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1.
In this paper, the authors have systematically studied the microphase separation and crystallization during spin coating of an ABC triblock copolymer, polystyrene-b-poly(2-vinylpyridine)-b-poly(ethylene oxide) (PS-b-P2VP-b-PEO). The microphase separation of PS-b-P2VP-b-PEO and the crystallization of PEO blocks can be modulated by the types of the solvent and the substrate, the spinning speed, and the copolymer concentration. Ordered microphase-separated pattern, where PEO and P2VP blocks adsorbed to the substrate and PS blocks protrusions formed hexagonal dots above the P2VP domains, can only be obtained when PS-b-P2VP-b-PEO is dissolved in N,N-dimethylformamide and the films are spin coated onto the polar substrate, silicon wafers or mica. The mechanism of the formation of regular pattern by microphase separation is found to be mainly related to the inducement of the substrate (middle block P2VP wetting the polar substrate), the quick vanishment of the solvent during the early stage of the spin coating, and the slow evaporation of the remaining solvent during the subsequent stage. On the other hand, the probability of the crystallization of PEO blocks during spin coating decreases with the reduced film thickness. When the film thickness reaches a certain value (3.0 nm), the extensive crystallization of PEO is effectively prohibited and ordered microphase-separated pattern over large areas can be routinely prepared. When the film thickness exceeds another definite value (12.0 nm), the crystallization of PEO dominates the surface morphology. For films with thickness between these two values, microphase separation and crystallization can simultaneously occur.  相似文献   

2.
We report observation of ring-shaped morphology formed in thin films of a cylinder-forming polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer cast from 1,1,2,2-tetrachloroethane (Tetra-CE) solution via relatively fast solvent evaporation rates, in which Tetra-CE is a good solvent for both blocks but preferential affinity for the minority PMMA block. We studied the microstructure of a set of solution-cast block copolymer films dried with different solvent evaporation rates, R. The control with different R leads to keeping microstructures in different solution concentrations (phi) and bringing mechanical strain fields with different strength in the film, for which faster evaporation rates result in microstructures of lower solution concentrations and mechanical strain fields of higher strength. As R decreases from rapid evaporation (approximately 0.1 mL/h), the film microstructure evolved from an intermediate ringlike morphology sequentially to ring-shaped morphologies including loose and tight rings and then inverted phase of PS spheres in a PMMA matrix and finally reached the equilibrium phase, namely, cylinders of PMMA in a PS matrix. In view of the influence of the film constraints, the microstructure of a film with a terraced free surface profile has been examined. The results indicate that the ring-shaped morphology can form as long as the film thickness is larger than a critical value of about one microdomain spacing. In the case where the film thickness is larger than that value, the nature of solvent and the kinetics of solvent evaporation are shown to be mainly responsible for the ring-shaped morphology formation.  相似文献   

3.
We report on the phase behavior and microdomain structure of two types of diblock copolymers containing a liquid crystal (LC) block joined to a flexible coil block. Consideration of the symmetry groups of the liquid crystalline phases and of the block copolymer microdomain structures provides a rationale for predicting the possible types of liquid crystalline block copolymer morphologies. Both previously reported and newly discovered structural types are identified. Possible organizational schemes are developed for the mesogens and periodic disclination defects with respect to the intermaterial dividing surfaces separating the liquid crystalline and flexible coil domains. The first type of copolymer investigated has a rod-like LC block whereas the second type copolymer has a side chain LC block. Five different rod-coil diblocks based on poly(hexyl isocyanate-b-styrene) P(HIC-b-S) were synthesized by anionic polymerization. Wavy lamellae, zig-zag and arrowhead microdomain morphologies corresponding to smectic-C and smectic-O structures were observed depending on the composition. These layered phases have the director (PHIC chain axis) tilted at various orientations with respect to the layer normal. Side-chain LC diblocks based on functionalized poly(isoprene-b-styrene) P(I-b-S) were also investigated. These polymers were synthesized using polymer analogous chemistry from P(I-b-S) precursors. Three different mesogenic groups were attached to the PI blocks: one based on biphenyl benzoate and two based on azobenzene. The microdomain structures found for the functionalized poly(isoprene side-chain LC-b-styrene) P(ILC-b-S) diblocks are typical of traditional coil-coil diblocks (lamellae and cylinders). However, these morphologies possess an additional smectic layering of the mesogens within the microdomains of the LC block. In the case of the rod-coil diblocks, the transformation from an initially isotropic state to the final microphase separated solid state occurs via nematic and then smectic liquid crystalline states, whereas for the side-chain LC-coil cases, the microphase separation transition occurs prior to development of orientational order. The long-range microdomain order of LC block-coil block copolymers can extend over very large distances due to the influence of the orientational ordering of the LC block.  相似文献   

