首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 0 毫秒
1.
Self‐assembled thin films of a lamellar forming polystyrene‐block‐poly(d,l )lactide (PS‐b‐PLA) block copolymer (BCP) contain a “reactive” block that can be readily removed to provide a template for substrate pattern formation. Various methods of PLA removal were studied here with a view to develop the system as an on‐chip etch mask for substrate patterning. Solvo‐microwave annealing was used to induce microphase separation in PS‐b‐PLA BCP with a periodicity of 34 nm (Lo) on silicon and silicon on insulator (SOI) substrates. Wet etches based on alkaline and enzymatic solutions were studied in depth. Fourier transform‐infrared (FT‐IR) analysis showed that basic hydrolysis using sodium hydroxide (NaOH) or ammonium hydroxide (NH4OH) solutions resulted in greater PLA removal in comparison to an enzymatic approach using Proteinase K in a Tris‐HCl buffer solution. However, in the enzymatic approach, the characteristic self‐assembled fingerprint patterns were retained with less damage. Comparison to a dry etch procedure using a reactive ion etch (RIE) technique was made. A detailed study of the etch rate of PS and PLA homopolymer and PS‐b‐PLA shows depending on DC bias, the etch selectivity of PLA and PS can be almost doubled from 1.7 at DC bias 145 V to 3 at DC bias 270 V. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40798. Together with Krebs et al., J. Appl. Polym. Sci. (2014) 131 , 40795, doi: 10.1002/app.40795 , this article is part of a Special Issue on Polymers for Microelectronics. The remaining articles appear in J. Appl. Polym. Sci. (2014) volume 131 , issue 24. This note was added on 1st July 2014.  相似文献   

2.
A novel approach to self‐assembled and shell‐crosslinked (SCL) micelles from the diblock copolymer poly(L ‐lactide)‐block‐poly(L ‐cysteine) to be used as drug and protein delivery carriers is described. Rifampicin was used as a model drug. The drug‐loaded SCL micelles were obtained by self‐assembly of the copolymer in the presence of the drug in aqueous media. Their morphology and size were studied with dynamic light scattering and field emission scanning electron microscopy. The rifampicin loading capacity and encapsulation efficiency were studied with ultraviolet–visible spectrophotometry. The drug‐release rate in vitro depended on the oxidizing and reducing environment. Moreover, a straightforward approach to the conjugation of the copolymer with bovine serum albumin (BSA) was developed, and a gel electrophoresis test demonstrated that this conjugated BSA could be reversibly released from the copolymer substrate under reducing conditions. In conclusion, this L ‐cysteine copolymer can be used in drug delivery and in protein fixation and recovery. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

3.
To mitigate the interface energies of block copolymers with high interaction parameters, a topcoat strategy has been experimentally proposed to produce perpendicular oriented domains on a length scale of sub‐10 nm. However, the origin of perpendicular oriented domains and the effect of topcoats on the self‐assembled nanostructures remain to be uncovered. Herein, we use the dynamic self‐consistent field theory to explore the self‐assembly behaviors of symmetric block copolymer films under homopolymer topcoats. It is clearly demonstrated that the introduction of homopolymer topcoats enables a wide formation range of perpendicular oriented lamellae, originating from the fluctuating diblock copolymer/homopolymer interfaces in the process of in‐plane microphase separation of block copolymer films. Our simulation results also demonstrate that the formation range of perpendicular oriented lamellae can be tuned by changing the wetting properties of homopolymer topcoats and the thickness of block copolymer films, but is weakly dependent upon the chain length of homopolymers. Our theoretical findings have wide implications for understanding the formation of perpendicular oriented domains of block copolymer films, which are important for the rational design of self‐assembled nanostructures with new horizons for block copolymer lithography. © 2020 Society of Chemical Industry  相似文献   

4.
Supported ordered nanoporous carbon membranes (ONCM) were prepared by coating a membrane‐forming solution of resorcinol‐formaldehyde (RF) resin on plate support through solvent evaporation and pyrolysis. The membrane solution was formed by the organic‐organic assembly of RF resin with Pluronic F127 in the presence of triethyl orthoacetate and catalyst hydrochloric acid. The thermal stability of precursor, the microstructure, functional groups, and morphology and porous structure of resultant support and ONCM were investigated by the techniques of thermogravimetry, X‐ray diffraction, Fourier transformed infrared spectroscopy, scanning electron microscopy/transmission electron microscopy and nitrogen adsorption‐desorption, respectively. Results have shown that the as‐obtained ONCM has well‐developed porous regularity with bi‐modal narrow pore size distribution. ONCM is tightly adhered to the adopted phenolic resin‐based carbon support. Gases permeating through the ONCM are dominated by molecular sieving mechanism. The ideal gas separation factor of the supported ONCM can be reached to 46.4, 4.7 and 3.3 for H2/N2, CO2/N2 and O2/N2, respectively. The supported ONCM obtained in this work exhibits most promising application for permanent gas separation. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39925.  相似文献   

