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1.
Polymers (Basel) ; 11(12)2019 Nov 20.
Artigo em Inglês | MEDLINE | ID: mdl-31757006

RESUMO

The fabrication of nanocomposite films and fibers based on cellulose nanocrystals (P-tCNCs) and a thermoplastic polyurethane (PU) elastomer is reported. High-aspect-ratio P-tCNCs were isolated from tunicates using phosphoric acid hydrolysis, which is a process that affords nanocrystals displaying high thermal stability. Nanocomposites were produced by solvent casting (films) or melt-mixing in a twin-screw extruder and subsequent melt-spinning (fibers). The processing protocols were found to affect the orientation of both PU hard segments and the P-tCNCs within the PU matrix and therefore the mechanical properties. While the films were isotropic, both the polymer matrix and the P-tCNCs proved to be aligned along the fiber direction in the fibers, as shown using SAXS/WAXS, angle-dependent Raman spectroscopy, and birefringence analysis. Tensile tests reveal that fibers and films, at similar P-tCNC contents, display Young's moduli and strain-at-break that are within the same order of magnitude, but the stress-at-break was found to be ten-times higher for fibers, conferring them a superior toughness over films.

2.
ACS Nano ; 13(4): 4018-4027, 2019 Apr 23.
Artigo em Inglês | MEDLINE | ID: mdl-30917283

RESUMO

Biological systems are able to control the assembly and positioning of proteins with nanoscale precision, as exemplified by the intricate molecular structures within cell membranes, virus capsids, and collagen matrices. Controlling the assembly of biomolecules is critical for the use of biomaterials in artificial systems such as antibacterial coatings, engineered tissue samples, and implanted medical devices. Furthermore, understanding the dynamics of protein assembly on heterogeneous templates will ultimately enable the control of protein crystallization in general. Here, we show a biomimetic, hierarchical bottom-up approach to direct the self-assembly of crystalline S-layers through nonspecific interactions with nanostructured block copolymer (BCP) thin-film templates. A comparison between physically and chemically patterned BCP substrates shows that chemical heterogeneity is required to confine the adhesion and self-assembly of S-layers to specific BCP domains. Furthermore, we show that this mechanism can be extended to direct the formation of collagen fibers along the principal direction of the underlying BCP substrate. The dynamics of protein self-assembly at the solid-liquid interface are followed using in situ high-resolution atomic force microscopy under continuous flow conditions, allowing the determination of the rate constants of the self-assembly. A pattern of alternating, chemically distinct nanoscale domains drastically increases the rate of self-assembly compared to non-patterned chemically homogeneous substrates.

3.
Adv Mater ; 31(2): e1803478, 2019 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-30393994

RESUMO

Optical metamaterials offer the tantalizing possibility of creating extraordinary optical properties through the careful design and arrangement of subwavelength structural units. Gyroid-structured optical metamaterials possess a chiral, cubic, and triply periodic bulk morphology that exhibits a redshifted effective plasma frequency. They also exhibit a strong linear dichroism, the origin of which is not yet understood. Here, the interaction of light with gold gyroid optical metamaterials is studied and a strong correlation between the surface morphology and its linear dichroism is found. The termination of the gyroid surface breaks the cubic symmetry of the bulk lattice and gives rise to the observed wavelength- and polarization-dependent reflection. The results show that light couples into both localized and propagating plasmon modes associated with anisotropic surface protrusions and the gaps between such protrusions. The localized surface modes give rise to the anisotropic optical response, creating the linear dichroism. Simulated reflection spectra are highly sensitive to minute details of these surface terminations, down to the nanometer level, and can be understood with analogy to the optical properties of a 2D anisotropic metasurface atop a 3D isotropic metamaterial. This pronounced sensitivity to the subwavelength surface morphology has significant consequences for both the design and application of optical metamaterials.