4.
Polystyrene (PST) macromonomers having several allyl groups at the ends were synthesized by the mechanical scission reaction of the main chain in the presence of diallylmalonic acid diethyl ester (DAME). Photosensitive benzophenone groups were introduced on a PST macromonomer molecule by the reaction of these PST macromonomers with benzoyl chloride. The palm-treelike (PST–poly-4-vinylpyridine (P4VP)) sequential copolymers with different compositions were prepared by the radical copolymerization of PST macromonomer with 4VP. The morphological observation of these sequential copolymers was carried out by the transmission electron microscopy. The PST block microdomains were fixed by photocrosslinks (UV irradiation) in the presence of mono- and bifunctional unsaturated compounds in the state of mesomorphic structures. The microdomain fixing of P4VP blocks was carried out by using the vapor of 1, 4-dibromobutane (DBB). After subsequent chemical modifications (quaternization of residual P4VP blocks and sulfonation of PST blocks), the effect of microdomain fixings was elucidated from the moisture content of positive and negative regions. These results are discussed in some detail.  相似文献   

5.
Sulfonated copolymers were synthesized, characterized and used as separation media in electrokinetic chromatography. The polymers used were synthesized from AMPS (2-acrylamido-2-methyl-1-propanesulfonic acid) and LMAm (lauryl methacrylamide) in different mole ratios (from 100:0 to 60:40). Electrophoretic mobilities and methylene selectivities were calculated, which showed the expected correlation with the monomer ratios. The chemical selectivities for the separation of nine solutes by the copolymers were compared with that of sodium lauryl sulfate micelles, showing significant differences. No significant difference in chemical selectivities was observed for copolymers with different monomer ratios. No significant change of hydrophobic microdomain of copolymers was found in background buffers with different ionic strength values, based on the investigation of the retention factors, methylene selectivities and polymer effective mobilities. No change of hydrophobic microdomain of the copolymer solutions was found at copolymer concentrations from 0.17 to 3% (w/v), however, plots of k' versus polymer concentration suggested a different copolymer phase at lower concentrations (from 0 to 0.1%, w/v) from that at higher concentrations (from 0.17 to 3%, w/v). The copolymer with AMPS-LMAm (80:20) could be chosen as optimum copolymer as far as the methylene selectivity, peak symmetry and polymer mobility were concerned.  相似文献   

6.
The water-induced aggregation behavior of rod-coil diblock copolymers based on poly(ethylene oxide) (PEO) and poly{(+)-2,5-bis[4'-((S)-2-methylbutoxy)phenyl]styrene} (PMBPS), PEO104-b-PMBPS53, was investigated in the common solvent THF and in the selective solvent dioxane. Before adding water, PEO104-b-PMBPS53 stayed as single polymer chains no matter what conformation the PEO block took (i.e., either the random coil conformation in THF or the compact globule conformation in dioxane). The critical water content ( approximately 6 wt %) at which PEO104-b-PMBPS53 began to aggregate was also similar in both solvents, indicating that PMBPS dominated the aggregation process. However, the size, the size distribution, and the morphology of aggregates in THF/water were quite different from those in dioxane/water. Narrowly distributed spheres with Rh approximately 20 nm were observed in dioxane, whereas in THF, a bimodal distribution peaked at 3 and approximately 300 nm, was observed. The results from 2D wide-angle X-ray diffraction and polarized optical microscopy demonstrated that the PMBPS blocks packed in a parallel pattern upon aggregation in dioxane/water. The anisotropic disclike structures observed in THF/water also indicated the orientation of the PMBPS blocks upon forming aggregates in dilute solution.  相似文献   

