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1.
Thin films of bromine‐terminated poly(bisphenol A octane ether) (BA‐C10) were prepared using 1,2‐dichlorobenzene (ODCB) as the solvent. The organization of the chains in these amorphous polymer films was evaluated using time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) depth profiling. For the thin films, the bifunctional polymer chains were folded and anchored to the substrate via their two Br end groups and a polymer brush of chain loops was formed on the substrate. As the film thickness increased, polymer chains in a random coil conformation were found to reside on the top of the polymer brush. Depth profiling revealed that the polymer chains were densely packed at the interface. Moreover, the polymer films showed thermal stability, implying strong interactions between the end groups and the substrate. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

2.
Polydimethylsiloxane (PDMS)‐grafted nanoparticles and PDMS were added, respectively, to inhibit the dewetting of polymer films and the formation of surface patterns in spin coating. Uniform and flat films were successfully achieved with the addition of PDMS‐grafted silica nanoparticles or PDMS. Time‐of‐flight secondary ion mass spectrometry depth profiling indicated that PDMS‐grafted silica nanoparticles and PDMS preferentially segregated to the surface. A high concentration of bromine end groups was observed at the interface. The surface layer of PDMS or PDMS‐grafted silica nanoparticles can decrease the surface tension of the polymer solutions and reduce the evaporation rates of the solvents, providing more time for the bromine end groups to anchor themselves at the silicon substrates. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

3.
The surface morphology of thin molecularly imprinted polymer films has been studied using atomic force microscopy (AFM). The films were produced by spin coating onto glass substrates and examined as a function of host polymer, imprinting template, casting solvent, spin‐coater rotation speed and post‐production treatment. It was observed that the gross features of such films are template controlled. The fine structure is determined by parameters such as solvent, spin speed or subsequent treatment. The relationship between these observations, polymer–template interactions and the mechanism of film formation in spin coating is discussed. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

4.
Microstructured surfaces have great potentials to improve the performances and efficiency of optoelectronic devices. In this work, a simple robust approach based on surface instabilities was presented to fabricate poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) films with ridge‐like/wrinkled composite microstructures. Namely, the hierarchically patterned films were prepared by spin coating the P3HT/tetrahydrofuran (THF) solution on a polydimethylsiloxane (PDMS) substrate to form stable ridge‐like structures, followed by solvent vapor swelling to create surface wrinkles with the orientation guided by the ridge‐like structures. During spin coating of the P3HT/THF solution, the ridge‐like structures were generated by the in‐situ template of the THF swelling‐induced creasing structures on the PDMS substrate. To our knowledge, it is the first report that the creasing structures are used as a recoverable template for patterning films. The crease‐templated ridge‐like structures were well modulated by the THF swelling time, the modulus of the PDMS substrate, the P3HT/THF solution concentration and the selective/blanket exposure of the PDMS substrate to O2 plasma. UV–vis and fluorescence spectrometry measurements indicated that the light absorption and fluorescent emission were improved on the hierarchically patterned P3HT films, which can be utilized to enhance the efficiencies of organic solar cells. Furthermore, this simple versatile method based on the solvent swelling‐induced crease as the in‐situ recoverable template has been extended to pattern other spin‐coated films with different compositions. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 928–939  相似文献   

5.
Poly(p‐phenylenebenzobisthiazole) (PBT) is a heterocyclic, aromatic rigid‐rod polymer with a fully conjugated backbone and excellent dimensional, thermo‐oxidative, and solvent stabilities. A PBT polymer with an intrinsic viscosity of 18.0 dL/g was dissolved in methanesulfonic acid or Lewis acid. The PBT solution was spin‐coated and doctor‐bladed for freestanding films or onto an indium tin oxide (ITO) substrate. The acid was removed via coagulation. Scanning electron microscopy determined that the resultant film thicknesses were about 340 and 60 nm for PBT freestanding films and films on the ITO substrate, respectively. X‐ray scattering demonstrated that the freestanding films were in‐plane isotropic without long‐range order. The freestanding films were excited with a He‐Cd laser at 325 nm for photoluminescence (PL) response. PL spectra showed a distinct intensity maximum at 580 nm, regardless of the film‐forming conditions. After the films cooled to 67 K, the PL maximum shifted to 566 nm with enhanced intensity. Aluminum was evaporated onto the monolayer PBT thin film on the ITO substrate as an electron injector for electroluminescence (EL) response. Diodic electric behavior was observed for all monolayer PBT EL devices for the first time. A threshold voltage as low as 4 V was achieved for the monolayer EL devices. In addition, PBT EL spectra were tunable, with a maximum intensity at 570 nm at a bias voltage of 4.5 V changing to 496 nm at 7.5 V (i.e., a blueshift) with greatly increased intensity. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1760–1767, 2002  相似文献   

