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The sequential layer by layer self‐assembly of block copolymer (BCP) nanopatterns is an effective approach to construct 3D nanostructures. Here large‐scale highly ordered metal nano­arrays prepared from solvent annealed thin films of polystyrene‐block‐poly(2‐vinylpyridine) (PS‐b‐P2VP) diblock copolymer are used to direct the assembly of the same BCP. The influence of initial loading concentration of metal precursor, the type of metal nanoparticle (gold, platinum, and silver), and the nanoparticle–substrate interaction on the directed assembly behavior of the upper BCP layer have been focused. It is found that the upper BCP film can be completely directed by the gold nanoarray with P2VP domain exclusively located between two adjacent gold nanowires or nanodots, which behaves the same way as on the platinum nanoarray. While the silver nanoarray can be destroyed during the upper BCP self‐assembly with the silver nanoparticles assembled into the P2VP domain. Based on the discussions of the surface energy of nanoparticles and the interplay between nanoparticle–substrate interaction and nanoparticle–polymer interaction, it is concluded that the effect of immobilization of nanoparticles on the substrate, together with entropy effect to minimize the energetically unfavorable chain stretching contributes to the most effective alignment between each layer.

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The formation of bend patterns using block copolymer (BCP) lamellae within trench‐type groove patterned with bend geometry is simulated by using a Monte Carlo simulation and a strong segregation theory. A tolerance of curvatures at the bend corners of the guide pattern for the formation of bent lamellae is proposed. It is found from the simulation and the strong segregation theory that the tolerance for the difference in curvature radii of two bend corners for the well‐patterned lamellar bends is proportional to the inverse of the trench width in the straight region.  相似文献   

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A self‐consistent field theoretic study is performed to study morphological development of lamellae‐forming diblock copolymers on substrates with a well‐defined roughness, modeled as trenches of varying depth and width engraved into the substrates. There are three possible lamellar orientations observed: horizontal lamellae, vertical lamellae that are parallel to the trench direction, and vertical lamellae that are perpendicular to the trench direction. Which of these three morphologies formed depends upon the trench width and surface affinity; however, trench depth has a relatively insignificant effect on the morphological development. Therefore, tuning trench width, but not trench depth, should allow for a reduction of the morphological defect density in directed self‐assembly of lamellar morphology of diblock copolymers.

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In this work, different poly (lactic acid) (PLA)-based nanocomposite electrospun fibers, reinforced with both organic and inorganic nanoparticles, were obtained. As organic fibers, cellulose nanocrystals, CNC, both neat and functionalized by “grafting from” reaction, chitosan and graphene were used; meanwhile, hydroxyapatite and silver nanoparticles were used as inorganic fibers. All of the nanoparticles were added at 1 wt% with respect to the PLA matrix in order to be able to compare their effect. The main aim of this work was to study the morphological, thermal and mechanical properties of the different systems, looking for differences between the effects of the addition of organic or inorganic nanoparticles. No differences were found in either the glass transition temperature or the melting temperature between the different electrospun systems. However, systems reinforced with both neat and functionalized CNC exhibited an enhanced degree of crystallinity of the electrospun fibers, by up to 12.3%. From a mechanical point of view, both organic and inorganic nanoparticles exhibited a decreased elastic modulus and tensile strength in comparison to neat electrospun PLA fibers, improving their elongation at break. Furthermore, all of the organic and inorganic reinforced systems disintegrated under composting conditions after 35 days.  相似文献   

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Over the past 15 years, block copolymer lithography has emerged as its own research field within the broader block copolymer and polymer thin film communities. This distinction is associated with the unique requirements set by the semiconductor device industry, such as low-defect densities, precise feature registration, and complex pattern layouts. To achieve perfection in block copolymer lithography, the surface and substrate interactions must be carefully tuned to control domain ordering in three dimensions. This perspective discusses recent modeling efforts that underline the challenges of predicting interfacial interactions and the resulting block copolymer structures. We emphasize studies that facilitate the design and interpretation of experiments, including materials selection, guiding pattern geometry, and selecting tools for three-dimensional metrology. Finally, we propose that translation of block copolymer lithography to semiconductor manufacturing will require integrated experimental and modeling efforts to interrogate the vast parameter space that controls both lateral and out-of-plane ordering. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 96–102  相似文献   

