegradable thin films with micro‐domains of cylindrical nanochannels through the solvent‐induced microphase separation of poly(L ‐lactide)‐block‐poly(ethylene glycol)‐block‐poly(L ‐lactide) (PLA‐b‐PEG‐b‐PLA) triblock copolymers with different block ratios. In our experimental scope, an increase in each of the block lengths of the PLA and PEG blocks led to both a variation in the average number density (146 to 32 per 100 µm2) and the size of the micro‐domains (140 to 427 nm). Analyses by atomic force microscopy (AFM) and fluorescence microscopy indicated that the hydrophilic PEG nanochannels were dispersed in the PLA matrix of the PLA‐b‐PEG‐b‐PLA films. We demonstrated that the micro‐domain morphology could be controlled not only by the block length of PEG, but also by the solvent evaporation conditions.
Ring‐opening metathesis polymerization (ROMP) was used for the synthesis of monolithic capillary columns with inner diameters of 200 µm. The resulting polymeric monoliths were characterized by inverse size‐exclusion chromatography (ISEC). Surface functionalization was carried out in situ using 2‐(N,N‐dimethylaminoethyl)norborn‐5‐ene‐2‐ylcarboxylic amide ( 1 ). The resulting functionalized monoliths were successfully used in anion‐exchange chromatography of oligodeoxynucleotides.
Via a batch process in an autoclave, the foam processing of neat polylactide (PLA) and two different types of PLA/layered silicate nanocomposites has been conducted using supercritical carbon dioxide as a foaming agent. The morphological correlation between the dispersed silicate particles with nanometer dimensions in the bulk and the obtained closed‐cell structure of the foam is discussed. This is the first report that deals with the possibility of preparing biodegradable nanocellular polymeric foams via nanocomposite technology.
SEM image of the freeze‐fracture surface of a PLA/layered silicate foam, exhibiting closed‐cell structure. 相似文献
Stimuli‐sensitive polymer materials have limited device functionality, design and manufacturing flexibility although they are pushed to enable smart device applications. Here we demonstrate the capability of integrating thermoresponsive poly(N‐isopropylacrylamide) (PNIPAAm) hydrogels with silicon nanoribbons, and enable the stiff silicon ribbons to become adaptive and drivable by the soft environmentally sensitive substrate, such as becoming mechanically stretched and compressed on temperature change. These and related soft/hard smart devices and systems may open new opportunities in biomedical applications.
A novel semi‐interpenetrating polymer network based on alginate and poly(N‐isopropylacrylamide) (PNiPAAm) has been synthesized that shows response to temperature and magnetic fields. Highly homogeneous porous hydrogels are obtained by copolymerizing N‐isopropylacrylamide and bis‐acrylamide in the presence of an aqueous alginate solution. The synthesis of magnetic iron oxides by in‐situ oxidation of iron cations coordinated to the alginate network results in a hydrogel with an enhanced deswelling rate with respect to pure PNiPAAm.
A novel amphiphilic diblock copolymer composed of a hydrophilic poly(ethylene oxide) and a hydrophobic polymethacrylate with photochromic azopyridine moieties in the side groups was synthesized by atom transfer radical polymerization. The copolymeric vesicles showed photoinduced circular process including fusion, damage and defect formation, disruption, disintegration and rearrangement in H2O/THF during the irradiation of UV light. The process of photoresponsive cycle can be inhibited at any moment by visible light.
Summary: We have successfully constructed a redox‐responsible hydrogel system by combination of β‐cyclodextrin (β‐CD), dodecyl‐modified poly(acrylic acid) [p(AA/C12)], and a redox‐responsive guest, ferrocenecarboxylic acid (FCA). In the reduced state of FCA, the ternary mixture exhibited a gel‐like behavior, whereas, in its oxidized state, the mixture exhibited a sol behavior.