6.
Acrylic polymer/silica hybrids were prepared by emulsifier‐free emulsion polymerization and the sol–gel process. Acrylic polymer emulsions containing triethoxysilyl groups were synthesized by emulsifier‐free batch emulsion polymerization. The acrylic polymer/silica hybrid films prepared from the acrylic polymer emulsions and tetraethoxysilane (TEOS) were transparent and solvent‐resistant. Atomic force microscopy studies of the hybrid film surface suggested that the hybrid films did not contain large (e.g., micrometer‐size) silica particles, which could be formed because of the organic–inorganic phase separation. The Si? O? Si bond formed by the cocondensation of TEOS and the triethoxysilyl groups on the acrylic polymer increased the miscibility between the acrylic polymer component and the silica component in the hybrid films, in which the nanometer‐size silica domains (particles) were dispersed homogeneously in the acrylic polymer component. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 273–280, 2006  相似文献   

7.
A Hoffman‐like coordination polymer with appreciable porosity and uncoordinated pyridyl groups, namely, [Fe(2,5‐bpp){Au(CN)2}2] ? x Solv (2,5‐bpp=2,5‐bis(pyrid‐4‐yl)pyridine; Solv=solvent), was synthesised and characterised. A series of fascinating spin‐crossover behaviours with abrupt, stepwise and hysteretic features were obtained by exchange with a range of protic solvents (ethanol, n‐propanol, isopropyl alcohol, sec‐butanol and isobutanol). Guest–host hydrogen‐bonding interactions involving the H‐accepting site of the framework are primarily responsible for the pronounced cooperativity of these spin‐crossover behaviours. Meanwhile, the tunable critical temperatures over a range of about 130 K are presumably attributable to a certain degree of competition between internal pressure and local electronic influences of solvents.  相似文献   

8.
Here we report syntheses, photophysical properties, and morphologies of a series of coil‐rod‐coil ABA triblock copolymers containing highly regioregular poly(3‐hexylthiophene) (P3HT) as the central rod block. A new methodology, based on the coupling reaction between living polymeric anions [polystyrene, polyisoprene, and poly(methyl methacrylate)] and aldehyde terminated P3HT, was successfully developed to synthesize the triblock copolymers with low polydispersities. This coupling reaction was effective for building blocks with a variety of molecular weights; therefore, a good variation in compositions of the triblock copolymers could be feasibly achieved. The non‐P3HT coil segments and the solvents were found to exhibit noticeable effects on morphologies of the spin‐coated thin films. Attachment of the coil segments to P3HT did not change the optical absorption of the P3HT segment as the block copolymers were dissolved in solution regardless the chemical structure and the molecular weight of the coil segment. Interestingly, different UV–vis absorption behaviors were observed for the spin‐coated thin films of the block copolymers, which closely related to their morphologies. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3311–3322, 2010  相似文献   

9.
New random copolymers, poly(N‐vinyl‐2‐pyrrolidone‐co‐mono‐6‐deoxy‐6‐methacrylate ethylamino‐β‐cyclodextrin) (PnvpCD) bearing pendent β‐cyclodextrin (CD) groups were synthesized. PnvpCD formed soluble graft‐like polymer complex with adamantane (AD) end‐capped poly(ε‐caprolactone) (PclAD) in their common solvent N‐methyl‐2‐pyrrolidone driven by the inclusion interactions between the CD and AD groups. The formation of the graft complex has been confirmed by viscometry, dynamic light scattering (DLS), and isothermal titration calorimeter. The graft complex self‐assembled further into noncovalently connected micelles in water, which is a selective solvent for the main chain PnvpCD. Transmission electron microscopy, DLS, and atomic force microscopy have been used to investigate the structure and morphology of the resultant micelles. A unique “multicore” structure of the micelles, in which small PclAD domains scattered within the micelles, was obtained under nonequilibrium conditions in the preparation. However, the micelles prepared in a condition close to equilibrium possess an ordinary core‐shell structure. In both cases, the core and shell are believed to be connected by the AD‐CD inclusion complexation. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4267–4278, 2009  相似文献   