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Thin films (monolayer and bilayer) of cylinder forming polystyrene‐block‐polydimethylsiloxane (PS‐b‐PDMS) were shear aligned by the swelling and deswelling of a crosslinked PDMS pad that was physically adhered to the film during solvent vapor annealing. The nanostructures formed by self‐assembly were exposed to ultraviolet‐ozone to partially oxidize the PDMS, followed by calcination in air at 500 °C. In this process, the PS segments were fully decomposed, while the PDMS yielded silica nanostructures. The highly aligned PDMS cylinders were thus deposited as silica nanolines on the silicon substrate. Using a bilayer film, the center‐to‐center distance of these features were effectively halved from 38 to 19 nm. Similarly, by sequential shear‐alignment of two distinct layers, a rhombic array of silica nanolines was fabricated. This methodology provides a facile route to fabricating complex topographically patterned nanostructures. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1058–1064  相似文献   

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This study aimed to produce electrospun nanofibers from a polyvinyl butyral polymer (PVB) solution enriched with red and grey selenium nanoparticles. Scanning electron microscopic analysis was used to observe the samples, evaluate the fiber diameters, and reveal eventual artifacts in the nanofibrous structure. Average fiber diameter is determined by manually measuring the diameters of randomly selected fibers on scanning electron microscopic (SEM) images. The obtained nanofibers are amorphous with a diameter of approximately 500 nm, a specific surface area of approx. 8 m2 g−1, and 5093 km cm−3 length. If the red and grey selenium nanoparticles were produced in powder form and suspended to the ethanolic solution of PVB then they were located inside and outside the fiber. When selenium nanoparticles were synthesized in the PVB solution, then they were located only inside the fiber. These nanofiber sheets enriched with selenium nanoparticles could be a good candidate for high-efficiency filter materials and medical applications.  相似文献   

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Herein, it is demonstrated that star pseudopolyrotaxanes (star‐pPRs) obtained from the inclusion complexation of α‐cyclodextrin (CD) and four‐branched star poly(ε‐caprolactone) (star‐PCL) organize into nanoplatelets in dimethyl sulfoxide at 35 °C. This peculiar property, not observed for linear pseudopolyrotaxanes, allows the processing of star‐pPRs while preserving their supramolecular assembly. Thus, original PCL:star‐pPR core:shell nanofibers are elaborated by coaxial electrospinning. The star‐pPR shell ensures the presence of available CD hydroxyl functions on the fiber surface allowing its postfunctionalization. As proof of concept, fluorescein isothiocyanate is grafted. Moreover, the morphology of the fibers is maintained due to the star‐pPR shell that acts as a shield, preventing the fiber dissolution during chemical modification. The proposed strategy is simple and avoids the synthesis of polyrotaxanes, i.e., pPR end‐capping to prevent the CD dethreading. As PCL is widely used for biomedical applications, this strategy paves the way for simple functionalization with any bioactive molecules.

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11.
The directed self-assembly of diblock copolymers in solvents is studied systematically using a simulated annealing method. Effects of the shape, scale, and adsorption capacity of the induced surface on the morphology of the aggregates are examined. A variety of morphologies are predicted. By increasing the scale of induced surface, the micellar shape transforms from cylinder to sheet with a tail and finally to thin sheet without tail. The shape of induced surface determines the sheet’s shape, such as rounded and square. Configurations of hydrophobic blocks and interfacial energies are investigated by calculating the mean square end-to-end distances and the contact numbers between hydrophobic monomer and other species, respectively.  相似文献   

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By simply blending two diblock copolymers with the same chemistry but with different compositions one is able to create well‐defined larger soft ­nanoparticles as well as bimodal soft nanoparticles. Specifically, blending two diblock copolymers in a solvent good for both blocks followed by a gradual introduction of a non‐solvent results in a mixed micelle, larger than their pure block‐copolymer‐forming micelles. The formation of well‐defined larger micelle is due to the balance between the ability of the mixed micelles to assemble or merge in comparison to their pure diblock copolymer micelles. Evidently, the blending ratio, the mixing protocol, and non‐solvent addition rate are crucial to achieving well‐defined larger or bimodal micelles.

