1. Field of the Invention
The present invention relates to network textures and their producing methods.
2. Description of Related Art
Soft matter such as block copolymers (BCPs), surfactant-water systems, and liquid crystals can form regular structures on the micron to nanometer scales. Much attention has been paid to complex three-dimensional (3D) interconnected network structures as they are self-supported and have high specific surface and high porosity.
In particular, three bi-continuous cubic phases formed by two continuous interpenetrating networks, including double gyroid (DG, Ia
The basic shape of the gyroid is a three-fold junction of three arms, in which each arm connects to another planar set of three arms that are each themselves rotated and connected to form a three-dimensional (3D) network. The double gyroid (DG) structure is composed of a cubic matrix and a pair of continuous, interpenetrating but independent, coherent single gyroid (SG, I4132) networks, one left- and one right-handed, to form an achiral structure in 3D space. By contrast, the single gyroid (SG) structure is a chiral structure with only one continuous network; the network can be left or right-handed. However, single gyroid (SG) is rare, and can only be found in some specific systems such as the butterfly wings from Papilionidae and Lycaenidae families (V. Saranathan, C. O. Osuji, S. G. J. Mochrie, H Noh, S. Narayanan, A. Sandy, E. R. Dufresne, R. O. Prum, Proc. Natl. Acad. Sci., U.S.A. 2010, 107, 11676) and triblock terpolymers (T H Epps, E W Cochran, T S Bailey, R S Waletzko, C M Hardy, F S Bates, Macromolecules 2004, 37, 8325-8341; S Vignolini, N A Yufa, P S Cunha, S Guldin, I Rushkin, M Stefik, K Hur, U Wiesner, J J Baumberg, U Steiner, Adv. Mater. Adv. Mate. 2012, 24(10), OP23-OP27). The butterflies develop the thermodynamically favored double gyroid (DG) precursors, in which one of the two single gyroid structures is decomposed to form a single gyroid (SG) structure with significant optical efficiency. This three dimensional (3D) periodicity potentially manipulates light in all directions, giving bright reflected color over a broad angle. Note that single gyroid (SG, I4132, No. 214) is the subgroup of the super group double gyroid (DG, Ia
In one general aspect, the present invention relates to network textures and their producing method.
According to an embodiment of this invention, a method is provided with the steps of: forming a porous structure as a matrix; forming two coherent, independent, and separated robust continuous network structures within the matrix by using the matrix as the template; and softening or removing the matrix to shift the two continuous network structures, leading to a novel network texture comprising two incoherent continuous network structures.
According to another embodiment of this invention, a network texture is provided with two incoherent continuous network structures.
Preferably, the network texture is made by the above-mentioned method.
Reference will now be made in detail to those specific embodiments of the invention. Examples of these embodiments are illustrated in accompanying drawings. While the invention will be described in conjunction with these specific embodiments, it will be understood that it is not intended to limit the invention to these embodiments. On the contrary, it is intended to cover alternatives, modifications, and equivalents as may be included within the spirit and scope of the invention as defined by the appended claims. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention may be practiced without some or all of these specific details. In other instances, well-known process operations and components are not described in detail in order not to unnecessarily obscure the present invention. While drawings are illustrated in detail, it is appreciated that the quantity of the disclosed components may be greater or less than that disclosed, except where expressly restricting the amount of the components. Wherever possible, the same or similar reference numbers are used in drawings and the description to refer to the same or like parts.
Varied continuous networks and their properties have been developed and studied by scientists, and it is difficult and interesting to find novel three-dimensional structures.
The inventors of the present invention discover novel network textures and their producing method.
In an embodiment, a network texture is provided with two incoherent (or subgroup symmetry) continuous network structures.
In an embodiment, the network texture is made by a method comprising the steps of: (1) forming a porous structure as a matrix; (2) forming two coherent, independent, and separated robust continuous network structures within the matrix by using the matrix as a template; and (3) softening or removing the matrix to shift the two continuous network structures, leading to a novel network texture comprising the two incoherent continuous network structures.
Preferably, the novel network texture is a polygrain configuration, and the displacements between two continuous network structures have various directions and magnitudes in a given grain.
In an embodiment, when a small-angle X-ray scattering (SAXS) analysis is performed to the two incoherent continuous network structures, only one of the two incoherent continuous network structures is identified by the small-angle X-ray scattering analysis.
In an embodiment, the two continuous network structures are made of a same material. In another embodiment, the two continuous network structures are made of two different materials. For example, the two continuous network structures can be made of organic materials (polymer, liquid crystal, organic polymers, etc.) or inorganic material (ceramic material, metal, etc.).
In an embodiment, the matrix is removed by thermal treatment, solvent, photo-decomposition, ozonolysis, and/or calcination.