10.
Novel types of dual‐functional surface‐attached polymer brushes were developed by interface‐mediated reversible addition‐fragmentation chain transfer (RAFT) polymerization of 6‐azidohexylmethacrylate using the surface‐immobilized RAFT agent and the free initiator. The interface‐mediated RAFT polymerization produced silicon substrate coated with dual‐functional (azido groups from monomer and carboxylic acid groups from RAFT agent) poly(6‐azidohexylmethacrylate) [poly (AHMA)] with a grafting density as high as 0.59 chains/nm2. Dual‐functional polymer brushes can represent an attractive chemical platform to deliberately introduce other molecular units at specific sites. The azido groups of the poly(AHMA) brushes can be modified with alkyl groups via click reaction, known for their DNA hybridization, while the carboxylic acid end groups can be reacted with amine groups via amide reaction, known for their antifouling properties. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1696–1706  相似文献   

11.
Five polyfluorenes bearing bulky trimethylsilyl (PTMS1 and PTMS2), tris(trimethylsilyl)silyl (PTTMS1), and silsesquioxane groups (PPOSS1 and PPOSS2) were synthesized through palladium‐catalyzed Suzuki coupling reactions. In the solution state, every polymer showed comparable ultraviolet–visible spectra, and they emitted blue light with high quantum efficiency. In the solid state, however, three trimethylsilyl‐functionalized polyfluorenes indicated redshifts of the fluorescence peak. In particular, PTMS1 and PTTMS1, having a hydrogen at the C‐9 position of fluorene, also showed green‐light emissions. After the annealing of the spin‐coated films, the blue‐emissive peak decreased and the green‐emissive peak became stronger in the photoluminescence spectra of three trimethylsilyl‐functionalized polyfluorenes. In contrast, PPOSS2 showed a pure blue‐light emission in the film state and even after the thermal treatment, which could be accomplished by the encapsulation of the polymer chains by the large polyhedral oligomeric silsesquioxane molecule. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2119–2127, 2005  相似文献   

12.
Lamellae (symmetric) forming polystyrene‐b‐poly(4‐vinylpyridine) (PS‐b‐P4VP) block copolymers (BCPs) were used to produce nanostructured thin films by solvent (toluene) casting (spin‐coating) onto silicon substrates. As expected, strong micellization of PS‐P4VP in toluene results in poorly ordered hexagonally structures films. Following deposition the films were solvent annealed in various solvents and mixtures thereof. A range of both morphologies including micelle and microphase separated structures were observed. It was found that nanostructures typical of films of regular thickness (across the substrate) and demonstrating microphase separation occurred only for relatively few solvents and mixtures. The data demonstrate that simple models of solvent annealing based on swelling of the polymer promoting higher polymer chain mobility are not appropriate and more careful rationalization is required to understand these data. Analysis suggests that regular phase separated films can only be achieved when the copolymer Hildebrand solubility parameter is very similar to the value of the solvent. It is suggested that the solvent anneal method used is best considered as a liquid phase technique rather than a vapor phase method. The results show that solvent annealing methods can be a very powerful means to control structure and in some circumstances dominate other factors such as surface chemistry and surface energies. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

13.
Solvent vapor annealing (SVA) is one route to prepare block copolymer (BCP) thin films with long‐range lateral ordering. The lattice defects in the spin‐coated BCP thin film can be effectively and rapidly reduced using SVA. The solvent evaporation after annealing was shown to have a significant impact on the in‐plane ordering of BCP microdomains. However, the effect of solvent evaporation on the out‐of‐plane defects in BCPs has not been considered. Using grazing‐incidence x‐ray scattering, the morphology evolution of lamellae‐forming poly(2‐vinlypyridine)‐b‐polystyrene‐b‐poly(2vinylpyridine) triblock copolymers, having lamellar microdomains oriented normal to substrate surface during SVA, was studied in this work. A micelle to lamellae transformation was observed during solvent uptake. The influence of solvent swelling ratio and solvent removal rate on both the in‐plane and out‐of‐plane defect density was studied. It shows that there is a trade‐off between the in‐plane and out‐of‐plane defect densities during solvent evaporation. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 980–989  相似文献   