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Solution‐, melt‐, and co‐axial electrospinning are well‐known methods for producing nano‐ and microfibers. The electrospinning of colloids (or colloid‐electrospinning) is a new field that offers the possibility to elaborate multicompartment nanomaterials. However, the presence of colloids in the electrospinning feed further complicates theoretical predictions in a system that is dependent on chemical, physical, and process parameters. Herein, we give a summary of recent important results and discuss the perspectives of electrospinning of colloids for the synthesis and characterization of multicompartment fibers.  相似文献   

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A new method is reported for minimizing the inherent fiber instability in the electrospinning process. The method, dubbed “biased AC electrospinning”, employs a combination of DC and AC potentials and results in highly‐aligned mats of polymer or composite polymer fibers. The relationship between specific processing variables such as the AC frequency and the magnitude of the DC offset was investigated and related to the resulting fiber stability and uniformity. For optimum fiber stability, the AC frequency must fall within a relatively narrow range. The upper and lower frequency limits were measured for a small group of polymers and polymer composites and were qualitatively related to solution properties and processing variables. Potential applications of well‐ordered nanofiber materials include tissue engineering, filtration, drug delivery, and microelectronics.

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15.
Lys-Lys诱导的金纳米粒子组装   总被引:1,自引:0,他引:1  
尝试利用赖氨酸分子作为连接剂将金纳米粒子组装成有序的纳米结构.首先通 过赖氨酸的氨基与金纳米粒子的作用将其固定在粒子表面,然后通过氨基酸的缩合 将金纳米粒子连接成有序的纳米结构。透射电子显微镜观察表明形成的纳米粒子网 络结构中,相邻粒子之间的距离约为1.5m,与由两个赖氨酸缩合而成的二肽(Lys- Lys)长度相符.  相似文献   

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Self‐assembly of amphiphilic ABA random triblock copolymers in water serves as a novel approach to create unique structure micelles connected with flexible linkages. The ABA triblock copolymers consist of amphiphilic random copolymers bearing hydrophilic poly(ethylene glycol) and hydrophobic dodecyl pendants as the A segments and a hydrophilic poly(ethylene oxide) (PEO) as the middle B segment. The A block is varied in dodecyl methacrylate content of 20%–50% and degree of polymerization (DP) of 100‐200. By controlling the composition and DP of the A block, various architectures can be tailor‐made as micelles in water: PEO‐linked double core unimer micelles, PEO‐looped unimer or dimer micelles, and multichain micelles. Those PEO‐linked or looped micelles further exhibit thermoresponsive solubility in water. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 313–321  相似文献   

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Ultrafine fibrous (? from 100 to 450 nm) cellulose membranes were generated by electrospinning of cellulose acetate [degree of substitution (DS): 2.45, weight‐average molecular weight: 30,000 Da], followed by alkaline deacetylation. Reaction of these ultrahigh surface‐area cellulose fibers with methacrylate chloride (MACl) produced activated surfaces without altering the fiber morphology. Surface methacrylation of these fibers was confirmed by the acquired hydrophobicity (θwater = 84°) as compared to the originally hydrophilic (θwater = 56°) cellulose. Changing the MACl:OH molar ratios could vary the overall DS of methacrylation. The very low overall DS values indicate the surface nature of the methacrylation reaction. At a DS of 0.17, the thermal properties of the surface methacrylated cellulose resemble those of cellulose derivatives at much higher DS values, an unusual behavior of the ultrafine fibers. The methacrylated cellulose could be further copolymerized with vinyl monomers (methyl methacrylate, acrylamide, and N‐isopropylacrylamide) as linear grafts or three‐dimensional (3D) networks. The morphology of cellulose fibers and the interfiber pore structure were not altered at 15–33% graft levels. This study demonstrates that either linear or 3D networks of vinyl polymers could be efficiently supported on ultrafine cellulose fibrous membranes via surface methacrylation. Through these surface reactions the chemical, thermal, and liquid wetting and absorbent properties of these ultrafine fibrous membranes were significantly altered with no change to the fiber dimensions or interfiber pore morphology. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 953–964, 2003  相似文献   

