An order–order transition (OOT) in the sequence of a hexagonally arranged core–shell cylinder to a double‐hexagonally arranged dot in polystyrene‐block‐poly(butadiene)‐block‐poly(2‐vinylpyridine) (SBV) triblock copolymer thin films is reported to be induced upon exposure to a solvent vapor that is strongly selective for the two end blocks. These two kinds of hexagonally arranged structures could form when the film thickness is 44, 123, and 223 nm. When the film thickness is decreased to 13 nm, the ordered structure is absent. The sizes of the core–shell cylinder structures formed with the same annealing time in films of different thickness are compared to address the effects of film thickness on the phase structure. The mechanism is analyzed from the total surface area of the blocks and the effective interaction parameter in the solvent vapor.
The free volume in thin films of poly(N‐isopropylacrylamid) end‐capped with n‐butyltriocarbonate (nbc‐PNIPAM) is probed with positron annihilation lifetime spectroscopy (PALS). The PALS measurements are performed as function of energy to obtain depth profiles of the free volume of nbc‐PNIPAM films. The range of nbc‐PNIPAM films with thicknesses from 40 to 200 nm is focused. With decreasing film thickness the free volume increases in good agreement with an increase in the maximum swelling capability of the nbc‐PNIPAM films. Thus in thin hydrogel films the sorption and swelling behavior is governed by free volume.
Summary: In this study, a method for producing super‐amphiphobic surfaces through plasma modification of benzoxazine films is presented. Microroughening and fluorination of the benzoxazine films occurs during the plasma treatment process and a rugged surface with a micro/nano binary structure is formed. The combined effect of low surface energy and substrate roughness results in high advancing contact angles (157° for water, 152° for diiodomethane) and low contact angle hysteresis.
SEM image of a cross‐linked polybenzoxazine film treated with Ar plasma (7 min) heated to 200 °C (1 h) and treated with CF4 plasma for 30 s. 相似文献
We recently reported the discovery of soliton‐like electrogenerated chemiluminescence (ECL) waves from pure conjugated polymer films and gold‐nanoparticles‐doped polymer films. In addition to a more detailed study of these polymer systems by changing the film thickness and the distribution of local leaks, we also apply the ECL wave phenomenon to polymer blends of conjugated and nonconjugated polymers. Poly(9,9‐dioctylfluorene‐co‐benzothiadiazole) (F8BT) is used as the active material that is oxidized and produces ECL with the presence of a co‐reactant, tri‐n‐propylamine (TPA). Several factors such as film thickness, artificial leaks, and solubility of doped polymers are examined for their effects on the ECL behavior. When polystyrene (PS), less soluble in the electrolyte, is blended with F8BT, dotted ECL signals are observed and transported as waves. When poly(methyl methacrylate) (PMMA), more soluble in the electrolyte, is blended with F8BT, PMMA serves as local scratches and ECL waves are triggered simultaneously from the whole film.
The effect of the initial states (disordered perpendicular cylinder structure vs. parallel cylinder structure) on the crystallization of polystyrene‐block‐poly(ethylene oxide) (PS‐b‐PEO) thin films during cyclohexane annealing was investigated. The cylindrical domains perpendicular or parallel to the surface were obtained by controlling the film thickness. During solvent annealing, for the film with the perpendicular cylinders, the ordering degree of cylinders was increased. The enthalpic increase is large enough for the forming of square‐shaped crystals, and subsequently the square‐shaped single crystals surrounded by the ordered hexagonally packed perpendicular cylinders evolved to the dendrite ones. For the film with the parallel cylinders, the parallel cylinders were translated to the perpendicular ones. The increased enthalpy was not large enough for the formation of square‐shaped single crystals. Instead, the dendrite‐like crystals started at the edge of terraces.
The application of the mapping method in finite element modeling is extended to quantitatively compare mixing in different twin‐screw extruder layouts. The mapping method provides volumetric quantities, which are crucial for the analysis and optimization of mixing based on the tracking of particles in the velocity field. A new approach to the mapping method is developed to analyze mixing in complex, dynamic open geometries. Several screw configurations and different types of conveying screws are compared, changing the pitch and gap widths. The volume‐weighted intensity of segregation is used as a mixing measure.
