不对称二聚物粒子在两嵌段共聚物形成的支撑膜上的自组装

结合自洽场理论和密度泛函理论,研究了不对称的二聚物粒子在AB两嵌段共聚物形成的支撑膜上的自组装行为. 不对称的二聚物粒子是由两个不同的球组成的两性分子. 其中一个球与A嵌段相亲,另外一个喜欢B嵌段. 不对称粒子能在支撑膜上形成一个双层结构. 由于衬底的存在,所形成的支撑膜上下两叶的对称性被破坏,导致了二聚物粒子在膜上形成的结构也变的不对称. 随着二聚物粒子浓度的增加,在膜上的二聚物粒子的结构将发生变化,从稀四方、六角、密四方再到圆柱结构. 在一个高浓度的密堆积下,二聚物粒子将形成弯曲的圆柱结构. 在支撑膜     

Dynamics of irregular copolymers

Reptation dynamics of AB copolymers with irregular chemical structure are considered theoretically. It is shown that interactions between A and B monomers could result in a significant slowdown of copolymer dynamics in the disordered (macroscopically homogeneous) state. The dynamical copolymer length N* showing the crossover to the strongly retarded dynamics is calculated. It is shown that contour-length fluctuations (internal reptation modes) give rise to a strong reduction of the slowdown effect and to a strong increase of N* which becomes unrealistically high in the case of a genuinely random chemical structure. The following scaling dependence of N* is predicted for irregular block copolymers: N* proportional, variant delta(-8)chi(-8)n(-8)(0)N(3)(e), where delta is the degree of block polydispersity, chi the Flory AB interaction parameter, and n(0) the mean block length. The strongest dynamical effect of AB interactions is predicted for correlated random copolymers near the critical point related to the formation of microdomain superstructures.     

Binary-component micelle and vesicle: Free energy and asymmetric distributions of amphiphiles between monolayers of vesicle

The real-space two-dimensional self-consistent field theory (SCFT) is employed to study the free energies of micelles and vesicles constituted by binary amphiphilic diblock copolymer AB in homopolymer A. With increasing volume fraction of copolymer AB, there are morphological transitions from the circle micelles to oblate circle-like micelles, to compound structure with inverted micelles in the inner center and micelles outer layer, and to vesicles. Special attentions are paid to the role of the copolymer AB in controlling free energies of the micelles and vesicles, by examining the effect of length ratio of A/B with the fixed whole chain length of AB copolymer, the length effect of A or B block with the corresponding fixed length of B or A block, for one component of copolymer, and the effect of different amphiphile compositions for binary-component copolymer system. The quantity η is provided to describe the asymmetric density distribution of amphiphiles between the inner and outer monolayers of vesicles, and to quantify the relative asymmetric extent of the density distribution between two species of copolymers in binary component vesicles.     

Copolymer at a selective interface and two-dimensional wetting: a grand canonical approach

We consider two different problems involving the localization of a single polymer chain: (i) a periodic AB copolymer at a selective fluid-fluid interface, with the upper (resp. lower) fluid attracting A (resp. B) monomers (ii) a homopolymer chain attracted to a hard wall (wetting). Self avoidance is neglected in both models, which enables us to study their localization transition in a grand canonical approach. We recover the results obtained in previous studies via transfer matrix methods. Moreover, we calculate in this way the loop length distribution functions in the localized phase. Some finite size effects are also determined and tested numerically. Received 13 April 2000     

Secondary super-structures in random copolymers

Secondary domain superstructures in correlated random block copolymers are considered theoretically using the concept of the second order parameter related to fluctuations of the local mean block length. It is shown that the size of secondary domains, , is much larger than the primary domain size, L: , while , where is a small parameter defining the composition asymmetry. Different secondary morphologies are characterized. It is also shown that separation of the system in two macroscopic phases with different primary morphologies predicted earlier using the free energy expansion up to ( is the usual order parameter related to local composition) is an artifact of this widely accepted theoretical model. Received 15 July 1998 and Received in final form 18 January 1999     

Miscibility in poly(L-lactide)- b -poly( $ \upvarepsilon$ -caprolactone) double crystalline diblock copolymers

Thermally stimulated depolarization currents, TSDC, wide-angle X-ray scattering, WAXS, differential scanning calorimetry, DSC, and polarized light optical microscopy, PLOM, have been used to examine poly(L-lactide)-b -poly( -caprolactone) diblock copolymers in a wide composition range. Both components are crystallizable and the miscibility in the amorphous phase has been determined from the behavior of the primary relaxations which are the dielectric manifestation of the glass transition, and also from the superstructural morphology revealed by PLOM and the compositional dependence of the melting points as determined by DSC. Distinct segmental mobilities in the amorphous phase which can be well resolved by TSDC are present; the mode of the slower component shifts to lower temperatures as the PCL content increases while the glass transition of neat PCL is present for all compositions. A relaxation times bimodal distribution is apparent for PCL-rich copolymers. The composition dependence of the multiple glass transitions detected in these weakly segregated copolymers are predicted by the self-concentration model for a miscible blend made of components with a large T_g contrast.     