14.
The fluorescence properties of polysilane can be strongly influenced by creating new excited states that involve electronic transitions and the relaxation to the ground state. This work presents the optical effects obtained by doping a specially designed polydiphenylsilane copolymer with Zn complex of N,N′‐bis(4‐hydroxysalicylidene)‐1,2‐phenylenediamine. The nanocomposites have been prepared in solution by mixing the polymer with low amounts of Zn–salophen and using tetrahydrofuran as solvent. The ultraviolet–visible spectrum has shown the occurrence of an intermolecular charge transfer between polysilane and the metal complex. Photoluminescence studies have revealed an interesting dual emission profile of nanocomposite. The origin of this phenomenon has been evidenced by molecular modeling and simulation of the electronic transitions. The modeling results have unveiled a new low‐lying excited state due to intermolecular interactions. The thin films of nanocomposites have been drop‐casted from solutions. The obtained films have been studied by Transmission Electron Microscopy (TEM)‐Scanning Transmission Electron Microscopy (STEM)‐Energy Dispersive X‐ray analysis (EDX) to gain information on the film‐forming capacity and surface morphology. The results have revealed a high potential of such materials for fluorescence sensing applications. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

15.
The two terminal pyridyl nitrogen atoms of 2,7‐bis(4‐pyridyl)fluorene ( 1 ) were coordinated to Pd(II) ions to give self‐assembled, multilayer films using the layer‐by‐layer (LbL) method. The films were prepared by alternately dipping the substrate, pre‐coated with a polyethyleneimine layer, in aqueous solutions of PdCl2 and ethanol solutions of 1 . The resulting films were characterized using UV–visible absorption spectroscopy, atomic force microscopy (AFM), X‐ray photoelectron spectroscopy, scanning electron microscopy (SEM) and inductively coupled plasma atomic emission spectroscopy (ICP‐AES). UV–visible spectra and SEM images show almost uniform growth of the film in a near ideal LbL manner. AFM images show that nanostructured aggregates of Pd(II) complexes form on the surface. With an increase in the number of Pd(II)/ 1 bilayers, more particulate aggregates are distributed on the surface. When released from the substrate, the Pd(II) complex nanostructure shows high catalytic activity for Suzuki–Miyaura and Mizoroki–Heck cross‐coupling reactions. The catalyst loading is as low as 9.1 × 10?3 mol% Pd, as measured using ICP‐AES, and high turnover numbers of up to 1.08 × 104 are obtained. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

16.
We report the preparation and characterization of a series of novel electrochromic, aromatic poly(amine amide)s with pendent triphenylamine units. The synthesis proceeded via direct phosphorylation polycondensation between a novel diamine, N,N‐bis(4‐aminophenyl)‐N′,N′‐diphenyl‐1,4‐phenylenediamine, and various aromatic dicarboxylic acids. All the poly(amine amide)s were amorphous and readily soluble in many common organic solvents and could be solution‐cast into transparent, tough, and flexible films with good mechanical properties. They exhibited good thermal stability and 10% weight‐loss temperatures above 540 °C. Their glass‐transition temperatures were 263–290 °C. These polymers in N‐methyl‐2‐pyrrolidinone solutions exhibited strong ultraviolet–visible absorption peaks at 307–358 nm and photoluminescence peaks around 532–590 nm in the green region. The hole‐transporting and electrochromic properties were studied with electrochemical and spectroelectrochemical methods. Cyclic voltammograms of poly(amine amide) films prepared by the casting of polymer solutions onto an indium tin oxide coated glass substrate exhibited two reversible oxidation redox couples at 0.65 and 1.03 V versus Ag/AgCl in an acetonitrile solution. All the poly(amine amide)s showed excellent stability with respect to their electrochromic characteristics; the color of the films changed from pale yellow to green and then blue at 0.85 and 1.25 V, respectively. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2085–2098, 2005  相似文献   

17.
The surface composition in spin‐coated films of polyfluorene:fullerene blends was determined quantitatively by near‐edge X‐ray absorption fine structure (NEXAFS) spectroscopy. By comparing partial and total electron yield spectra, we found vertical compositional differences in the surface region. Furthermore, the orientation of the polymer chains was investigated by variable‐angle NEXAFS. Blend films of poly[(9,9‐dioctylfluorenyl‐2,7‐diyl)‐co‐5,5‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothiadiazole] with [6,6]‐phenyl‐C61‐butyric acid methyl ester in two different blend ratios were studied. Results showed polymer enrichment of the surfaces for films with a polymer:fullerene weight ratio of 20:80 and of 50:50, spin‐coated from both chlorobenzene and chloroform solutions. The angular dependence of the NEXAFS spectra of the pure polymer films showed a preferential plane‐on orientation, which was slightly stronger in the subsurface region than at the surface. In blend films, this orientational preference was less pronounced and the difference between surface and subsurface vanished. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013  相似文献   

