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1.
Diffusion coefficient of oxygen penetrating into polystyrene (PS) latex/poly (N‐isopropylacrylamide) (PNIPAM) microgel composite films were measured using Fluorescence technique. Three different (5, 15, and 40 wt%) PS content films were prepared from PS/PNIPAM mixtures. Diffusivity of PS/PNIPAM composite films were studied by diffusion measurements which were performed over the temperature range of 24–70°C. Pyrene was used as the fluorescent probe. The diffusion coefficients (D) of oxygen were determined using the Stern–Volmer fluorescence quenching method combined with Fickian transport and were computed as a function of temperature for each PS content film. The results showed that D values were strongly dependent on both temperature and PS content in the film. Diffusion energies were measured and found to be dependent on the composition of the composite films. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

2.
The electropolymerization of N, N-dimethylaniline (DMA) was carried out in an aqueous CF3COONa solution (pH 1.0) containing DMA in the presence of tris(bathophenanthroline disulfonato)iron(II), Fe(bphen)3 4-. Poly(N, N-dimethylanilinium trifluoroacetate) (PDMA) film was formed on electrode surfaces and, at the same time, Fe(bphen)3 4- ions were stably confined in the formed PDMA film by electrostatic interaction between them and the positively charged quaternary ammonium sites of the PDMA film. The PDMA-Fe(bphen)3 4-/3- film thus prepared displayed well-defined reversible electroactivity and electrochromic properties ascribable to those of the Fe(bphen)3 4-/3- couple confined in the film. The PDMA-Fe(bphen)3 4- film is red, and the PDMA-Fe(bphen)3 3- film is colorless. The response rate of the color change to a potential pulse was found to be correlated with the kinetic parameters characterizing the rate of the overall charge-transfer reaction at the PDMA-Fe(bphen)3 4-/3- film-coated electrode, that is, the apparent diffusion coefficient (D app) for the homogeneous charge-transport process within the film and the standard rate constant (k) of the heterogeneous electron-transfer reaction at the electrode/film interface. For the PDMA-Fe(bphen)3 4-/3- film with larger k° and D app values, the response rate of the color change was larger, Further, k°, D app, and response rate depended on the concentration (C°) of the Fe(bphen)3 4- (or Fe(bphen)3 3-) confined in the PDMA film; and at a given film thickness, the lower C°, the higher were k°, D app, and response rate. At a given C°, the thinner the film thickness, the greater was the response rate.  相似文献   

3.
New films of iron complex with 4,7-bis(2-aminophenyl)-methylaminosulfonylphenyl)-1,10-phenanthroline (APP) and 5-amino-1,10-phenanthroline (AP) are prepared on the electrode surface of In–Sn oxide conducting glass (ITO) by electrochemical oxidation. The thickness (Φ) of the films prepared on the ITO can be controlled by the number of cycles of the potential scan. The resulting film-coated electrodes show well-defined reversible vol-tammograms corresponding to the redox reaction of the Fe(II/III) complexes in 0.1 M NaClO4 acetonitrile (AN), a mixture of butylene carbonate (BC) and propylene carbonate (PC) and poly2-hydroxyethylmethacrylate gel containing BC and PC. The electron transfer processes within the films can be treated apparently as diffusional processes characterized by the rate constants of the apparent diffusion coefficient (Dapp). The value of Dapp increase from 1.0 × 10?9 to 1.6 × 10?8 cm2 sec?1 as the Fe complex concentration (CFe) increases from 0.06 to 1.04 M for the [Fe(AP)3] complex film (Φ=0.80 μm) in 0.2 M NaClO4/AN solution. The Dapp value for the [Fe(APP)3) complex film (CFe = 0.19 M , Φ= 0.78 μm) is 3.5 × 10?9 cm2 sec?1 in 0.2 M NaClO4/AN solution. The Dapp values of the [Fe(AP)3] complex film in the PC + BC mixture and gel containing 1.0 M NaClO4 were smaller than those obtained in AN solution by an order of magnitude. The dependence of the apparent formal potential of the Fe(II/III) redox reaction for the [Fe(AP)3] complex film on the activity of NaClO4 supporting electrolyte in AN shows that Na+ moves preferentially across the polymer/solution interfaces during the redox reaction. The Fe(II/III) redox reaction of the Fe complex films shows reversible electrochromic response between red and colorless.  相似文献   