7.
This paper describes the preparation of two layered device comprising of tenoxicam containing layer and a drug free membrane layer based on Geomatrix Technology. Our device based on bilaminated films which produced by a casting/solvent evaporation technique. The drug-hydroxypropyl methylcellulose (HPMC) layer was covered by drug free membrane layer composed of a mixture of different ratios of HPMC and ethyl cellulose (EC). The prepared devices were evaluated for thickness, weight, drug content uniformity, water absorption capacity and in-vitro drug release. The films were also evaluated for appearance, smoothness and transparency. The influence of drug free membrane layer composition and thickness on the drug release pattern was studied on 12 devices (D1 to D12). The results indicate that, the release of drug from HPMC matrixes without the drug free membrane layer was fast and follows diffusion controlled mechanism. The release of drug from the devices D1, D4, D9 and D12 follow the same mechanism, while the release of drug from other devices become linear with time (zero order) and extended for long time especially when thickness and the ratio of EC was increased in the drug free membrane layer. From this study it is concluded that, changing the geometry of drug layer by addition of drug free membrane layer and changing its composition and thickness plays an important role in determining whether the drug free membrane layer is rate-controlling or modulator membrane. Hence it can facilitate the development of different pharmaceutical products with different release pattern.  相似文献   

8.
In this paper, monodisperse poly(styrene-co-divinylbenzene) (PS-DVB) capsules with a bowl-like morphology were prepared controllably by regulating the content of DVB and dispersant. Using as-prepared PS-DVB capsules as building blocks, two-dimensional (2D) uniform hexagonal close-packed array with same orientation of each bowl was successfully fabricated by solvent evaporation. The size distribution showed that the capsules were still spherical in acetone before assembly and thus certified that the capsules caved in after self-assembly. Many factors including DVB content in capsules, experimental temperature and dispersants play important roles on regularity of orientation. Besides, "local self-assembly" array using multi-caved capsule as building blocks was obtained. More study proceeds with it, further advanced materials with complex functionalities or peculiar behavior could be expected.  相似文献   

9.
An order–order transition (OOT) in the sequence of a hexagonally arranged core–shell cylinder to a double‐hexagonally arranged dot in polystyrene‐block‐poly(butadiene)‐block‐poly(2‐vinylpyridine) (SBV) triblock copolymer thin films is reported to be induced upon exposure to a solvent vapor that is strongly selective for the two end blocks. These two kinds of hexagonally arranged structures could form when the film thickness is 44, 123, and 223 nm. When the film thickness is decreased to 13 nm, the ordered structure is absent. The sizes of the core–shell cylinder structures formed with the same annealing time in films of different thickness are compared to address the effects of film thickness on the phase structure. The mechanism is analyzed from the total surface area of the blocks and the effective interaction parameter in the solvent vapor.

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10.
A 3,4-O-unprotected galactal derivative having bulky 6-O-TIPS protection (compound 2) could be regioselectively 3-O-glycosylated with O-(galactopyranosyl) trichloroacetimidates; depending on the protecting group pattern stereoselectively alpha- and beta-linked disaccharides were obtained. With O-(2-azido-2-deoxyglucopyransyl) trichloroacetimidate as donor (compound 10A), glycosylation of 2 and of a 6-O-unprotected galactal derivative led in acetonitrile as solvent exclusively to a beta(1-3)- and a beta(1-6)-linked disaccharide, respectively. Nitration of the galactal moieties of the saccharides followed by Michael-type addition of serine and threonine derivatives (7a,b) installed the alpha-galacto-configuration, thus readily furnishing O-glycosyl amino acid building blocks for the incorporation of core 1, core 2, core 3, core 6, and core 8 structures into glycopeptides. 2-Nitrogalactal and 2-nitroglucal derivatives could be also successfully employed in glycoside bond formation via Michael-type addition in a reiterative manner, affording the corresponding core 5, core 7, and core 6 building blocks. In this approach, highly stereoselective glycoside bond formations were based exclusively on Michael-type addition to the nitro-enol ether moiety of the 2-nitroglycals. Hence, 2-nitroglycals are versatile intermediates for base-catalyzed glycoside bond formation.  相似文献   