This review deals with nanoporous materials made from the self‐assembly of block copolymers with a special interest in the chemical functions covering the surface of their nanopores. A detailed overview of the existing methods and strategies to generate well‐defined organic functional groups covering the surface of the pore walls is provided. This further enables to finely tune the affinity of the pore walls and to perform well‐defined chemical reactions onto them, which is essential for further dedicated applications.
Using two‐photon absorption, an array of spots in a dye‐doped polymer film can be bleached, creating a three‐dimensional structure that can be imaged with two‐photon or confocal microscopy. Microscopic deformations resulting from various treatments to the film can be characterized, for example, swelling or shrinking. This technique is demonstrated on dye‐doped poly(vinyl alcohol), in which the effect of swelling with the addition of water to the film is shown.
A compositional graded film of poly(ε‐caprolactone) (PCL) with 4,4′‐thiodiphenol (TDP), in the film thickness direction, was fabricated by self‐diffusing of TDP in the PCL melt. We found out the self‐bending deformation of the gradient film, which bent into a rolled‐up shape by itself. The initial shape of the film was flat when the sample was quenched from the melt. Upon the fast crystallization of PCL, the gradient film bent to the side with low TDP content. Then, after PCL crystallized the film bent to the opposite direction, that is, to the side with high TDP content. This bending to the TDP rich region was induced by not only the crystallization of PCL but also mass transfer due to the diffusion of TDP from TDP rich region to poor region.
Poly(ethylene glycol) (PEG)‐based films, nanotubes, and nanotube arrays were successfully made using layer‐by‐layer (LbL) assembly ion‐containing PEO derivatives on porous templates and planar substrates. PEG nanotubes are challenging to produce because PEG dissolves into solutions and solvents used during nanotube processing, but our techniques circumvent the issue. Nanotube dimensions were verified using microscopy and the average observed diameter was 155 nm. The PEG‐based structures showed remarkable stability in water, salt water, and sodium hydroxide solution.
Summary: A water‐soluble gold nanoparticle aggregate 2 was prepared by chloroauric acid and a polypseudorotaxane 1 of mono‐6‐thio‐β‐cyclodextrin with poly(propylene glycol) bis(2‐aminopropyl ether) ( ≈ 2 000) in the presence of sodium borohydride in N,N‐dimethylformamide (DMF) solution. The investigative results indicated that the gold nanoparticle aggregate 2 might act as an efficient DNA‐cleavage reagent.
A typical TEM image of gold nanoparticle aggregate 2 . 相似文献
A general approach to fabricate a magnetic field responsive colloidal crystal film has been developed. This is carried out by depositing monodisperse Fe3O4/PS composite magnetic nanospheres on the surface of an agarose‐gel coated substrate. The optical properties of the resultant film can be easily controlled by an external magnetic field, which is caused by assembly of the magnetic nanospheres and alteration of the interparticle distance. With the help of a designed array of small magnets, both the color and pattern of the film can be conveniently modulated and the tuning range covers almost the whole visible spectrum. This work will be important for the potential application of monodisperse magnetic nanospheres in fabricating novel sensors, displays and optoelectronic devices.
Summary: The chain‐length dependence of the Flory‐Huggins (FH) interaction parameter is introduced into the FH lattice theory for polydisperse polymer‐blend systems. The spinodals are calculated for the model polymer blends with different chain lengths and distributions. It is found that all the related variables, rn, rw, rz, and chain‐length distribution, have effects on the spinodals for polydisperse polymer blends.
Effects of hydration on silk fibroin film properties were investigated for water‐annealed and MeOH‐treated samples. Hydration increased thickness by 60% for MeOH‐immersed films, while water‐annealed samples remained constant. MeOH‐immersed films showed an 80% mass loss due to water, while water‐annealed lost only 40%. O2 permeability was higher in MeOH‐immersed films with Dk values of 10?10 (mL O2 · cm) · (cm?1 · s?1 · mmHg?1), while those of water‐annealed films reached only one fifth of this value. All films showed a decrease in Young's modulus and increased plastic deformation by two orders of magnitude when submerged in saline solution. FT‐IR showed that β‐sheet content in water‐annealed films increased with increasing water vapor pressure, while MeOH‐immersed films showed no change.