4.
The composite nanofibers of xSrSiO3/(100 − x)SrFe12O19 (x = 0–13 wt%) with diameters around 110 nm have been prepared by calcination of the electrospun SrSiO3/SrFe12O19/poly (vinyl pyrrolidone) (PVP) composite fibers at 800–900 °C. The composite nanofibers were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy and vibrating sample magnetometer. After calcined at 800° the M-type strontium ferrite is formed and the strontium silicate exists as an amorphous state when the calcination temperature below about 950 °C. The addition of SrSiO3 has an obvious suppression effect on the strontium ferrite grain growth and the ferrite grain size decreases from 66.9 to 33.5 nm corresponding SrSiO3 content from 0 to 9 wt% in the composite. The specific saturation magnetization (Ms) of the xSrSiO3/(100 − x)SrFe12O19 composite nanofibers exhibits a continuous reduction from 58.0 to 45.6 A m2 kg−1 with the increase of SrSiO3 content from 0 to 13 wt%. With addition of SrSiO3 from 0 to 13 wt%, the coercivity of the composite nanofibers obtained at 900 °C initially increases, reaching a maximum value 501.1 kA m−1 at the silicate content 7 wt%, and then shows a reduction tendency with the strontium silicate content increase further up to 13 wt%. This influence on the coercivity by strontium silicate can be attributed mainly to the ferrite grain growth suppression and the non-magnetic phase barrier for the domains misalignment.  相似文献   

5.
The positive liquid crystals, 4′-heptyl-4-biphenylcarbonitrile (7CB), are used to functionalize carbon nanotubes (LC-CNT), which can be aligned in the liquid crystalline polyimide (LC-PI) matrix under an alternating electric field to fabricate the thermally conductive LC-CNT/LC-PI composite films. The efficient establishment of thermal conduction pathways in thermally conductive LC-CNT/LC-PI composite films with a low amount of LC-CNT is achieved through the oriented alignment of LC-CNT within the LC-PI matrix. When the mass fraction of LC-CNT is 15 wt %, the in-plane thermal conductivity coefficient (λ) and the through-plane thermal conductivity coefficient (λ) of the LC-CNT/LC-PI composite films reach 4.02 W/(m ⋅ K) and 0.55 W/(m⋅K), which are 90.5 % and 71.9 % higher than those of the intrinsically thermally conductive LC-PI films respectively, also 28.8 % and 5.8 % higher than those of the CNT/LC-PI composite films respectively. Meanwhile, the thermally conductive LC-CNT/LC-PI composite films also possess excellent mechanical and heat resistance properties. The Young's modulus and the heat resistance index are 2.3 GPa and 297.7 °C, respectively, which are higher than the intrinsically thermally conductive LC-PI films and the thermally conductive CNT/LC-PI composite films under the same amount of CNT.  相似文献   

6.
Composite films of polyaniline (PANI) and molybdenum oxide (MoOx) were afforded through a convenient route of electrocodeposition from aniline and (NH4)6Mo7O24. The composite films showed characteristic redox behaviors of PANI and MoOx, respectively, on the cyclic voltammograms. Chlorate and bromate were catalytically electroreduced with an enlarged current on the composite film at a potential ca. 0.2 V more positive than that on MoOx. The potential window for the composite film to display pseudocapacitive properties in 1.0 mol·dm−3 NaNO3 was −0.6 ∼ 0.6 V vs SCE. The cathodic potential limit shifted at least 0.4 V negatively from that of polyaniline (PANI)-based materials reported so far. The specific capacitance was 363.6 F·g−1 when the composite film was charged–discharged at 1.5 mA·cm−2, about two times of that of the similarly prepared PANI. The composite film was characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Molybdenum existed in a mixed state of +5 and +6 in the composite film based on XRD and XPS investigations. Figure PANI and (MoOx) were electrocodeposited in aqueous solutions from aniline and (NH4)6Mo7O24. The composite film obtained displayed catalytic activities toward the electroreduction of oxoanions. The pseudocapacitance of the composite film is nearly two times of that of PANI with the potential window extended negatively up to −0.6 V vs SCE  相似文献   

7.
A highly stable 75 wt % BiOClxBr1?x‐loaded alumina composite film has been developed for the fabrication of glass‐based photoreactors. A very simple approach has been adopted that does not involve the use of a special instrument and can be applied to all types of substrates irrespective to their size and shape. The structure and morphology of the films were well characterized by XRD, SEM, TEM, N2‐sorption, IR, Raman, and UV/Vis diffuse reflectance spectroscopy. BiOClxBr1?x microspheres (1–3 μm) with closely packed thin nanoplates (width ≈10 nm) were integrated within alumina to develop a hybrid film. The photocatalytic capacity of the films was evaluated for the decomposition of Rhodamine B (RhB) and naphthalene under visible‐light irradiation. The composite films showed a remarkable photocatalytic activity and stability and have been reused for several cycles without any deterioration of their original activity.  相似文献   