11.
Lamellae orientation in lithium-complexed polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) copolymer films on natively oxidized silicon wafers is investigated as a function of film thickness and percentage of carbonyl groups coordinated with lithium ions using cross-sectional transmission electron microscopy and grazing incidence small-angle X-ray scattering. For films with a lower percentage of ionic complexes, the strong surface interaction of the PMMA blocks with the substrate is not changed significantly and the orientation of the lamellar microdomains depends on the film thickness and is dictated by a coupling of the interfacial interactions and the degree of microphase separation. For films with a higher percentage of ionic complexes, the surface interaction is mediated. Along with the enhanced immiscibility between the two blocks, which drives the self-assembly into a stronger microphase segregation, an orientation of the lamellar microdomains normal to the surface is seen, independent of film thickness. Thus, by tuning the amount of ionic complexes, the orientation of lamellar microdomain can be controlled from a random arrangement to being oriented parallel or perpendicular to the film surface without any surface modification or use of external fields, which opens a simple and general route for the fabrication of nanostructured materials.  相似文献   

12.
We developed a novel self-assembly process to fabricate an orderly array of particle wires constructed from a close-packed colloidal crystal without preparation of patterned templates. A substrate was immersed vertically into a SiO2 colloidal solution, and the liquid surface moved downward upon evaporation of solution. Particles formed a mono-/multiparticle layer, which was cut by the periodic drop-off of solution. The orderly array of particle wires was successfully fabricated, showing the suitability of the self-assembly process for the fabrication of nano-/microstructures constructed from nano-/microparticles or blocks. The mechanism of the assembly process and control of thickness, width, and interval of particle wires were further discussed. Moreover, an array of particle wires constructed not from close-packed face-centered cubic (or hexagonal close packed) structure but from two kinds of particles was realized to fabricate an array of particle wires with NaCl structure by this self-assembly process.  相似文献   

13.
Honeycomb macroporous films fabricated by the "breath figures" method were composed of poly2-vinylpyridine (P2VP) distributed in the holes of polystyrene (PS). The porous films exhibited reversible behavior responding to water and different solvent vapors. When the porous film was treated with water, the honeycomb pattern would change to the hexagonal islandlike pattern. Once heated to remove the water, the honeycomb pattern emerged again. When the porous film was exposed to different solvent vapors, the same reversible process appeared. Carbon disulfide (CS(2)), toluene (TOL), and tetrahydrofuran (THF) solvent vapors induced the honeycomb pattern into the ordered islandlike pattern, and ethanol, chloroform, methyl ethyl ketone (MEK), and dimethylformamide (DMF) solvent vapors made the islandlike pattern come back to the honeycomb pattern. The hygroscopic property of P2VP and the polymer-solvent interaction are the driving force for the reversibly switchable morphology. The appropriate control of the hole depth is very crucial in determining the reversible changes.  相似文献   

14.
The surface pressure of monolayers of insoluble diblock copolymers has been measured. One of the blocks is made of poly(t-butyl acrylate) (PtBA), and the other one by polystyrene (PS). The interface is a good solvent for PtBA, while it is a poor solvent for PS. For the sake of comparison, monolayers of a PtBA homopolymer (good solvent conditions) and of poly(4-hydroxy styrene) (P4HS) (poor solvent conditions) have been also measured. It has been found that the relative length of the blocks plays an important role on the shape of the surface pressure Pi versus surface concentration Gamma curves and also on the shape of the equilibrium compressibility versus Gamma curves. However, it does not affect the maximum value of Pi reached at high Gamma's. Surprisingly, the ellipsometric thickness of the copolymer monolayers is almost independent of the relative length of the blocks. The dynamics of the monolayers has been studied by step compression and by surface-light scattering techniques. When M(w,PtBA) > M(w,PS) single exponential relaxations are observed. However, stretched exponentials are obtained for M(w,PS) > or = M(w,PtBA). The relaxation times decrease with increasing Gamma for all the copolymers studied. This is the behavior usually found for poor solvent conditions (P4HS) and opposite to that found for homopolymers under good solvent conditions [PtBA, poly(vinylacetate)]. This means that the solvent quality of the interface does not determine the pressure dependence of tau. The elasticity modulus of the monolayers in the kilohertz range takes values that are similar to those of the high-frequency limit of the relaxation experiments. This means that the relaxation processes have characteristic frequencies below 1 Hz.  相似文献   