Complex nanostructured materials from segmented copolymers prepared by ATRP

The development of new controlled/living radical polymerization processes, such as Atom Transfer Radical Polymerization (ATRP) and other techniques such as nitroxide mediated polymerization and degenerative transfer processes, including RAFT, opened the way to the use of radical polymerization for the synthesis of well-defined, complex functional nanostructures. The development of such nanostructures is primarily dependent on self-assembly of well-defined segmented copolymers. This article describes the fundamentals of ATRP, relevant to the synthesis of such systems. The self-assembly of block copolymers prepared by ATRP is illustrated by three examples. In the first, block copolymers of poly(butyl acrylate) with polyacrylonitrile phase separate, leading to spherical, cylindrical or lamellar morphologies, depending on the block copolymer composition. At a higher temperature, polyacrylonitrile block converts to nanostructured carbon clusters, whereas poly(butyl acrylate) block serves as a sacrificial block, aiding the development of designed nanostructures. In the second example, conductive nanoribbons of poly(n-hexylthiophene) surrounded by a matrix of organic polymers are formed from block copolymers prepared by ATRP. The third example describes an inorganic-organic hybrid system consisting of hard nanocolloidal silica particles (20 nm) grafted by ATRP with well-defined polystyrene-poly(benzyl acrylate) block copolymer chains (1000 chains per particle). Silica cores in this system are surrounded by a rigid polystyrene inner shell and softer polyacrylate outer shell. Received 9 July 2002 Published online: 11 March 2003     

Amphiphilic diblock copolymers with adhesive properties: I. Structure and swelling with water

We study asymmetric block copolymers with the simple diblock AB architecture, in the case where the longer block A is both hydrophobic and “soft”, whereas the shorter block B is hydrophilic and “hard”. Materials with such a particular combination of physico-chemical and mechanical properties have distinctive advantages, in particular for designing water-compatible adhesive materials. The phase diagram is established, combining NMR and SAXS characterisations of the materials. The swelling with water is monitored through gravimetry and “time-resolved” SAXS. Indications of maintained adhesive properties in a wet environment are given.     

Effects of polydispersity on the order-disorder transition of diblock copolymer melts

The effect of polydispersity on an AB diblock copolymer melt is investigated using lattice-based Monte Carlo simulations. We consider melts of symmetric composition, where the B blocks are monodisperse and the A blocks are polydisperse with a Schultz-Zimm distribution. In agreement with experiment and self-consistent field theory (SCFT), we find that polydispersity causes a significant increase in domain size. It also induces a transition from flat to curved interfaces, with the polydisperse blocks residing on the inside of the interfacial curvature. Most importantly, the simulations show a relatively small shift in the order-disorder transition (ODT) in agreement with experiment, whereas SCFT incorrectly predicts a sizable shift towards higher temperatures.     

Phase behavior of binary blends of symmetric polystyrene-polybutadiene diblock copolymers studied using SANS

Binary blends of compositionally symmetric diblock copolymers are investigated using small-angle neutron scattering. The study focuses on the miscibility of blends of polystyrene-polybutadiene diblock copolymers as a function of chain length ratio and blend composition, and the results are related to the theoretical phase diagram put forward by M.W. Matsen (J. Chem. Phys. 103, 3268 (1995)). Three different low molar mass copolymers were blended with a high molar mass copolymer. We find very good coincidence with the theoretical phase diagram obtained. Only for blends having a chain length ratio of 0.06, theory predicts that a larger amount of short copolymers can be dissolved in the matrix of long copolymers, and vice versa. With the latter blends and volume fractions of short chains between 0.11 and 0.70, the second-order Bragg-peaks do not vanish, which indicates that the lamellae are asymmetric. Received: 9 February 1998 / Revised: 20 April 1998 / Accepted: 24 April 1998     