5.
Diblock copolymer poly(methyl methacrylate)‐b‐poly(vinyl acetate) (PMMA‐b‐PVAc) was prepared by 1,1‐diphenylethene (DPE) method. First, free‐radical polymerization of methyl methacrylate was carried out with AIBN as initiator in the presence of DPE, giving a DPE containing PMMA precursor with controlled molecular weight. Second, vinyl acetate was polymerized in the presence of the PMMA precursor and AIBN, and PMMA‐b‐PVAc diblock copolymer with controlled molecular weight was obtained. The formation of PMMA‐b‐PVAc was confirmed by 1H NMR spectrum. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) were used to detect the self‐assembly behavior of the diblock polymer in methanol. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

6.
The synthesis and properties of crosslinked diblock copolymers for use as proton‐conducting membranes are presented. A polystyrene‐b‐poly(hydroxyl ethyl methacrylate) diblock copolymer at 56 : 44 wt % was sequentially synthesized via atom transfer radical polymerization. The poly(hydroxyl ethyl methacrylate) (PHEMA) block was thermally crosslinked by sulfosuccinic acid (SA) via the esterification reaction between  OH of PHEMA and  COOH of SA. Proton nuclear magnetic resonance and Fourier transfer infrared spectra revealed the successful synthesis of the diblock copolymer and the crosslinking reaction under the thermal condition of 120°C for 1 h. The ion‐exchange capacity continuously increased from 0.25 to 0.98 mequiv/g with increasing SA concentration because of the increasing number of charged groups in the membrane. However, the water uptake increased up to an SA concentration of 7.6 wt %, above which it decreased monotonically (maximum water uptake ∼ 27.6%). The membrane also exhibited a maximum proton conductivity of 0.045 S/cm at an SA concentration of 15.2 wt %. The maximum behavior of the water uptake and proton conductivity with respect to the SA concentration was considered to be due to a competitive effect between the increase of ionic sites and the crosslinking reaction according to the SA concentration. All the membranes were thermally quite stable at least up to 250°C, presumably because of the block‐copolymer‐based, crosslinked structure of the membranes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008  相似文献   

7.
A series of well‐defined amphiphilic poly[(2‐hydroxyethyl methacrylate)‐block‐(N‐phenylmaleimide)] diblock copolymers containing hydrophilic and hydrophobic blocks of different lengths were synthesized by atom transfer radical polymerization. The properties of the diblock copolymers and their ability to form large compound spherical micelles are described. Their optical, morphological and thermal properties and self‐assembled structure were also investigated. The chemical structure and composition of these copolymers have been characterized by elemental analysis, Fourier transform infrared, 1H NMR, UV–visible and fluorescence spectroscopy, and size exclusion chromatography. Furthermore, the self‐assembly behavior of these copolymers was investigated by transmission electron microscopy and dynamic light scattering, which indicated that the amphiphilic diblock copolymer can self‐assemble into micelles, depending on the length of both blocks in the copolymers. These diblock copolymers gave rise to a variety of microstructures, from spherical micelles, hexagonal cylinders to lamellar phases. © 2013 Society of Chemical Industry  相似文献   

8.
The kinetics of surface structure evolution in ultrathin films of low‐molecular‐weight polystyrene‐block‐polyisoprene (Mw: 7300 g mol?1–7300 g mol?1) diblock copolymer at temperatures below the bulk order‐to‐disorder transition temperature are presented. Films with two different thicknesses were studied as a function of annealing temperature using atomic force microscopy. These film thicknesses enabled the investigation of the competition between microphase separation and dewetting that resulted in two different morphologies: long‐range bicontinuous structures and random holes. Three distinctive stages of structure evolution were observed in bicontinuous structure, with the underlying mechanism compared with spinodal dewetting. Thicker films presented holes on their surfaces upon annealing at elevated temperatures, and kinetics of formation of the holes were discussed. We found that the molecular mobility determined the rates of dewetting, while the microphase separation hardly affected the dewetting process. © 2015 Society of Chemical Industry  相似文献   

