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1.
Qunwei Tang  Qinghua Li  Jianming Lin 《Polymer》2008,49(24):5329-5335
Exfoliated graphite (G) nanoplatelet was modified with hexadecyltrimethylammonium bromide (C16TAB) and was constructed as multilayer films by electrostatic self-assembly. A [poly(sodium styrenesulfonate)/graphite]n (PSS/G)n multilayer film was self-assembled by alternate adsorption of polyanionic PSS and cationic graphite nanoplatelets G. An uniform deposition process was detected by UV-vis absorption spectra. The (PSS/G)n multilayer film exhibits an excellent electrical conductivity in the range of 50-200 S cm−1, when bilayer number (n) exceeds a threshold value four, the conductivity of the multilayer film increases dramatically. Cyclic voltammogram measurement reveals that the (PSS/G)n film with more bilayer has small charge-transfer resistance and high electrocatalytic activity.  相似文献   

2.
In this article, we report on electrostatically self‐assembled thin films prepared by the alternative immersion of quartz‐coated and indium tin oxide coated glass substrates in aqueous solutions of a copolymer of poly(4‐styrenesulfonic acid‐co‐maleic acid) (PSSMA) and a hemicyanine of (E)?1,1′‐(propane‐1,3‐diyl)bis{4‐[4‐(dimethylamino)styryl]pyridinium} bromide (H3Br2). The films were studied by means of ultraviolet–visible absorption and X‐ray photoelectron spectroscopies, scanning electron microscopy, and photoelectrochemical measurements. When irradiated with white light, the PSSMA/H3 monolayer film gave a stable cathodic photocurrent. The effects of the applied bias voltages, layer numbers of the (PSSMA/H3)n films (where n stands for the number of bilayer films on both sides of the substrates), light intensities, pH value, and electron acceptor on the photocurrent generation of the (PSSMA/H3)n film were examined. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39871.  相似文献   

3.
In this study, we made a new attempt to examine the relationship between the conductivity and the concentration of a polyelectrolyte solution and to prepare multilayer films with cationic lignin and polyanions through layer‐by‐layer self‐assembly. The nitrogen content of trimethyl lignin quaternary amine salt (TLQA) was 3.56%, and the carboxyl content of carboxymethylated poly (vinyl alcohol) (CMPVA) was 0.62 mmol/g. Attenuated total reflectance spectra confirmed that TLQA and CMPVA were fabricated and assembled successfully. The concentration of TLQA had a polynomial correlation with the conductivity [correlation coefficient (R2) = 0.9953], and the concentration of CMPVA was linear with the conductivity (R2 = 0.9819). The electrostatic sequential adsorption process was monitored with a UV–visible spectrophotometer, and the morphology of the (TLQA/CMPVA)n (where n is the number of double membranes) multilayer film was observed by atomic force microscopy and scanning electron microscopy. When the absorbance of the (TLQA/CMPVA)n multilayer film increased linearly, the linear equation was y = 0.0267x + 0.07453 and R2 was 0.9735. When five layers of TLQA and CMPVA were assembled, the surface root mean square roughness of TLQA and CMPVA were 21.07 and 65.28 nm, respectively. When the number of layers increased, the film surface roughness increased. The stability of the multilayer films in aqueous solution was determined by a conductivity meter. The (TLQA/CMPVA)n multilayer film was stable in water. The results of the research demonstrate for the first time that TLQA and CMPVA could be assembled and successfully driven by electrostatic forces. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44416.  相似文献   