8.
Plasma-chemical reduction of SiCl4 in mixtures with H2 and Ar has been studied by optical emission spectroscopy (OES) and laser interferometry techniques. It has been found that the Ar:H2 ratio strongly affects the plasma composition as well as the deposition (r D) and etch (r E) rates of Si: H, Cl films and that the electron impact dissociation is the most important channel for the production of SiClx species, which are the precursors of the film growth. Chemisorption of SiClx and the reactive surface reaction SiClx+H–SiCl(x–1)0+HCl are important steps in the deposition process. The suggested deposition model givesr D [SiClx][H], in agreement with the experimental data. Etching of Si: H, Cl films occurs at high Ar: H2 ratio when Cl atoms in the gas phase become appreciable and increases with increasing Cl concentration. The etch rate is controlled by the Cl atom chemisorption step.  相似文献   

9.
Ferrofluid containing highly conductive polyaniline (PANI) was prepared, in which soluble PANI solutions dopedwith 10-camphorsulfonic acid (CSA) and dodecyl benzenesulfonic acid (DBSA) were used as the basic solution and Fe_3O_4nanoparticles (d = 10 nm) as the magnetic material. Moreover, the freestanding films of the resulting ferrofluid can beobtained by an evaporation method. The electrical and magnetic properties of the ferrofluid or its films can be adjustedthrough changing the content of PANI and Fe_3O_4. High saturated magnetization (≈ 30 emu/g) and high conductivity(≈ 250 S/cm) of the composite films can be achieved when the composite film contains 26.6 wt% of Fe_3O_4. In particular, itwas found that the composite films exhibit a super-paramagnetic behavior (Hc = 0) attributed to the size of Fe_3O_4 particles on the nanometer scale.  相似文献   

10.
The results of the investigation of the chemical constitution and structure of (HfO2) x (Sc2O3)1−x thin films are reported. The films are obtained by chemical vapor deposition (CVD) from hafnium 2,2,6,6-tetramethyl-3,5-heptandionate (Hf(thd)4) and scandium 2,2,6,6-tetramethyl-3,5-heptandionate (Sc(thd)3) coordination compounds. It is demonstrated by powder X-ray diffraction and infrared spectroscopy that depending on the scandium content in the films the structure is changed from monoclinic to cubic. Voltage-capacity dependences of test Al/(HfO2) x (Sc2O3)1−x /Si structures are used to calculate the dielectric constant of the films. For the films with the cubic structure it is found that k = 21, while for the films with the monoclinic structure k = 9.  相似文献   

11.
Nanostructured TiO2 films were synthesized by a modified sol–gel method using Pluronics P-123 (EO20PO70EO20) as templating agent, titanium n-butoxide [Ti(OC4H9)4] as inorganic precursor, and ammonium fluoride (NH4F) as the source of N and F dopant atoms in order to prepare sols of x(NF) TiO2 (x=2, 5, 10, 20 wt%). The thin film preparation was made by spin coating, followed by calcination at 400 °C. The as-prepared TiO2 and xNF-TiO2 films were characterized by XRD, Raman spectroscopy, FTIR, TGA-DTA, SEM, UV–Vis diffuse reflectance spectroscopy and EPR. XRD and Raman spectroscopy show that the crystalline structure of these samples consists exclusively of the anatase phase. The band gap (E g ) values for the doped 10 and 20 NF-TiO2 film systems were found to be significantly smaller than those corresponding to the rest of the other TiO2 films. The photocatalytic properties of these films are investigated by following the degradation of methyl orange in aqueous solution under UV irradiation. The photodecomposition is mainly a direct function of the amount of NF present in the TiO2 matrix. The 20NF-TiO2 sample shows the highest activity of all the samples studied.  相似文献   

12.
The preferential formation of a pyrochlore structure is a knotty problem in the preparation of Pb(Zn1/3Nb2/3)O3 (PZN)-based thin film materials and its presence is significantly detrimental to the dielectric and piezoelectric properties. In this study, 40 mol% of PZN was replaced with Pb(Mg1/3Nb2/3)O3 (PMN) for obtaining a perovskite composition around a morphotropic phase boundary (MPB), (1−x)(0.6PZN-0.4PMN)-xPT ((1−x)PZMN-xPT, PT: PbTiO3) where x = 0.23. The thin films with this composition were prepared with a polyethylene glycol (PEG) modi-fied sol-gel method on LaAlO3 substrates. The microstructural evolution of the films on heat treatment was examined with X-ray diffraction. With the aid of PEG, the formation of the pyrochlore phase was suppressed and the perovskite phase formed directly from the amorphous gel film. The multilayer films with a thickness around 0.25 μm showed a single perovskite phase without any detectable pyrochlore structure. Microscopic images showed uniform grain size of a few tens of nanometers. The role of the polymer dramatically promoting the perovskite phase was investigated with the aid of X-ray photoelectron spectroscopy and thermal analysis. The dielectric constant of the obtained film was 4160 at 1 kHz. The film demonstrated typical ferroelectric hysteresis loops and exhibited excellent piezoelectric performance.  相似文献   