9.
Poly(n‐butyl methacrylate)‐block‐polydimethylsiloxane‐block‐poly(n‐butyl methacrylate) (PBMA‐block‐PDMS‐block‐PBMA) ABA triblock copolymers were synthesized successfully via atom‐transfer radical polymerization using PDMS as macroinitiator. The effects of PDMS content and substrate nature on self‐assembly behaviors of PBMA‐block‐PDMS‐block‐PBMAs were systematically studied using atomic force microscopy. Two series of triblock copolymers with different molecular weights and compositions, i.e. PBMA‐block‐PDMSA12‐block‐PBMAs and PBMA‐block‐PDMSA21‐block‐PBMAs, were used, where the latter were of a higher PDMS content than the former. On silicon wafer, it was found that only spherical structures formed after annealing films spin‐coated from chloroform solutions of PBMA‐block‐PDMSA12‐block‐PBMAs. In contrast, films of PBMA‐block‐PDMSA21‐block‐PBMAs formed semi‐continuous structures. On mica wafer, it was found that ordered cylindrical pores formed after annealing films spin‐coated from chloroform solutions of PBMA‐block‐PDMSA12‐block‐PBMAs. In contrast, films of PBMA‐block‐PDMSA21‐block‐PBMAs formed isolated cylinders or worm‐like morphologies. Copyright © 2011 Society of Chemical Industry  相似文献   

10.
Biodegradable amphiphilic copolymers were successfully synthesized by the conjugation of various densities of hydrophobic biocompatible cholesterol (Chol) moieties onto poly(2‐hydroxyethyl aspartamide) and poly(N‐isopropylaminoethyl‐co‐2‐hydroxyethyl aspartamide). These were obtained from polysuccinimde, the thermal polycondensation product of L‐aspartic acid, via a ring‐opening reaction with multifunctional pendant groups, including ethanolamine and N‐isopropylethylenediamine (NIPEDA). Copolymers containing 5–30 mol % Chol showed self‐aggregation behavior in aqueous solution, as evidenced by the dynamic light scattering measurement of their particle size distribution. The average particle size of these copolymers increased linearly with increasing Chol content. Moreover, the presence of secondary amine groups in the poly(2‐hydroxyethyl aspartamide)–NIPEDA system made the conjugation more efficient; however, these also seemed to accelerate the degradation of the copolymers in an aqueous medium. The degradation behavior and pH dependence of the particle size of these copolymers in aqueous solution were also examined. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

11.
Two polyisoprene‐block‐poly(tert‐butyl acrylate) (PI‐b‐PtBA) samples and a poly(tert‐butyl acrylate) (PtBA) homopolymer (hPtBA) were prepared by anionic polymerization and characterized by light scattering, size exclusion chromatography, and NMR. The tert‐butyl groups were removed from one of the diblocks to yield amphiphilic polyisoprene‐block‐poly(acrylic acid) (PI‐b‐PAA). PI‐b‐PAA was then used as the surfactant to disperse dichloromethane containing PI‐b‐PtBA and hPtBA at different weight ratios as oil droplets in water. Solid microspheres containing segregated polyisoprene (PI) and PtBA/hPtBA domains were obtained after dichloromethane evaporation. Permanent microspheres were obtained after PI domain crosslinking with sulfur monochloride. Porous microspheres were produced after the hydrolysis of PtBA and the extraction of the homopoly(acrylic acid) chains. The shape and connectivity of the poly(acrylic acid)‐lined pores were tuned by changes in the PtBA/hPtBA content in the precursor microspheres. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2785–2793, 2003  相似文献   

12.
Superstructures composed of diblock copolymer micelles and inorganic nanoparticles are quite interesting because the specific arrangement of inorganic nanoparticles within the micellar structure can reveal interesting opportunities in many field of science. In this perspective, we report a simple method to produce clustered assembly of Au nanoparticles in the micelles in attempt to induce plasmonic coupling among multiple Au nanoparticles in the assembled structures. Here, we utilized polystyrene‐block‐poly(acrylic acid), PS‐PAA, micelles containing single Au nanoparticle in the core (Au@PS‐PAA micelles) as building materials to initiate next‐level assembling process. In particular, the addition of HCl to the solution of Au@PS‐PAA micelles affected the overall equilibrium condition as well as kinetic process in the micellar solution. As a result, individual Au@PS‐PAA micelles could be merged together to form more large micelles with inclusion of multiple nanoparticles in the core, the process of which was accompanied with plasmonic coupling of Au nanoparticles. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44693.  相似文献   