4.
The organic–inorganic hybrid multilayered composites are prepared using a unique combination of poly[(o‐cresyl glycidyl ether)‐co‐formaldehyde] (CNER), amino modified montmorillonite (NH2‐MMT), and polyethyleneimine (PEI). This tricomponent composite multilayer PEI(CNER/NH2‐MMT/PEI)n deposited via layer ‐ by ‐ layer technique is based upon synergistic combination of covalent and hydrogen bonding. The growth of multilayer was monitored using UV–vis spectroscopy and ellipsometry. When subjected to optical analyses, the prepared multilayered composite films revealed profound optical transmittance ~83%–87%. The surface morphological analysis by atomic force microscopy and scanning electron microscopy revealed uniform arrangement of organic–inorganic components with relative increase in intensity of elements (C, N, O, Si) as confirmed by X‐ray photoelectron spectroscopy studies. The multilayered composites possess 1.99 GPa hardness making them potential candidate for a number of applications where mechanical strength is desired. Moreover, significant resistance against alkaline and organic solvents at minimal deterioration of circa 0.12% has also been observed for the prepared films. The epoxy clay based thin films being robust, scratch resistant, hydrophilic, chemically inert, and mechanically strong are potential candidates for advanced environmental applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46079.  相似文献   

5.
Polyelectrolyte multilayer films deposited onto various substrates have been used extensively as drug delivery systems. However, little attention has been paid to the release of drugs from free‐standing polymeric films. Herein, we report the construction of thermal crosslinked free‐standing poly(acrylic acid) (PAA)/branched poly(ethyleneimine) (PEI) multilayer films composed of 25 double layers [(PAA/PEI)25] and their use in sorption/release of diclofenac sodium (DS). The (PAA/PEI)25 multilayer films were characterized by scanning electron microscopy, potentiometric titrations and Fourier transform infrared spectroscopy, while the sorption/release of DS was monitored by UV – Vis spectroscopy. The DS sorption equilibrium data were fitted with five isotherm models (Langmuir, Freundlich, Sips, Dubinin–Radushkevich, and Temkin). The maximum equilibrium sorption capacity, qm, given by the Langmuir model was 32.42 mg DS/g. The Korsmeyer–Peppas semiempirical equation showed that the release of DS from the free‐standing (PAA/PEI)25 films proceeded by pseudo‐Fickian diffusion, irrespective of the releasing media. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43752.  相似文献   

6.
The layer‐by‐layer assembly technique is a method that widely used in the preparation of nanostructured multilayer ultrathin films. We fabricated a hydrogel nanocomposite film by alternating the deposition of a core–shell poly[(dimethylimino)(2‐hydroxy‐1,3‐propanedily) chloride] (PDMIHPC)–laponite solution and poly(acrylic acid). The growth of the deposition procedure was proven by ultraviolet–visible spectroscopy and spectroscopic ellipsometry. The surface morphology of the films was observed by scanning electron microscopy. The films could reversibly load and release methylene blue (MB) dye, which was used as an indicator. It took about 4.5 h to reach loading equilibrium at pH 9.0. The loading capacity of the film for MB was as large as 4.48 μg/cm2 per bilayer because of the introduction of the core–shell PDMIHPC–laponite as a film component. Nearly 90% of MB was released at pH 3.0 or in a 300 mM NaCl solution within 2.5 h. The loading and release processes were greatly influenced by the ionic strength and pH value of the MB solution. The hydrogel nanocomposite film showed good pH‐triggered loading‐release reversibility and suggested potential applications in controlled drug‐delivery systems and smart materials. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39352.  相似文献   

7.
The composite double‐layered films, for the packaging application of postharvest fruits and vegetables, were prepared by laminating low‐density polyethylene (LDPE) and poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] (SEBS) modified with zeolite ZSM‐5. The film was characterized by scanning electron microscope and differential scanning calorimeter and tested for permeation of ethylene (C2H4), oxygen (O2), carbon dioxide (CO2), and water vapor. It was found that the C2H4 permeability of the films was improved because of an enhanced adsorption of C2H4 by the incorporated zeolite (0–10 wt%). The preconcentrated layer (zeolite/SEBS) leads to a higher C2H4 concentration gradient across the film. Moreover, the high dispersion of zeolite increased the C2H4 permeation. When compared with O2 and CO2, the composite films were more selective to C2H4. However, the C2H4 permeation decreased in the presence of O2 because of a competitive adsorption. In addition, the films possessed appreciate tensile properties for packaging application. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers  相似文献   