4.
Small ; 14(46): e1802872, 2018 11.
Artigo em Inglês | MEDLINE | ID: mdl-30318828

RESUMO

Self-assembling block copolymer films provide access to a variety of different nanostructured patterns in one, two, and three dimensions. However, in the absence of any templating, these nanostructures suffer from defects, often limiting utility. Directed block copolymer self-assembly uses patterned substrates that effectively suppress defect formation and allow the creation of desired patterns. The two main directed self-assembly techniques, chemoepitaxy and graphoepitaxy, employ chemically and topographically patterned substrates, respectively, to direct the block copolymer assembly in thin films. Their successful application in generating defect-free patterns in films of block copolymers exhibiting particular morphologies is summarized in this concept article. The possible role of directed self-assembly in extending nanostructured patterning from two to three dimensions is also discussed.

5.
Small ; 14(46): e1802401, 2018 11.
Artigo em Inglês | MEDLINE | ID: mdl-30252206

RESUMO

The efficacy with which solvent vapor annealing (SVA) can control block copolymer self-assembly has so far been demonstrated primarily for the simplest class of copolymer, the linear diblock copolymer. Adding a third distinct block-thereby creating a triblock terpolymer-not only provides convenient access to complex continuous network morphologies, particularly the gyroid phases, but also opens up a route toward the fabrication of novel nanoscale devices such as optical metamaterials. Such applications, however, require the generation of well-ordered 3D continuous networks, which in turn requires a detailed understanding of the SVA process in terpolymer network morphologies. Here, in situ grazing-incidence small-angle X-ray scattering (GISAXS) is employed to study the self-assembly of a gyroid-forming triblock terpolymer during SVA, revealing the effects of several key SVA parameters on the morphology, lateral order, and, in particular, its preservation in the dried film. The robustness of the terpolymer gyroid morphology is a key requirement for successful SVA, allowing the exploration of annealing parameters which may enable the generation of films with long-range order, e.g., for optical metamaterial applications.

6.
Macromolecules ; 51(20): 8332, 2018 10 23.
Artigo em Inglês | MEDLINE | ID: mdl-31186588

RESUMO

[This corrects the article DOI: 10.1021/acs.macromol.7b01567.].

7.
Macromolecules ; 50(16): 6255-6262, 2017 Aug 22.
Artigo em Inglês | MEDLINE | ID: mdl-28919648

RESUMO

Block copolymer (BCP) self-assembly is a promising route to manufacture functional nanomaterials for applications from nanolithography to optical metamaterials. Self-assembled cubic morphologies cannot, however, be conveniently optically characterized in the lab due to their structural isotropy. Here, the aligned crystallization behavior of a semicrystalline-amorphous polyisoprene-b-polystyrene-b-poly(ethylene oxide) (ISO) triblock terpolymer was utilized to visualize the grain structure of the cubic microphase-separated morphology. Upon quenching from a solvent swollen state, ISO first self-assembles into an alternating gyroid morphology, in the confinement of which the PEO crystallizes preferentially along the least tortuous pathways of the single gyroid morphology with grain sizes of hundreds of micrometers. Strikingly, the resulting anisotropic alignment of PEO crystallites gives rise to a unique optical birefringence of the alternating gyroid domains, which allows imaging of the self-assembled grain structure by optical microscopy alone. This study provides insight into polymer crystallization within a tortuous three-dimensional network and establishes a useful method for the optical visualization of cubic BCP morphologies that serve as functional nanomaterial templates.

8.
Nanoscale ; 9(39): 14888-14896, 2017 Oct 12.
Artigo em Inglês | MEDLINE | ID: mdl-28949359

RESUMO

A simple and robust method has been developed for the generation of macroscopically ordered hexagonal arrays from the directed self-assembly (DSA) of cylinder-forming block copolymers (BCPs) based on minimal trench patterns with solvent vapor annealing. The use of minimal trench patterns allows us to probe the guided hexagonal arrays of cylindrical microdomains using grazing incidence small angle X-ray scattering (GISAXS), where the sample stage is rotated on the basis of the six-fold symmetry of a hexagonal system. It is found that the (10) planes of hexagonal arrays of cylindrical microdomains are oriented parallel to the underlying trench direction over macroscopic length scales (∼1 × 1 cm2). However, there are misorientations of the hexagonal arrays with short-range ordering. GISAXS patterns show that the hexagonal arrays on the minimal trench pattern are distorted, deviating from a perfect hexagonal lattice. This distortion has been attributed to the absence of topographic constraints in the unconfined direction on the 1-D minimal trench pattern. Also, the frustration of BCP microdomains, arising from the incommensurability between the trench pitch and natural period of the BCP at the base of the trench, influences the distortion of the hexagonal arrays.