18.
Elaboration of mesostructured silica films with a triblock copolymer polyethylene oxide-polypropylene oxide-polyethylene oxide, (PEO-PPO-PEO) and controlled growth of silver nanoparticles in the mesostructure are described. The films are characterized using UV-visible optical absorption spectroscopy, TEM, AFM, SEM, X-ray diffraction (XRD) and Rutherford backscattering spectrometry (RBS). Organized arrays of spherical silver nanoparticles with diameter between 5 and 8 nm have been obtained by NaBH4 reduction. The size and the repartition of silver nanoparticles are controlled by the film mesostructure. The localization of silver nanoparticles exclusively in the upper-side part of the silica-block copolymer film is evidenced by RBS experiment. On the other hand, by using a thermal method, 40 nm long silver sticks can be obtained, by diffusion and coalescence of spherical particles in the silica-block copolymer layer. In this case, migration of silver particles toward the glass substrate-film interface is shown by the RBS experiment.  相似文献   

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Nanoparticles provide an attractive route to modifying polymer thin film properties, yet controlling the dispersion and morphology of functionalized nanoparticle filled films is often difficult. Block copolymers can provide an ideal template for directed assembly of nanoparticles under controlled nanoparticle‐polymer interactions. Previously we observed that neat films of cylinder forming poly(styrene‐b‐methyl methacrylate) PS‐b‐PMMA block copolymer (c‐BCP) orient vertically with dynamic sharp thermal cold zone annealing (CZA‐S) over wide range of CZA‐S speed (0.1–10) μm/s. Here, we introduce a low concentration (1–5 wt %) of nanoparticles of phenolic group functionalized CdS (fCdS‐NP), to PMMA cylinder forming polystyrene‐b‐poly (methyl methacrylate) block copolymer (c‐BCP) films. Addition of the fCdS‐NP induces a vertical to horizontal orientation transition at low CZA‐S speed, V = 5 μm/s. The orientation flip studies were analyzed using AFM and GISAXS. These results confirm generality of our previously observed orientation transition in c‐BCP under low speed CZA‐S with other nanoparticles (gold [Au‐NP], fulleropyrrolidine [NCPF‐NP]) in the same concentration range, but reveal new aspects not previously examined: (1) A novel observation of significant vertical order recovery from 5–10% vertical cylindrical fraction at V = 5 μm/s to 46–63% vertical cylindrical fraction occurring at high CZA‐S speed, V = 10 μm/s for the fCdS nanoparticle filled films. (2) We rule out the possibility that a nanoparticle wetting layer on the substrate is responsible for the vertical to horizontal flipping transition. (3) We demonstrate that the orientation flipping results can be achieved in a nanoparticle block copolymer system where the nanoparticles are apparently better‐dispersed within only one (matrix PS) domain unlike our previous nanoparticle system studied. We consider facile processing conditions to fabricate functionalized nanoparticles filled PS‐PMMA block copolymer films with controlled anisotropy, a useful strategy in the design of next generation electronic and photonic materials. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 604–614  相似文献   

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Summary: Polystyrene (PS) micro‐ and nanospheres with uniform dimensions and smooth surfaces have been produced by electrospray. The effect of PS molecular weight on beads morphology and the fundamental role of concentration have been investigated. Moreover, a new apparatus was designed to collect the polymer spheres during the process and to prevent the coalescence among the spheres.

PS micro‐ and nanospheres produced by electrospray  相似文献   


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