8.
This study reports the modification of commercial cation‐exchange membrane by layer‐by‐layer adsorption of polyethyleneimine and poly(acrylic acid) (PAA) to endow them with monovalent ion selectivity. The chemical and morphological changes of the modified membrane surface were examined by ATR‐FTIR and SEM, respectively. The permselectivity for monovalent cations of the membranes was investigated by electrodialysis experiments. The effects of deposited bilayer number, the salt concentration, and pH of the dipping polyelectrolyte solutions on selectivity were investigated. Meanwhile, the resistance of membranes was measured taking energy consumption into consideration. The polyelectrolyte multilayer was crosslinked using epichlorohydrin to improve stability, and the durability of the composite membrane was studied. Separation mechanism of the composite membrane was also investigated. It is demonstrated that the bivalent cations are mainly rejected by electrostatic repulsion from the positive charge on the surface of the composite membranes. The sieving effect of the dense structure of skin layer becomes more pronounced with the number of deposited layers increased. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41488.  相似文献   

9.
We demonstrate here the layer‐by‐layer (LbL) self‐assembly of conducting [poly(styrene sulfonate)‐poly(vinyl alcohol)/polypyrrole]n [(PSS‐PVA/PPy)n] multilayer film with interesting electrical and photoelectric features. Increments in sheet conductivity and photoelectric response with increasing bilayer number are pioneerly recorded. The fantastic phenomenon is determined as the accumulative electrons tunneled across insulating PSS from bottom to top PPy chains. The resulting multilayer films give a linear growth in bulk conductivity and maximum photocurrent density. Careful examination of data and characterizations indicates that the fantastic effects in electrical conduction and photocurrent are accumulative electrons tunneled across PSS from bottom to top PPy. POLYM. ENG. SCI., 55:107–112, 2015. © 2014 Society of Plastics Engineers  相似文献   

10.
To investigate the effect of reactive end‐capping groups on film‐forming quality and processability, a series of molecular weight‐controlled aromatic poly(amic acid) (PAA) resins functionalized with phenylethynyl end groups were prepared via the polycondensation of 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), para ‐phenylenediamine (PDA), and 4‐phenylethynyl phthalic anhydride (PEPA) served as molecular‐weight‐controlling and reactive end capping agent. The PAA resins with relatively high concentrations endow enhanced wetting/spreading ability to form PAA gel films by solution‐cast method which were thermally converted to the fully‐cured polyimide (PI) films. The mechanical and thermal properties of PI films were investigated as a function of PAA molecular weights (Mn ) and thermal‐curing parameters. Mechanical property, dimensional stability and heat resistance of the fully‐cured PI films with PAA Mn > 20 ×103 g mol?1 are found to be better than that of their unreactive phthalic end‐capped counterparts. The covalent incorporation of chain‐extension structures in the backbones, induced by thermal curing of phenylethynyl groups, might facilitate yielding a higher degree of polymer chain order and consequently improved resistance strength and elongation at break to tensile plastic deformation. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45168.  相似文献   

11.
Potassium persulfate (K2S2O8) was used to initiate the polymerization of acrylic acid (AA) monomer in a chitosan (CS) solution. Both a poly(acrylic acid) (PAA) homopolymer and a CS‐co‐PAA copolymer were produced. When the amount of AA was increased from 5 to 40 g with 5 g of CS, the total monomer conversion was found to increase from 89 to 98% after 2 h of reaction at 70°C. In addition, the percentage of reacted AA monomer being converted to the CS‐co‐PAA copolymer (copolymerization efficiency) and the weight composition of the PAA portion in the copolymer (copolymer composition) both increased with the amount of AA added. The structures and properties of the synthesized CS‐modified PAA polymers were studied. In Fourier transform infrared spectra, the formation of a polyelectrolyte complex between CS chains and PAA chains could be observed. From the thermograms obtained via differential scanning calorimetry, we found that the presence of rigid CS chains increased the glass‐transition temperature of PAA. Thermogravimetric analysis revealed three stages of degradation of the synthesized CS‐modified PAA polymers. The swelling ratio of the CS‐modified PAA polymers depended on the pH value and had a maximum value in a buffer solution at pH 7. This was due to the changes in the morphological structure with the pH value. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