13.
《先进技术聚合物》2018,29(1):61-68
Bio‐based nanocomposites of poly (butylene adipate‐co‐terephthalate) (PBAT)/silver oxide (Ag2O) were prepared by the composite film casting method using chloroform as the solvent. The prepared Ag2O at different ratios (1, 3, 5, 7, and 10 wt%) is incorporated in the PBAT. The PBAT nanocomposite films were subjected to structural, thermal, mechanical, barrier, and antimicrobial properties. The electron micrographs indicated uniform distribution of Ag2O in the PBAT matrix. However, the images indicated agglomeration of Ag2O particles at 10 wt% loading. The thermal stability of the nanocomposite films increased with Ag2O content. The tensile strength and elongation of the composite films were found to be higher than those of PBAT and increased with Ag2O content up to 7 wt%. The PBAT‐based nanocomposite films showed the lower oxygen and water vapor permeability when compared to the PBAT film. Antimicrobial studies were performed against two food pathogenic bacteria, namely, Klebsiella pneumonia and Staphylococcus aureus.  相似文献   

14.
 The structure and the gasochromic properties of sol-gel-derived WO3 films with a monoclinic structure (m-WO3) were studied by focusing attention on the size of the monoclinic grains. The size of the m-WO3 grains is modified by the addition of an organic–inorganic hybrid to the initial peroxopolytungstic acid (W-PTA) sols which are based on chemically bonded poly-(propylene glycol) to triethoxysilane end-capping groups (ICS-PPG). The results obtained with scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show that the heat treatment (500°C) of WO3/ICS-PPG (0.5, 1, 2, 5, and 10 mol%) composite films results in a change of their morphology, and nanodimensional pores are formed between the grains. High-resolution TEM (HRTEM) analysis revealed the presence of an amorphous phase on the outside of the m-WO3 grains, whereas energy-dispersive X-ray spectra (EDXS) showed that this amorphous phase contained W and Si. Impregnation of the WO3/ICS-PPG film with H2PtCl6/i-propanol solution followed by heat treatment at 380°C gave the films their gasochromic properties. Infrared and Raman spectroscopic studies of the WO3/ICS-PPG film confirmed the results of the corresponding HRTEM and EDXS analysis. In situ UV/Vis and in situ IR spectra of the films were measured in hydrogen and in air, and colouring/bleaching changes and the corresponding kinetics were assessed. The IR spectra of gasochromically coloured films showed that the mesoporous WO3/ICS-PPG (1 mol%) film transforms to tetragonal H x WO3 bronze. The IR spectra of the H x WO3 bronze are discussed with the aim to establish the existence of the metal-OH vibrations of gasochromically formed oxyhydroxide tungsten bronze.  相似文献   

15.
Polymer diffusion across interfaces at room temperature (21°C) was analyzed by direct nonradiative energy transfer (DET) in labeled latex films. Two modellatex polymers were examined: poly(butyl methacrylate) [PBMA, Mw = 3.5 × 104, Tg (dry) = 21°C] and a copolymer of 2-ethylhexyl methacrylate with 10 wt % (acetoacetoxy)-ethyl methacrylate [P(EHMA-co-AAEM), Mw = 4.8 × 104, Tg (dry) = −7°C]. Little energy transfer due to polymer diffusion was detected for the P(EHMA-co-AAEM) latex samples in the dispersed state or dried to solids content below ca. 90%, but above 90% solids, diffusion occurs among particles. For PBMA, diffusion occurs only after the film is dried (>97% solids) and aged. In the dry PBMA films, it requires 4–5 days at 21°C to reach a significant extent of mixing (fm = 0.3–0.4). This corresponds to an estimated penetration depth dapp of 30–40 nm and a mean apparent diffusion coefficient (Dapp) of 5 × 10−4 nm2/s. The corresponding Dapp value for the dry P(EHMA-co-AAEM) sample is 5 × 10−2 nm2/s, and it takes about 25–40 min for this polymer to reach fm of 0.3–0.4 with dapp of 20–30 nm. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1129–1139, 1998  相似文献   