Conceptual illustration for the redox‐responsive hydrogel system. 相似文献
Shining a light on click chemistry: The use of UV‐radiation as trigger signal provides a facile means to obtain spatial and temporal control over polymer conjugation reactions in addition to providing a further means of achieving orthogonality in click transformations. In the current contribution, UV‐radiation was employed to induce a highly efficient Diels–Alder conjugation of polymeric building blocks via the photo‐induced in situ formation of highly reactive cis‐dienes from a 2‐methylbenzophenone precursor.
A rod‐coil block copolymer consisting of poly(3‐hexylthiophene) (P3HT) and poly(N‐vinylcarbazole) (PVK) ( P3HT‐ b ‐PVK ) in a single molecular architecture is prepared as the first example for WOLEDs. By obtaining the phase separated domains in thin film of the resulting block copolymer, it is possible to suppress energy transfer from PVK as wide bandgap units to P3HT as low bandgap blocks, yielding dual emissions for white electroluminescence with CIE coordination of (0.34, 0.33).
The mechanical behaviour of monodomain nematic side‐chain liquid‐crystalline elastomers containing azoderivatives as pendant groups or crosslinkers has been studied under UV irradiation and in the darkness at different temperatures. From the evaluation of the opto‐mechanical experiments, the mechanical efficiency, kinetic rates, activation energies and the isomerization mechanism of the azocompounds in the liquid‐crystalline matrix could be determined, as well as the effect of the chemical constitution of the azobenzene derivatives and their role in the elastomeric network.
Summary: Low‐bandgap π‐conjugated polymers that consist of alkyl thiophene/alkoxy phenylene and 2,3‐diphenylthieno[3,4‐b]pyrazine units have been prepared in high yields by a Sonogashira polycondensation. The copolymers are characterized by NMR, IR, UV, GPC, and elemental analysis. Thin films of the polymers P1 , P2 , and P3 exhibit an optical bandgap of ≈1.57–1.60 eV. Under simulated AM 1.5 conditions P2/PCBM devices on polyester foil provide a short circuit current of ISC = 10.72 mA · cm−2, an open circuit voltage of Voc = 0.67 V, and a power conversion efficiency of 2.37%.
Schematic of the photovoltaic device made from the polymers synthesized here. 相似文献
A series of π‐conjugated polymers linked by benzocarborane (1,2‐(buta‐1′,3′‐diene‐1′,4′‐diyl)‐1,2‐dicarbadodecaborane) were synthesized via Sonogashira–Hagihara polycondensation reaction. The opened molecular structure of diiodo monomer containing benzocarborane resulted in fast polymerization and high molecular weights. The obtained polymers were fully characterized by 1H, 13C, and 11B NMR spectroscopies. UV‐vis absorption and photoluminescence studies revealed the acceptor‐profile of benzocarborane. Unlike the polymers linked by o‐carborane, these polymers exhibited strong luminescence in the solution state, presumably because the inductive effect of carborane is dominant, rather than cage‐π interactions.
Summary: The synthesis of well‐defined uniform and spherical sub‐micron polymeric spheres, specifically poly[styrene‐co‐(glycidyl methacrylate)] (PSGMA) with a uniform size distribution and surface chemical functionality, is described. It is shown that the surface can be modified with a multi‐amine functional polymer, polyethyleneimine (PEI), most likely through covalent bonding in addition to electrostatic attraction. The PEI acts both as a stabilizing agent and a complexation agent for the deposition of noble metal Ag nanoparticles.
Reaction of PSGMA samples with excess PEI, and its TEM image. 相似文献
A Monte Carlo simulation procedure has been set up and applied to generate representative ensembles of randomly branched step‐growth polymers based on their reaction recipe. The molecular distributions thus obtained are consistent with those from statistical/analytical approaches. However, because the current method gives access to the complete ensemble of simulated molecules, a very detailed structural analysis is possible. Our procedures are applicable to any ‘AfBg’ system with f + g ≥ 1. We apply this approach to randomly branched polyamides in order to gain insight into their molecular structure and understand the effect of the reaction recipe on the final product.