12.
A capacitively coupled parallel‐plate reactor has been used to deposit plasma‐polymerized pyrrole (PPPy), plasma‐polymerized N,N,3,5‐tetramethylaniline (PPTMA), and plasma‐polymerized pyrrole‐N,N,3,5‐tetramethylaniline (PPPy‐PPTMA) bilayer thin films on to glass substrates at room temperature. To deposit the bilayer films, pyrrole monomer has been used as the mother material and N,N,3,5‐tetramethylaniline monomer has been deposited in different deposition time ratios after the pyrrole films were formed. Fourier transform infrared (FTIR) and ultraviolet–visible (UV–vis) spectroscopy techniques have been used to characterize the as‐grown thin films of about 500‐nm thick. The structural analyses by FTIR spectroscopy have indicated that the monomer has undergone the reorganization and the ring structure is retained during the plasma polymerization. From the UV–vis absorption spectra, allowed direct transition (Eqd) and allowed indirect transition (Eqi) energy gaps were determined. The Eqd for PPPy, PPTMA, and PPPy‐PPTMA bilayer films are found to be 3.30, 2.85, and 3.65 eV respectively. On the other hand, the Eqi for the same series are 2.25, 1.80, and 2.35 eV, respectively. From these results, it is seen that the energy gaps of the PPPy‐PPTMA bilayer films have been increased compared with the PPPy and PPTMA films. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

13.
We report a power conversion efficiency of ~0.01% in multistacking of BiFeO3/BiCrO3 bilayer thin films used as active layers in a photovoltaic (PV) device. The films were epitaxially deposited by pulse laser deposition onto (100) oriented CaRuO3‐coated LaAlO3 substrates and were subsequently illuminated with 1 sun (AM 1.5). The fill factor is determined to be 0.31%, a remarkable value for ferroelectric‐ and multiferroic‐based PV devices. Our results demonstrate that photocurrent density and photovoltage can be tuned by varying the thickness and number of respective bilayers in the improvement of PV properties of multiferroic heterostructures. The maximum photocurrent is generated at an optimal multilayer thickness of 60 nm, with its origin being mainly ascribed to the contribution of ferroelectric polarization.  相似文献   

14.
A series of narrow‐band‐gap conjugated copolymers (PFO‐DPT) derived from pyrrole, benzothiadiazole, and 9,9‐dioctylfluorene (DOF) is prepared by the palladium‐catalyzed Suzuki coupling reaction with the molar feed ratio of 4,7‐bis(N‐methylpyrrol‐2‐yl)‐2,1,3‐benzothiadiazole (DPT) around 1, 5, 15, 30, and 50%. The obtained polymers are readily soluble in common organic solvents. The solutions and the thin solid films of the copolymers absorb light from 300 nm to 600 nm with two absorbance peaks at around 380 nm and 505 nm. The PL emission consists mainly of DPT unit emission at around 624–686 nm depending on the DPT content in solid film. The EL emission peaks are red‐shifted from 630 nm for PFO‐DPT1 to 660 nm for PFO‐DPT50. Bulk heterojunction photovoltaic cells fabricated from composite films of copolymer and [6,6]‐phenyl C61 butyric acid methyl ester (PCBM) as electron donor and electron acceptor, respectively, in device configuration: ITO/PEDOT : PSS/PFO‐DPT : PCBM/Ba/Al shows power conversion efficiencies 0.15% with open‐circuit voltage (Voc) of 0.60 V and short‐circuit current density (Jsc) of 0.73 mA/cm2 under AM1.5 solar simulator (100 mW/cm2). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