16.
Novel zinc oxide thin films with nano-screw superstructure were prepared via a soft solution route without any polymer additives. A ZnO thin film could be produced directly on the substrates. The ZnO thin film with nano-screw superstructure was prepared using visible-light-induced nitrogen-doped titania nano-particles. The ZnO nano-screw/TiO2−x N y composite film showed excellent photocatalytic deNO x ability and quantum efficient.  相似文献   

17.
Sorption and permeation of CO2 in various annealed polyimide (PI) films were investigated. Dual-mode sorption and partial immobilization models were used to analyze the data. Sorption of CO2 in PI film quenched from above the glass transition temperature (Tg) is greater than in film as received. In fact, sorption is decreased over the entire pressure range by cooling the film slowly. These changes in sorption of CO2 can be attributed to a change in the Langmuir sorption capacity C′H by annealing, since the other dual-mode sorption parameters, kD and b, are almost independent of annealing. The value of C′H is increased by quenching, and decreased by slow cooling from above Tg. The two diffusion coefficients DD and DH according to the Henry and Langmuir modes, respectively, for CO2 also depend markedly on annealing. Diffusion coefficients of quenched PI films are increased and those of film cooled slowly are decreased compared with values for PI film as received. The change in DH is larger than that in DD. The permeability coefficient of quenched PI films at 100 cmHg is about 1.7 times that of PI film as received. The film structure formed by quenching can enhance permselectivity.  相似文献   

18.
Development of high performance cathodes with low polarization resistance is critical to the success of solid oxide fuel cell (SOFC) development and commercialization. In this paper, (La0.8Sr0.2)0.9MnO3 (LSM)–Gd0.2Ce0.8O1.9(GDC) composite powder (LSM ~70 wt%, GDC ~30 wt%) was prepared through modification of LSM powder by Gd0.2Ce0.8(NO3) x solution impregnation, followed by calcination. The electrode polarization resistance of the LSM–GDC cathode prepared from the composite powder was ~0.60 Ω cm2 at 750 °C, which is ~13 times lower than that of pure LSM cathode (~8.19 Ω cm2 at 750 °C) on YSZ electrolyte substrates. The electrode polarization resistance of the LSM–GDC composite cathode at 700 °C under 500 mA/cm2 was ~0.42 Ω cm2, which is close to that of pure LSM cathode at 850 °C. Gd0.2Ce0.8(NO3) x solution impregnation modification not only inhibits the growth of LSM grains during sintering but also increases the triple-phase-boundary (TPB) area through introducing ionic conducting phase (Gd,Ce)O2-δ, leading to the significant reduction of electrode polarization resistance of LSM cathode.  相似文献   

19.
We have compared the structure, microstructure, and electrochemical characteristics of xLi2MnO3–(1−x)Li(Mn0.375Ni0.375Co0.25)O2 (0.0 ≤ x ≤ 1.0) thin films with their bulk cathode laminate counterparts of identical compositions. Pure Li(Mn0.375Ni0.375Co0.25)O2 as well as the synthesized composite films partially transform into cubic spinel structure during charge–discharge cycling. In contrast, such layered to spinel phase transformation has only been identified in bulk cathode laminates with x ≥ 0.75. At a current density 0.05 mAcm−2, the discharge capacity of Li(Mn0.375Ni0.375Co0.25)O2 thin film was measured to be ∼60 μAhcm−2. The discharge capacity (∼217 μAhcm−2) was markedly improved in x∼0.5 composite thin film. The capacity retention after 20 charge discharge cycles are improved in composite films; however, their capacity fading could not be eliminated completely.  相似文献   

20.
Composite films of polyethylene (PE) and polypyrrole (PPy) were prepared by polymerization of PPy on an ultradrawn polyethylene film with high modulus and high strength in ferric chloride (FeCl3) aqueous solution. The electrical conductivity of the composite film was found to be related to the polymerization conditions, such as polymerization temperature, polymerization time, the concentration and the oxidation potential of the FeCl3 solution. Scanning electron microscopy, FTIR and 13C NMR spectra were used to elucidate the morphological and structural variations of PPy prepared under different conditions, which lead to the differences in the electrical properties of the resultant composite films. The best electrical conductivity of the composite was about 5.5 S/cm for the film prepared under optimum conditions. The Young's modulus and the tensile strength reached 80 GPa and 3.2 GPa, respectively, which indicated the successful production of a conductive polymer with high strength and high modulus.  相似文献   

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