9.
ACS Appl Mater Interfaces ; 9(27): 22388-22397, 2017 Jul 12.
Artigo em Inglês | MEDLINE | ID: mdl-28609102

RESUMO

Mesoporous titania microspheres (MTMs) have been employed in many applications, including (photo)catalysis as well as energy conversion and storage. Their morphology offers a hierarchical structural design motif that lends itself to being incorporated into established large-scale fabrication processes. Despite the fact that device performance hinges on the precise morphological characteristics of these materials, control over the detailed mesopore structure and the tunability of the pore size remains a challenge. Especially the accessibility of a wide range of mesopore sizes by the same synthesis method is desirable, as this would allow for a comparative study of the relationship between structural features and performance. Here, we report a method that combines sol-gel chemistry with polymer micro- and macrophase separation to synthesize porous titania spheres with diameters in the micrometer range. The as-prepared MTMs exhibit well-defined, accessible porosities with mesopore sizes adjustable by the choice of the polymers. When applied as an anode material in lithium ion batteries (LIBs), the MTMs demonstrate excellent performance. The influence of the pore size and an in situ carbon coating on charge transport and storage is examined, providing important insights for the optimization of structured titania anodes in LIBs. Our synthesis strategy presents a facile one-pot approach that can be applied to different structure-directing agents and inorganic materials, thus further extending its scope of application.

10.
Macromolecules ; 50(21): 8637-8646, 2017 Nov 14.
Artigo em Inglês | MEDLINE | ID: mdl-30174341

RESUMO

We have investigated PLLA crystallization in lamellae-forming PS-b-PLLA confined to straight cylindrical nanopores under weak confinement (nanopore diameter D/equilibrium PS-b-PLLA period L0 ≥ 4.8). Molten PS-b-PLLA predominantly forms concentric lamellae along the nanopores, but intertwined helices occur even for D/L0 ≈ 7.3. Quenching PS-b-PLLA melts below TG(PS) results in PLLA cold crystallization strictly confined by the vitrified PS domains. Above TG(PS), PLLA crystallization is templated by the PS-b-PLLA melt domain structure in the nanopore centers, while adsorption on the nanopore walls stabilizes the outermost cylindrical PS-b-PLLA shell. In between, the nanoscopic PS-b-PLLA melt domain structure apparently ripens to reduce frustrations transmitted from the outermost immobilized PS-b-PLLA layer. The onset of PLLA crystallization catalyzes the ripening while transient ripening states are arrested by advancing PLLA crystallization. Certain helical structure motifs persist PLLA crystallization even if PS is soft. The direction of fastest PLLA crystal growth is preferentially aligned with the nanopore axes to the same degree as for PLLA homopolymer, independent of whether PS is vitreous or soft.

11.
ACS Photonics ; 3(10): 1888-1896, 2016 Oct 19.
Artigo em Inglês | MEDLINE | ID: mdl-27785456

RESUMO

Gold gyroid optical metamaterials are known to possess a reduced plasma frequency and linear dichroism imparted by their intricate subwavelength single gyroid morphology. The anisotropic optical properties are, however, only evident when a large individual gyroid domain is investigated. Multidomain gyroid metamaterials, fabricated using a polyisoprene-b-polystyrene-b-poly(ethylene oxide) triblock terpolymer and consisting of multiple small gyroid domains with random orientation and handedness, instead exhibit isotropic optical properties. Comparing three effective medium models, we here show that the specular reflectance spectra of such multidomain gyroid optical metamaterials can be accurately modeled over a broad range of incident angles by a Bruggeman effective medium consisting of a random wire array. This model accurately reproduces previously published results tracking the variation in normal incidence reflectance spectra of gold gyroid optical metamaterials as a function of host refractive index and volume fill fraction of gold. The effective permittivity derived from this theory confirms the change in sign of the real part of the permittivity in the visible spectral region (so, that gold gyroid metamaterials exhibit both dielectric and metallic behavior at optical wavelengths). That a Bruggeman effective medium can accurately model the experimental reflectance spectra implies that small multidomain gold gyroid optical metamaterials behave both qualitatively and quantitatively as an amorphous composite of gold and air (i.e., nanoporous gold) and that coherent electromagnetic contributions arising from the subwavelength gyroid symmetry are not dominant.