15.
Multiple bilayered polysaccharide biofilms have been assembled by electrostatic layer‐by‐layer (LBL), alternating deposition of cationic chitosan (CS, Mv = 405 kDa) and anionic dextran sulfate (DXS, Mw = 500 kDa) onto ultra‐fine cellulose (CELL) and partially hydrolyzed cellulose acetate fibers with diameters ranging from 350 to 410 nm. While the surfaces of partially hydrolyzed (degrees of substitution of 1.14 or 0.2) and CELL fibers were equally hydrophilic, higher surface charges on the more hydrolyzed fibers afford thicker bilayers. The elestrostatic interactions between CS and DXS were enhanced by the presence of NaCl in the dipping and rinsing solutions to allow uniform deposition of sequential polysaccharide bilayers. At 0.25M NaCl, each CS/DXS bilayer averaged 6.4 to 9.0 nm thick with the total thickness of the five bilayer (CS/DXS)5 varied from 64 to 77 nm. The CS/DXS bilayers exhibited much reduced BET surface area and pore volume indicating that these polysaccharides were much more densely packed on the fully hydrolyzed CELL fibers. The findings proofed the concept that long chain polysaccharide electrolytes can be self‐assembled as nanometer scale tubular bilayers on ultra‐fine cellulose fibers to afford wholly polysaccharidic fibrous architecture. The electrolytic nature, chemical reactivity, and structural versatility of these ultra‐high specific surface polysaccharides are advantageous and can be further tuned to serve biological functions and for biomedical applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

16.
Chitosan (CH), ammonium polyphosphate (APP), CH and poly(acrylic acid) (PAA)‐stabilized kaolin (KAO) clay are deposited as quadlayers onto the surface of flexible polyurethane foam (PUF) via layer‐by‐layer assembly in order to improve the fire resistance of the foam. The effectiveness of this nanocoating on flame suppression is compared to control films without KAO and bilayer coatings. PUF coated with only five CH/APP/CH/PAA‐KAO quadlayers (around 184 nm thick) maintains its open porous structure and self‐extinguishes upon exposure to a butane torch flame for 10 s. Cone calorimetry reveals that this coating reduces the peak heat release rate and total smoke release by 66.8% and 59.3%, respectively, compared with uncoated foam. Thermogravimetric analysis under nitrogen indicates the combination of intumescent components and clay promotes char formation and improves the thermal stability of the polyurethane substrate. This multilayer coating has the potential to improve the fire safety for PUF, commonly used in home furnishings, and a variety of other polymeric substrates.  相似文献   

17.
Poly(α‐hydroxy acrylic acid) (PHA) and poly(acrylicacid) (PAA) gels were prepared by irradiating the respective 15 wt% aqueous solutions with γ‐rays. Swelling ratios for PHA gel were measured as a function of pH and divalent cation (Mg2+, Ca2+, Mn2+, Co2+, Ni2+, Cu2+) concentration C2 in the external solution to provide a comparison with the results for PAA gels. It was found that the swelling ratio of PHA gel steeply increases between pH 2 and 4, followed by a gradual swelling in the higher pH region. The corresponding steep swelling of PAA gel was observed at pH 3–6. Cation specificity in the equilibrium swelling ratio at a lower C2 value (1.0 × 10−3 M) was approximately consistent with the binding selectivity in the solution system. Typically, the swelling ratio of PHA gel in the presence of Ca2+ was significantly lower than in the Mg2+ system, while the difference was slight for PAA gel. The response of the swelling ratio to changes in pH and C2 was analysed as a first order relaxation to estimate the time constants. The (de)swelling kinetics measured by both the pH and C2 jump were qualitatively interpreted in terms of main‐chain stiffness and intermolecular hydrogen bonding in the respective polymers. © 2000 Society of Chemical Industry  相似文献   