In an embodiment, the two coherent continuous network structures are two single gyroid network structures (construct a double gyroid), and transform to two incoherent single gyroid network structures after the network shifting.
In an embodiment, the two coherent continuous network structures are two single diamond network structures (construct a double diamond), and transform to two incoherent single diamond network structures after the network shifting.
In an embodiment, the two coherent continuous network structures construct a plumber's nightmare structure (double P (DP), Im
Without limiting the scope of the present invention, an embodiment of the present invention illustrates a novel network texture and its fabrication method as follows.
Firstly, a block copolymer with porous structure is formed and is used as a matrix. Then the block copolymer matrix is used a template, and a material fills the porous structure of the matrix, so as to form a double gyroid (DG) within the matrix. The matrix is then softened to shift two single gyroids of the double gyroid and hence form a novel network texture. The following describes more detail.
A polystyrene (PS) and poly-L-lactide (PLLA) block copolymer (PS-PLLA BCP) is prepared by a double-headed polymerization sequence. The molecular weight of polystyrene (Mn,PS) and poly-L-lactide (Mn,PLLA) are 34000 g mol−1 and 27000 g mol−1, respectively. The polydispersity index (PDI) of the block copolymer is 1.21 and the volume ratio of poly-L-lactide (fPLLAv) is 0.39. A PS-PLLA film is solution cast from dichloromethane (CH2Cl2) solution (10 wt % of PS-PLLA) at room temperature and then dried in a vacuum.
To eliminate the undesirable disturbance of poly-L-lactide (PLLA) crystallization on the shape of the domains during microphase separation, the as-cast samples are annealed at temperature above the melting temperature of poly-L-lactide (PLLA) but below its order-disorder transition temperature. For example, the annealing temperature is about 185° C. The produced PS-PLLA film is then rapidly cooled below the glass temperatures of polystyrene (PS) and poly-L-lactide (PLLA), yielding the micro-phase-separated double gyroid (DG) domain structure as expected from the phase diagram of PS-PLLA. The one-dimensional small-angle X-ray scattering (1D SAXS) profile shows characteristic reflections from the Ia
After that, precursors of SiO2 are infiltrated into the nanoporous polystyrene (PS) template with precursors and a sol-gel reaction is conducted to obtain PS/SiO2 nanohybrids. The one-dimensional small-angle X-ray scattering (SAXS) profile of the PS/SiO2 nanohybrids with the diffraction peaks at the relative q values of √{square root over (6)}:√{square root over (8)} suggests the formation of a well-ordered PS/SiO2 double gyroid (DG) nanohybrid structure. The d211 as determined by the primary peak is reduced to approximately 36 nm from 40 nm, most likely because of the swelling of the polystyrene (PS) matrix by methanol, resulting in a reduction in the dimension of the double gyroid (DG) during the aging period for the formation of SiO2 microdomains.
Next, the fabricated PS/SiO2 double gyroid (DG) nanohybrids are further heated at a rate of 1° C./min to 180° C. To trace the morphological evolution and to find any corresponding phase transition behavior, temperature-resolved small-angle X-ray scattering (SAXS) experiments from 30° C. to 180° C. are carried out, as shown in
Comparing
To further understand and interpret such non-DG projections, electron tomography (3D TEM) is carried out to directly visualize the new structure in real space.
There are many grain boundaries resulting from the intrinsic nature of bulk self-assembled SiO2 networks after the thermal treatment. The grain size of the double gyroid (DG) phase is usually 10×10×10 μm3, giving more than 106 grains in a sample with one mm3 in size so that it is impossible for coherent network shifting (i.e., a fixed displacement along a particular direction) due to the restriction of the displacements of the networks at grain boundaries and defects, there are connections between the networks. As a result, the network morphology after the thermal treatment will exhibit a variety of geometric dispositions due to the set of small arbitrary shifts with various directions and magnitudes between two networks in a given double gyroid (DG) grain. The overall network shifting will be nearly random due to the various constraints on coherent shifting, consistent with observations of various unusual patterns from transmission electron microscopy (TEM). After the thermal treatment, the displacements between two single gyroid (SG) networks have various directions and magnitudes in a given double gyroid (DG) grain.
Network shifting will break the inversion symmetry of the DG phase, resulting in two incoherent single gyroid networks. The single gyroid network pairs will have various registrations, varying from grain to grain. The resultant overall morphology from the random shifting in the polygrain samples will therefore lead to x-ray diffraction as from a single gyroid (SG), consistent to the SAXS results at which the low q reflection can be clearly identified in different samples after the thermal treatment but with the intensity and sharpness of the low q reflection varying from sample to sample due to the variation in grain size and local defect content from self-assembly. Also, there are no reflections different to single gyroid (SG) after the thermal treatment, indicating that the set of reflections can be attributed to the set of single gyroid networks with incoherent character. In other words, the fabricated two asymmetric single gyroid networks have the same SAXS results (characteristics) as a true single gyroid network. Therefore, the fabricated two asymmetric single gyroid networks can be referred to as a “single gyroid-like” network. The displacements between two single gyroid (SG) networks have various directions and magnitudes in a given double gyroid (DG) grain causing this unique property.