12.
Nano Lett ; 15(5): 3420-4, 2015 May 13.
Artigo em Inglês | MEDLINE | ID: mdl-25867200

RESUMO

We report the first in situ measurement of the helical pitch of the helical nanofilament B4 phase of bent-core liquid crystals using linearly polarized, resonant soft X-ray scattering at the carbon K-edge. A strong, anisotropic scattering peak corresponding to the half-pitch of the twisted smectic layer structure was observed. The equilibrium helical half-pitch of NOBOW is found to be 120 nm, essentially independent of temperature. However, the helical pitch can be tuned by mixing guest organic molecules with the bent-core host, followed by thermal annealing.

13.
Adv Mater ; 26(2): 273-81, 2014 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-24282077

RESUMO

In situ grazing-incidence small-angle X-ray scattering experiments on thin films of block copolymers during annealing in neutral solvent vapors are reported. By removing the solvent in a controlled manner, the period of the microphase separated morphology is found to increase with increasing block copolymer concentration in a power law manner with an exponent ∼ 2/3. By venting the systems at different rates during the solvent removal process, kinetically arresting the system, the period of the microphase separated morphology in the dried film can be varied.

14.
Philos Trans A Math Phys Eng Sci ; 371(2000): 20120306, 2013 Oct 13.
Artigo em Inglês | MEDLINE | ID: mdl-24000358

RESUMO

To meet the increasing demand for patterning smaller feature sizes, a lithography technique is required with the ability to pattern sub-20 nm features. While top-down photolithography is approaching its limit in the continued drive to meet Moore's law, the use of directed self-assembly (DSA) of block copolymers (BCPs) offers a promising route to meet this challenge in achieving nanometre feature sizes. Recent developments in BCP lithography and in the DSA of BCPs are reviewed. While tremendous advances have been made in this field, there are still hurdles that need to be overcome to realize the full potential of BCPs and their actual use.

15.
Adv Mater ; 24(42): 5688-94, 2012 Nov 08.
Artigo em Inglês | MEDLINE | ID: mdl-22903820

RESUMO

High-aspect-ratio sub-15-nm silicon trenches are fabricated directly from plasma etching of a block copolymer mask. A novel method that combines a block copolymer reconstruction process and reactive ion etching is used to make the polymer mask. Silicon trenches are characterized by various methods and used as a master for subsequent imprinting of different materials. Silicon nanoholes are generated from a block copolymer with cylindrical microdomains oriented normal to the surface.


Assuntos
Nanoporos/ultraestrutura , Polímeros/química , Silício/química , Polietilenoglicóis/química , Poliestirenos/química , Polivinil/química , Solventes/química
17.
ACS Appl Mater Interfaces ; 2(8): 2436-41, 2010 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-20672830

RESUMO

A few percent of transition metals impregnated inside some biological organisms in nature remarkably improve such organisms' mechanical stability. Although the lure to emulate them for development of new biomimetic structural materials has been great, the practical advances have been rare because of the lack of proper synthetic approaches. Multiple pulsed vapor phase infiltration proved successful for the preparation of such transition metal impregnated materials with highly improved mechanical stability. The artificially infiltrated metals (Al, Ti, or Zn) from gas phase lead to around 3 times increase of toughness (in terms of breaking energy) of natural collagen in a dried state. In addition, the infiltrated metals apparently induce considerable crystallographic changes in the natural collagen structures. This infiltration approach can be used as guide for the synthesis of bioinspired structural materials related to metal infiltration.


Assuntos
Biomimética/métodos , Colágeno/química , Dessecação , Metais/química , Alumínio/química , Animais , Galinhas , Cristalografia , Microscopia Eletrônica de Transmissão e Varredura , Conformação Proteica , Análise Espectral Raman , Estresse Mecânico , Titânio/química , Zinco/química
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