13.
In this study, two approaches are compared to develop nanostructured membrane electrode assemblies (MEA) using layer‐by‐layer (lbl) technique. The first is based on the direct deposition of polyallylamine hydrochloride (PAH) and sulfonated polyaniline (sPAni) on Nafion support to prepare lbl composite membrane. In the second approach, sPAni is coated on the support in the presence of platinum (Pt) salt, Nafion solution and Vulcan for obtaining catalyst containing membranes (CCMs). SEM and UV–vis analysis show that the multilayers are deposited on both sides of Nafion successfully. Although H2/O2 single cell performances of acid doped lbl composite membrane based MEA are found to be at the range of 126 and 160 mW cm?2 depending on the number of deposited layers, the cell performance of MEA obtained from catalyst containing lbl self‐assembled thin membrane (PAH/sPAni‐H+)10‐Pt is found to be 360 mW cm?2 with a Pt utilization of 720 mW mgPt?1. This performance is 82% higher as compared to original Nafion®117 based MEA (198 mW cm?2). From the cell performance evaluations for different structured MEAs, it is mainly found out that the use of lbl CCMs instead of composite membranes and fabrication of thinner electrolytes result in a higher H2/O2 cell activity due to significant reduction in ohmic resistivity. Also, it is observed that the use of sPAni slightly improves the cell performance due to an increased probability of the triple phase contact and it can lead to superior physicochemical properties such as conductivity and thermal stability. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40314.  相似文献   

14.
Nanocomposites based on organically modified montmorillonites (OMMTs) and sodium montmorillonite (CLO‐Na+) with poly(styrene‐b‐butadiene‐b‐styrene) (SBS) diblock copolymer have been investigated. Solution blending of OMMT suspension in toluene with SBS and subsequent static casting and annealing resulted in transparent films. Final samples were processed by compression molding. The intercalation spacing in the nanocomposites, microphase separation of the SBS, and the degree of dispersion of nanocomposites were investigated by X‐ray diffraction (Wide and small‐angle X‐ray scattering), transmission optical microscopy (TOM), atomic force microscopy (AFM), and transmission electron microscopy (TEM). The increase of basal spacing of OMMT in the nanocomposites suggested the intercalation of SBS. The lamellar structure perfection was extensively affected by both OMMT. AFM images and TOM micrographs only showed well dispersed but not exfoliated nanocomposites. On the other hand, TEM showed inserted tactoids into both blocks depending on the surfactant used (stained samples) and the dispersion of those tactoids (unstained samples). Fourier transform infrared spectroscopy indicated only the presence of the OMMT into the SBS. Deviations of the decomposition pathway of pristine SBS with addition of the OMMT were found by thermogravimetric analysis. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

15.
The poly(2‐methacryloyloxyethyl phosphorylcholine)‐block‐poly(D ,L ‐lactide) (PMPC‐b‐PLA) was specially designed to develop biomimetic giant vesicles (GVs) and giant large compound vesicles via a simple spontaneous assemble in aqueous solution. The weight fraction of the hydrophilic PMPC block (fPC) was proved to play an important role in the size and morphology control of the self‐assembled aggregates. The GVs with controlled micrometer size and biomimetic PMPC corona have great potential as artificial cell models. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

16.
Diblock copolymers with different poly(ε‐caprolactone) (PCL) block lengths were synthesized by ring‐opening polymerization of ε‐caprolactone in the presence of monomethoxy poly(ethylene glycol) (mPEG‐OH, MW 2000) as initiator. The self‐aggregation behaviors and microscopic characteristics of the diblock copolymer self‐aggregates, prepared by the diafiltration method, were investigated by using 1H NMR, dynamic light scattering (DLS), and fluorescence spectroscopy. The PEG–PCL block copolymers formed the self‐aggregate in an aqueous environment by intra‐ and/or intermolecular association between hydrophobic PCL chains. The critical aggregation concentrations of the block copolymer self‐aggregate became lower with increasing hydrophobic PCL block length. On the other hand, reverse trends of mean hydrodynamic diameters were measured by DLS owing to the increasing bulkiness of the hydrophobic chains and hydrophobic interaction between the PCL microdomains. The partition equilibrium constants (Kv) of pyrene, measured by fluorescence spectroscopy, revealed that the inner core hydrophobicity of the nanoparticles increased with increasing PCL chain length. The aggregation number of PCL chain per one hydrophobic microdomain, investigated by the fluorescence quenching method using cetylpyridinium chloride as a quencher, revealed that 4–20 block copolymer chains were needed to form a hydrophobic microdomain, depending on PCL block length. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3520–3527, 2006  相似文献   