It is speculated that the reflection could be more if the matrix is removed from the nanohybrids. The matrix may limit the shifting of the two single gyroid networks, and the displacements between two single gyroid (SG) networks may be more random after removing the matrix.
Therefore, to obtain network morphologies with SG-like properties and enhance the dielectric contrast for optical performance, a calcination process may be performed by heating the PS/SiO2 nanohybrids to 550° C. for complete removal of the PS matrix, so as to release the constraints from the PS matrix and give expected random shifting.
As shown in
To examine the feasibility of exploiting the produced novel nanoporous material with SG-like properties for optical applications, the corresponding dispersion relations (band structure) w(k) were simulated using the software package Lumerical Solutions based on the finite-difference time-domain (FDTD) method. The geometry of the gyroid surface is approximated by the function:
sin x cos y+sin y cos z+cos x sin z=t
Because the shrinkage of the SiO2 gel monoliths is between approximately 20% and 30% after removal of the remaining liquid, a volume fraction of the double gyroid (DG) skeleton is set to 30%. A double gyroid structure with a two networks each of 15% volume fraction can be made by choosing t=+/−1.055. Periodic boundary conditions are used to create a three-dimensional lattice structure, and the unit cell “a” (lattice parameter) is set to 100 nm according to the small-angle X-ray scattering (SAXS) results.
As shown in
It is appreciated that the novel asymmetric single gyroid-like network texture, is unwittingly found by the inventers. The inventers discover the asymmetric single gyroid-like network texture has unique properties, and then think the rationale for the unique properties and the principle to fabricate the novel network texture.
In this embodiment, a double gyroid form of block copolymer with a segment capable of being removed, such as polystyrene and poly-L-lactide block copolymer (PS-PLLA BCP), is selected to use as a matrix. After the poly-L-lactide block is hydrolyzed, a double gyroid form of polystyrene matrix is formed. The polystyrene matrix is then used as a matrix and a nanoreactor, and a sol-gel reaction in introduced within the porous structure of the matrix, so as to produce a double gyroid form of PS/SiO2 nanohybrids. After that, the PS/SiO2 nanohybrids is annealed to soften the polystyrene matrix, resulting in a network shifting of the two independent and interpenetrating single gyroid SiO2 network structures. The two independent, interpenetrating single gyroid SiO2 network structures gradually approach and contact each other, so as to form a robust single gyroid-like network structure. Note that both the two independent, interpenetrating single gyroid network structures are composed of SiO2, and the thermal treatment to the PS/SiO2 will not soften or damage the SiO2. Therefore, the thermal treatment of the two single gyroid SiO2 network structures render the network shifting rather than collapse.
The same principle as mentioned in above embodiment can be used to develop other bi-continuous network structures, e.g., double diamond or plumber's nightmare structure.
As shown in
As shown in
In the above embodiments, a simple method is provided for the preparation of new material systems by random network shifting from materials with high symmetry (e.g., supergroup symmetry) to lower symmetry (e.g., subgroup symmetry). For example, breaking of the inversion symmetry of a double gyroid structure comprised of polymer/ceramic nanohybrids is used as a model system for the demonstration of how shifting networks can achieve subgroup symmetry properties (i.e., SG-like properties) from the materials with supergroup symmetry (i.e., DG) properties. The new three-dimensional network morphology may give desirable nanophotonic properties similar to those of the butterfly wing structure. The mechanism of network shifting can be applied in other registered bi-continuous cubic networks through the supergroup/subgroup transformation. For example, from coherent network structures to incoherent networks such as double diamond (DD, Pn
Although specific embodiments have been illustrated and described, it will be appreciated by those skilled in the art that various modifications may be made without departing from the scope of the present invention, which is intended to be limited solely by the appended claims.
Number | Date | Country | Kind |
---|---|---|---|
103116721 | May 2014 | TW | national |
This application is a divisional application of application Ser. No. 14/287,352, filed May 27, 2014 and entitled “NETWORKS AND METHOD FOR PRODUCING THE SAME,” which claims priority to Taiwan Patent Application No. 103116721, filed on May 12, 2014, the entire contents both of which are incorporated herein by reference.
Number | Date | Country | |
---|---|---|---|
Parent | 14287352 | May 2014 | US |
Child | 15218290 | US |