18.
Polyesters and polyethers containing norbornadiene (NBD) and 1,2,3‐triazole units in the main chain are prepared by step growth polymerization of diester or diether NBD‐based dialkynes with different aromatic diazides using copper‐catalyzed azide–alkyne cycloaddition. The solubility and the physical properties of the resulting polytriazoles are investigated by differential scanning calorimetry, thermogravimetric analysis, size exclusion chromatography, and 1H NMR spectroscopy, and are discussed taking into account of the chemical structures of the monomers. All of them are amorphous with glass transition temperatures ranging from 51 to 117 °C, number average molecular weight (Mn) values from 16 to 43 kDa and thermal degradation (Td10) values from 175 to 292 °C. The photochemical valence isomerization (PVI) of the NBD units into quadricyclanes (QC) is investigated using UV–vis spectroscopy of polymer films spin‐coated onto quartz substrates. For the first time the PVI of NBD into QC is demonstrated by 1H NMR spectroscopy. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 223–231  相似文献   

19.
Fluorinated poly‐acrylate films coated on continuous Co‐based metal substrate show significant IR absorption enhancement. The degree of enhancement depends greatly on the type of chemical bonds in the polymer molecules and the corresponding vibrations of chemical dipoles. Strong polar groups like C? O, C? F and C?O show the strongest absorption enhancement that also coincides with significant blueshift of the corresponding IR bands. In this paper, the possible mechanism for IR absorption enhancement and band shift are discussed on the basis of the electric field intensification on metal surface, charge transfer and dipole reorientation of the polymer molecules adsorbed on the metal surface. Chemisorption of the polymer molecules on Co‐alloy is established through the interaction between the oxygen atoms in carboxylic group and the substrate cobalt atoms reacting through electron overlap and spin‐coupling of oxygen π‐orbital and cobalt d‐orbital. Copyright © 2006 John Wiley & Sons, Ltd.  相似文献   

20.
A new triphenylamine‐containing aromatic diamine monomer, N,N‐bis(4‐aminophenyl)‐N,N′‐bis(4‐tert‐butylphenyl)‐1,4‐phenylenediamine, was synthesized by an established synthetic procedure from readily available reagents. A novel family of electroactive polyamides with di‐tert‐butyl‐substituted N,N,N,N′‐tetraphenyl‐1,4‐phenylenediamine units were prepared via the phosphorylation polyamidation reactions of the newly synthesized diamine monomer with various aromatic or aliphatic dicarboxylic acids. All the polymers were amorphous with good solubility in many organic solvents, such as N‐methyl‐2‐pyrrolidinone (NMP) and N,N‐dimethylacetamide, and could be solution‐cast into tough and flexible polymer films. The polyamides derived from aromatic dicarboxylic acids had useful levels of thermal stability, with glass‐transition temperatures of 269–296 °C, 10% weight‐loss temperatures in excess of 544 °C, and char yields at 800 °C in nitrogen higher than 62%. The dilute solutions of these polyamides in NMP exhibited strong absorption bands centered at 316–342 nm and photoluminescence maxima around 362–465 nm in the violet‐blue region. The polyamides derived from aliphatic dicarboxylic acids were optically transparent in the visible region and fluoresced with a higher quantum yield compared with those derived from aromatic dicarboxylic acids. The hole‐transporting and electrochromic properties were examined by electrochemical and spectro‐electrochemical methods. Cyclic voltammograms of the polyamide films cast onto an indium‐tin oxide‐coated glass substrate exhibited two reversible oxidation redox couples at 0.57–0.60 V and 0.95–0.98 V versus Ag/AgCl in acetonitrile solution. The polyamide films revealed excellent elcterochemical and electrochromic stability, with a color change from a colorless or pale yellowish neutral form to green and blue oxidized forms at applied potentials ranging from 0.0 to 1.2 V. These anodically coloring polymeric materials showed interesting electrochromic properties, such as high coloration efficiency (CE = 216 cm2/C for the green coloring) and high contrast ratio of optical transmittance change (ΔT%) up to 64% at 424 nm and 59% at 983 nm for the green coloration, and 90% at 778 nm for the blue coloration. The electroactivity of the polymer remains intact even after cycling 500 times between its neutral and fully oxidized states. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2330–2343, 2009  相似文献   

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