17.
Polymer vesicles, so‐called polymersomes, gain more and more attention as potential carriers for medical and biotechnological applications. To put the production of these nanocompartments into action at an industrial scale, an efficient and scalable process has to be established. Moreover, being able to control the resulting particle size distribution (PSD) is vital. In this work, the amphiphilic triblock copolymer poly(2‐methyloxazoline)15–poly(dimethylsiloxane)68–poly(2‐methyloxazoline)15 is formed into polymersomes in miniaturized stirred‐tank reactors. Varying flow conditions have a huge impact on the resulting PSD. Dynamic light scattering measurements show that driving a S‐shaped stirrer at 4000 rpm in unbaffled reactors leads to a monomodal PSD with a low polydispersity index (PDI<0.2). Vesicles with a mean diameter of 200 nm are achieved within less than 1 h in a single production step. The robustness of the established process is shown by producing uniform polymersomes at different temperatures and varying pH and buffer molarities. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43274.  相似文献   

18.
Uniform polymersomes (polymer vesicles) made of poly(2‐methyloxazoline)15b‐poly(dimethylsiloxane)68b‐poly(2‐methyloxazoline)15 (PMOXA15–PDMS68–PMOXA15) can be formed in miniaturized‐stirred tank reactors by the aid of a recently published process. In this study, the occurring self‐assembly mechanism was elucidated by using transmission electron microscopy. Subsequent to the initial formation of small spherical micelles and the following fusion to worm‐like micelles, two simultaneously occurring pathways, describing the transformation of further intermediate structures to the desired vesicles, were found. The resulting particle increase was followed by dynamic light scattering. Thus, the vesicle formation rate was judged by the linear increase of the particle diameter over time. While temperature showed no influence, higher initial polymer concentrations and lower final solvent concentrations accelerated the polymersome formation. Besides, the process was crucially dependent on the agitation speed. While spherical micelles did not transform into polymersomes when no stirring or too slow stirring is applied, the self‐assembly process was accelerated by increasing the agitation speed. Uniform polymeric vesicles can be formed under vigorous stirring in stirred‐tank reactors in short process times. In this study, the underlying mechanisms of vesicle formation were elucidated, showing that the polymer forms small micellar structures before undergoing two separate pathways to form the desired vesicular structures. The formation rate of the polymer vesicles was mainly dependent on the agitation speed but also on the polymer and solvent concentrations, highlighting the need for controlled formation conditions. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46077.  相似文献   

19.
Amphiphilic block comb‐shaped copolymers, poly[poly(ethylene oxide) methyl ether acrylate]‐block‐polystyrene [P(A‐MPEO)‐block‐PSt] with PSt as a handle, were successfully synthesized via a macromonomer technique. The reaction of MPEO with acryloyl chloride yielded a macromonomer, A‐MPEO. The macroinitiator PSt capped with the dithiobenzoate group (PSt‐SC(S)Ph) was prepared by reversible addition–fragmentation transfer (RAFT) polymerization of styrene in the presence of benzyl dithiobenzoate, and used as macroinitiator in the controlled radical block copolymerization of A‐MPEO at room temperature under 60Co irradiation. After the unreacted macromonomer A‐MPEO had been removed by washing with hot saturated saline water, block comb‐shaped copolymers were obtained. Their structure was characterized by 1H NMR spectroscopy and gel permeation chromatography. The phase transition and self‐assembling behaviour were investigated by atomic force microscope and differential scanning calorimetry. Copyright © 2004 Society of Chemical Industry  相似文献   

20.
This review summarizes recent advances in the preparation of hydrogen bonding block copolymer mixtures and the supramolecular structures they form through multiple hydrogen bonding interactions. Hydrogen bonding in block copolymer mixtures that form nanostructures and have unusual electronic, photonic and magnetic properties is a topic of great interest in polymer science. Combining the self‐assembly of block copolymers with supramolecular structures offers unique possibilities to create new materials with tunable and responsive properties. The self‐assembly of structures from diblock copolymer mixtures in the bulk state is readily controlled by varying the weight fraction of the block copolymer mixture and the copolymer composition; in solution, the morphologies are dependent on the copolymer composition, the copolymer concentration, the nature of the common solvent, the amount of the selective solvent and, most importantly, the hydrogen bonding strength. Copyright © 2008 Society of Chemical Industry  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号