18.
Atomic force microscopy was used to study the characteristics of polymer films formed via admicellar polymerization (the polymerization of monomers solubilized in adsorbed surfactant aggregates). The investigated system included cetyltrimethylammonium bromide (C16TAB) as a cationic surfactant, styrene, 2,2′‐azobisisobutyrilnitrile as an initiator, and polished silica disk substrates. Our goal was to examine changes in the properties and morphology of the formed polymer films due to changes in the surfactant and monomer feed levels. Normal tapping and phase‐contrast modes in air were used to image the nanoscopic and microscopic morphologies of the polystyrene‐modified silica. The root‐mean‐square roughness of the surface before and after modification was statistically analyzed and compared. The images were captured with loading‐force set‐point ratios of 0.2–0.9, and this allowed us to examine the stability of the polystyrene films. In the first series, for which the feed ratio of C16TAB to styrene was kept constant and the total feed concentration was varied, a uniform layer of a polystyrene film was observed along with some nanometer‐size aggregates at high feed concentrations of both C16TAB and styrene. These droplets eventually agglomerated with the film beneath and formed larger macrodroplets in a ring arrangement. At lower concentrations, droplets and holes were observed that eventually agglomerated to form a bicontinuous thin film. In the second experimental series, the concentration of C16TAB was kept constant, and the feed ratio of C16TAB to styrene was varied. A smooth thin film was observed at high concentrations of styrene. This film could be deformed and/or removed to expose the silica surface beneath. At lower styrene loadings, the polystyrene film became unstable and formed dropletlike aggregates, possibly because of either the uneven adsolubilization of the styrene monomer within the admicelle or the dewetting effect during washing and drying. The structure of the polystyrene film formed on a smooth silica disk was very dependent on the amount of the surfactant fed to the system; this contrasted with the results on precipitated silica. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 36–46, 2003  相似文献   

19.
The influence of CnTAB cationic surfactant chain length (n = 8, 10, and 12) on the reaction rate of zinc powder and 0.1 M HCl hydrochloric acid in aqueous solutions was determined at room temperature. Solutions of single surfactants consisting of dodecyl, decyl, and octyl-trimethyl-ammonium bromide surfactants CnTAB were prepared at room temperature. From the surface tension and conductivity measurements, the critical micelle concentration (CMC) values of the three surfactants were obtained in the presence and absence of the acid. No significant change was observed for CMC values in pure water and in 0.01 M HCl. Adsorption of CnTAB surfactants onto 1% wt./vol zinc (in powder form), using surface tension measurements, was then investigated. The adsorption tendency of CnTAB surfactants onto zinc powder followed the order: C8TAB > C10TAB > C12TAB. The role of surfactants in the reaction rate between zinc powder and 0.1 M M HCl was then investigated using conductivity measurements. A significant difference in the reaction rate was found depending on the surfactant chain length. Reaction times of 3830, 4963, 14,172, and 20,053 s were found for the zinc reaction with (0.1 M HCl), (0.1 M HCl + 40 mM C8TAB), (0.1 M HCl + 40 mM C10TAB), and (0.1 M HCl + 40 mM C12TAB), respectively, suggesting a significant dependency of the reaction rate on the CnTAB chain length. Finally, some corrosion parameters such as the corrosion rate, corrosion inhibition efficiency, and their dependency on CnTAB chain length were presented and discussed.  相似文献   

20.
The aim of this article was to evaluate the effects of β‐cyclodextrin (β‐CD) on doxorubicin (DOX)‐loaded alginate esters (SA‐C16) micelles (DOX/SA‐C16) in aqueous solution. DOX was physically loaded into SA‐C16 micelles by an o/w emulsion method with a substantial encapsulation efficiency (EE) level (36.12%), and DOX/SA‐C16 was distributed in size diameters of approximately 254 nm. SA‐C16 as carriers for the DOX can lead to the formation of associative networks in aqueous solutions between the hydrophobic tails of SA‐C16 and DOX, and the dried morphology of DOX/SA‐C16 aggregate was spherical shape. Addition of β‐CD to the system of DOX/SA‐C16 facilitated decoupling of these associations via inclusion complex formation between β‐CD cavities and the polymer hydrophobic tails that produced the release of DOX immediately, and the EE level was dropped to 0.08%, and at the same time the size distribution of aggregate was increased to about 413 nm, moreover, the aggregate was relatively large and becoming irregular spherical shape. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40702.  相似文献   

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