15.
Free-standing silica membranes with hierarchical porosity (ca. 300 nm macropores surrounded by 6-8 nm mesopores) and controllable mesopore architecture were prepared by a dual-templating method, with the structural design aided by mesoscale simulation. To create a two-dimensional, hexagonal macropore array, polymeric colloidal hemisphere arrays were synthesized by a two-step annealing process starting with non-close-packed polystyrene sphere arrays on silicon coated with a sacrificial alumina layer. A silica precursor containing a poly(ethylene) oxide-poly(propylene oxide)-poly(ethylene) oxide (PEO-PPO-PEO) triblock-copolymer surfactant as template for mesopore creation was spin-coated onto the support and aged and then converted into the free-standing membranes by dissolving both templates and the alumina layer. To test the hypothesis that the mesopore architecture may be influenced by confinement of the surfactant-containing precursor solution in the colloidal array and by its interactions with the polymeric colloids, the system was studied theoretically by dissipative particle dynamics (DPD) simulations and experimentally by examining the pore structures of silica membranes via electron microscopy. The DPD simulations demonstrated that, while only tilted columnar structure can be formed through tuning the interaction with the substrate, perfect alignment of 2D hexagonal micelles perpendicular to the plane of the membrane is achievable by confinement between parallel walls that interact preferentially with the hydrophilic components (PEO blocks, silicate, and solvent). The simulations predicted that this alignment could be maintained across a span of up to 10 columns of micelles, the same length scale defined by the colloidal array. In the actual membranes, we manipulated the mesopore alignment by tuning the solvent polarity relative to the polar surface characteristics of the colloidal hemispheres. With methanol as a solvent, columnar mesopores parallel to the substrate were observed; with a methanol-water mixed solvent, individual spherical mesopores were present; and with water as the only solvent, twisted columnar structures were seen.  相似文献   

16.
The self-assembly of diaminododecane solubilised by different dendritic peptides, possessing increasing levels of dendritic branching, was investigated. The dendritic peptides were based on l-lysine building blocks and were of first, second and third generation, containing one, three and seven amino acid repeat units respectively. By applying these structures as potential gelator units, the dendritic effect on gelation was investigated. The degree of structuring was modulated, with the dendritic peptide controlling the aggregate morphology and the ability of the self-assembled state to manifest itself macroscopically as gelation. First generation gelator units (G1) did not induce macroscopic gelation with diaminododecane under any conditions, whilst those self-assemblies based on second (G2) and third (G3) generation branches did form gel-phase materials. Furthermore, gel-phase materials based on G2 exhibited optimum gelation behaviour compared to those based on G3(in terms of the thermal strength of the materials). Circular dichroism showed that the dendritic effect, programmed in at the molecular level, is directly related to the degree of chiral organisation within the self-assembled state. The dendritic generation of the peptide controls the pattern of amide-amide hydrogen bonding in terms of binding strength and alignment as determined using NMR methods. The mode of self-assembly can be qualitatively rationalised in terms of an attractive enthalpic interaction (i.e., amide-amide hydrogen bonding), a repulsive interaction (i.e., steric interactions between dendritic peptides) and an entropic term related to the hierarchical organisation of the gelator building blocks. It is argued that the balance between these factors determines the nature of the dendritic effect.  相似文献   

17.
The real time changes occurring within films of cylinder-forming poly(α-methylstyrene-block-4-hydroxystyrene) (PαMS-b-PHOST) were monitored as they were swollen in tetrahydrofuran (THF) and acetone solvent vapors. In situ information was obtained by combining grazing incidence small angle X-ray scattering (GISAXS) with film thickness monitoring of the solvent vapor swollen films. We show that for self assembly to occur, the polymer thin film must surpass a swollen thickness ratio of 212% of its original thickness when swollen in THF vapors and a ratio of 268% for acetone vapor annealing. As the polymer becomes plasticized by solvent vapor uptake, the polymer chains must become sufficiently mobile to self assemble, or reorganize, at room temperature. Using vapors of a solvent selective to one of the blocks, in our case PHOST-selective acetone, an order-order transition occured driven by the shift in volume fraction. The BCC spherical phase assumed in the highly swollen state can be quenched by rapid drying. Upon treatment with vapor of a non-selective solvent, THF, the film maintained the cylindrical morphology suggested by its dry-state volume fraction. In situ studies indicate that self-assembly occurs spontaneously upon attaining the threshold swelling ratios.  相似文献   