In this Communication, the effect of varying mass fractions (0–20 wt.‐%) of calcium chloride (CaCl2) salt on the α‐ and β‐phase content of poly(vinylidene fluoride) (PVDF) as‐cast films were investigated. Spectral and X‐ray studies revealed the maximum ferroelectric β‐phase for the addition of 15 wt.‐% of CaCl2 in PVDF compared to neat PVDF samples. The dense β‐phase dominant PVDF–CaCl2 (15 wt.‐%) thick film used as a ferroelectric insulator in one‐capacitor (1C) type random access memory device exhibited a remnant polarization of 3.1 µC · cm2, and is a good indication that the unoriented PVDF–CaCl2 films can be used in electronic applications without further stretching process.
A novel, pyrene‐functionalised copolymer has been synthesised in a single step via imidisation of poly(maleic anhydride‐alt‐1‐octadecene) with 1‐pyrenemethylamine, and its potential for the detection of volatile nitro aromatic compounds (NACs) evaluated. The new copolymer forms complexes in solution with NACs such as 2,5‐dinitrobenzonitrile, as shown by 1H NMR, UV‐vis and fluorescence spectroscopy. Moreover, thin films of this copolymer, cast from THF solution, undergo almost instantaneous fluorescence quenching when exposed to the vapour of 2,5‐dinitrobenzonitrile (a model for TNT) at ambient temperatures and pressures.
To fabricate ferroelectric ultrathin polymer films with large dielectric constants for potential all‐organic electronic devices, ferroelectric polymer nanotubes and a composite of the nanotubes with a dispersed organic semiconductor have been fabricated by template‐assisted methods. The ferroelectricity drops markedly in spin‐coated ultrathin films less than 100 nm thick, whereas P(VDF‐TrFE) nanotubes with a wall thickness of a few ten nm sustain ferroelectricity. The composite nanotubes exhibit a giant dielectric constant as a result of significantly enhanced interface polarization between the nanosized fillers and the polymer matrix. They could be of practical use in supercapacitors, optoelectronic devices, and sensors.
Acrylate–alkyd hybrid latex via miniemulsion polymerizations show promise as water‐borne coating systems. However, poor homogeneity of the particles caused by the immiscibility of the alkyd in polyacrylate limits monomer conversion and film formation. To resolve this problem, the hybrid miniemulsion polymerization of acrylate in the presence of linoleic acid and sunflower seed oil was carried out. Products were characterized by solvent extraction, dynamic light scattering, gel permeation chromatography (GPC), differential scanning calorimeter (DSC), and transmission electron microscopy (TEM). The results provide clear evidence that substituting a fatty acid or natural oil with smaller molecular size (weight) for a conventional alkyd improves the grafting efficiency, and enhances the homogeneity of the hybrid polymer particles in water‐borne latex systems.
In polystyrene‐block‐poly(ethylene oxide) thin films, microphase‐separated brushes on the square platelets can be obtained via fast solvent evaporation by controlling the tethering density (0.08 < σ < 0.11). The tethering density of the brushes is proportional to the thickness of the PEO crystal and increases with increasing initial solution heating temperature (Ti). When Ti < Tm, where Tm is the melting point of PEO, brushes with microphase‐separated structures are observed. The formation of microphase‐separated brushes depends on two factors: the strong incompatibility between PS and noncrystalline PEO chains (attached to the crystalline PEO) and the weak interaction between PS‐PS brushes.
A dielectric elastomer derived from a polystyrene‐block‐poly(ethylene‐co‐butylene)‐block‐polystyrene triblock copolymer swollen with a midblock‐selective solvent is reported to show promise as a nanostructured organic actuator requiring no pre‐strain. This might provide an attractive alternative to conventional acrylic, siloxane, and polyurethane elastomers since the electromechanical properties are composition‐tunable.