18.
Trinuclear building block {Fe(2)NiO(Piv)(6)} (Piv = pivalate), which possessed pseudo-D(3h) symmetry, was linked by two ligands, pseudo-D(3h) ligand tris-(4-pyridyl)pyridine (L1) and C(2v) ligand 4-(N,N-dimethylamino)phenyl-2,6-bis(4-pyridyl)pyridine (L2) into two products with different topologies: 2D coordination polymer [Fe(2)NiO(Piv)(6)(L1)](n) (1), and discrete molecule [{Fe(2)NiO(Piv)(6)}(8) {L2}(12)], which had a nanocube structure (2). In compound 1, trinuclear {Fe(2)NiO(Piv)(6)} blocks were linked through ligand L1 into layers with honeycomb topology. In compound 2, eight trinuclear blocks were located in the vertices of the nanocube, with each L2 ligand linked to two {Fe(2)NiO(Piv)(6)} units. In the crystal structure, these nanocubes formed infinite catenated chains. Analysis of possible structures that could be assembled from these building blocks showed that compounds 1 and 2 corresponded to their respective predicted topologies. Compound [1?solvent] possessed a porous structure, in which the voids were filled by solvent molecules (DMF or DMSO). This structure was retained following desolvation, and compound 1 absorbed significant quantities of N(2) and H(2) at 78?K (S(BET) = 730?m(2) g(-1), H(2) sorption capacity: 0.9?% by weight at 865?Torr). Desolvation of [2?solvent] led to disorder of its crystal structure, and compound 2 only adsorbed negligible quantities of N(2) but adsorbed 0.27?% H(2) (by weight) at 855?Torr and 78?K. The magnetic properties of these complexes (temperature dependence of molar magnetic susceptibility) were governed by the magnetic properties of the trinuclear "building block".  相似文献   

19.
Mg(AlH(4))(2) was produced as a nanocrystalline powder by metathesis of NaAlH(4) and MgCl(2). Starting with a structure estimation which was developed from an evaluation of FTIR data and comparison of structural properties of two solvent adducts, quantum chemical calculations were performed on the density functional theory (DFT) level. The calculated atomic positions were used to simulate an X-ray powder diffraction pattern, based on a trigonal unit cell. The simulated pattern was congruent to experimental data. Thus, magnesium alanate exhibits a CdI(2) layer structure, the layers being formed by Mg atoms occupying the Cd sites and AlH(4) tedrahedra occupying the sites of the iodine atoms in CdI(2).  相似文献   

20.
A novel, simple, and rapid detector using a fluorescent sensor array for discrimination and quantification of different concentrations (ppb level) of pesticides was proposed in this paper. Employing porphyrin, porphyrin derivatives, and chemically responsive dyes as the sensing elements, the developed sensor array based on a cross-responsive mechanism showed a unique pattern of fluorescence changes upon the reaction that lasted just 10 min. The eigenvalues from raw fluorescence spectra were analyzed via a pattern recognition algorithm, including hierarchical cluster analysis (HCA), principal component analysis (PCA), and back-propagation neural network (BPNN). The results showed that HCA, which were used to assess the feasibility and effectiveness of discrimination of the fluorescent sensor array, revealed a distinct separation between different pesticides. PCA and BPNN were used for automatically predicting the concentration of pesticides, and the recovery was 91.29–109.81 % while the lowest relative standard deviation was up to 3.12 %. It indicates a detector based on the fluorescent sensor array is a rapid and feasible sensing platform for the discrimination and quantitative analysis of pesticides, and also shows the possibilities in the related fields of pesticides identification and detection.  相似文献   

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