Ultrasonic degradation of poly (styrene-co-alkyl methacrylate) copolymers

The ultrasonic degradation of poly (styrene-co-methyl methacrylate) (SMMA), poly (styrene-co-ethyl methacrylate) (SEMA) and poly (styrene-co-butyl methacrylate) (SBMA) copolymers of different compositions was studied. The copolymers were synthesized and NMR spectroscopy was used to determine the composition, and the glass transition temperatures were determined by DSC. The reactivity ratios were determined by the Kelen–Tudos method and it indicated that the copolymers were random. The effect of solvent, temperature and copolymer composition on the ultrasonic degradation rate of these copolymers was investigated. A model based on continuous distribution kinetics was employed to study the degradation kinetics. The degradation rate coefficients of the copolymers decreased with an increase in the styrene content in the copolymer. At any particular copolymer composition the rate of degradation follows the order: SBMA > SEMA > SMMA. Thermogravimetric analysis (TGA) of the copolymers was carried in order to assess their thermal stability. The same order of degradation was observed for the thermal degradation of the copolymers as that observed for ultrasonic degradation.     

The effect of conjugation length distribution on the properties of modified PPV

The aim of this work was to demonstrate the optical properties of a copolymer involving alternating poly(para-phenylene–vinylene) and ether groups derived from the conjugation length distribution. For this, the time-dependent density functional theory (TD-DFT) was used. Thus, different conjugation lengths were considered, where the correlation of the corresponding theoretical spectra, including Raman, optical absorption and photoluminescence, allows us to conclude that the conjugation length distribution is caused by a random distribution of the ether blocks. The weight of each conjugation length representing its contribution is shown by the use of the Raman spectra. Furthermore, the theoretical spectra arising from the response of different conjugation lengths are obtained and compared with the experimental ones.     

Hydrodynamic-flow-driven phase evolution in a polymer blend film modified by diblock copolymers

We have studied surface-directed phase separation in thin films of deuterated polystyrene and poly(bromostyrene) (with 22.7% of monomers brominated) using ³He nuclear reaction analysis, dynamic secondary ion mass spectroscopy and atomic force microscopy combined with preferential dissolution. The crossover from competing to neutral surfaces of the critical blend film (cast onto Au) was commenced: polyisoprene-polystyrene diblock copolymers were added and segregated to both surfaces reducing in a tuneable manner the effective interactions. Two main stages of phase evolution are characterised by i) the growth of two surface layers and by ii) the transition from the four-layer to the final bilayer morphology. For increasing copolymer content the kinetics of the first stage is hardly affected but the amplitude of composition oscillations is reduced indicating more fragmented inner layers. As a result, a faster mass flow to the surfaces and an earlier completion of the second stage were observed. The hydrodynamic flow mechanism, driving both stages, is evidenced by nearly linear growth of the surface layer and by mass flow channels extending from the surface layer into the bulk. The final bilayer structure, formed even for the surfaces covered by strongly overlapped copolymers, is indicative of long-range (antisymmetric) surface forces. Received 15 March 2000 and Received in final form 9 February 2001     

Self-assembly of block copolymers grafted onto a flat substrate:Recent progress in theory and simulations

Block copolymers are a class of soft matter that self-assemble to form ordered morphologies on the scale of nanometers, making them ideal materials for various applications. These applications directly depend on the shape and size of the self-assembled morphologies, and hence, a high degree of control over the self-assembly is desired. Grafting block copolymer chains onto a substrate to form copolymer brushes is a versatile method to fabricate functional surfaces. Such surfaces demonstrate a response to their environment, i.e., they change their surface topography in response to different external conditions. Furthermore, such surfaces may possess nanoscale patterns, which are important for some applications; however, such patterns may not form with spun-cast films under the same condition. In this review, we summarize the recent progress of the self-assembly of block copolymers grafted onto a flat substrate. We mainly concentrate on the self-assembled morphologies of end-grafted AB diblock copolymers, junction point-grafted AB diblock copolymers(i.e.,Y-shaped brushes), and end-grafted ABA triblock copolymers. Special emphasis is placed on theoretical and simulation progress.     

Ellipsometry measurements of glass transition breadth in bulk films of random, block, and gradient copolymers

Bulk films of random, block and gradient copolymer systems were studied using ellipsometry to demonstrate the applicability of the numerical differentiation technique pioneered by Kawana and Jones for studying the glass transition temperature (T _g) behavior and thermal expansivities of copolymers possessing different architectures and different levels of nanoheterogeneity. In a series of styrene/n -butyl methacrylate (S/nBMA) random copolymers, T _g breadths were observed to increase from ～ 17^° C in styrene-rich cases to almost 30^° C in nBMA-rich cases, reflecting previous observations of significant nanoheterogeneity in PnBMA homopolymers. The derivative technique also revealed for the first time a substantial increase in glassy-state expansivity with increasing nBMA content in S/nBMA random copolymers, from 1.4×10^-4 K-1 in PS to 3.5×10^-4 K-1 in PnBMA. The first characterization of block copolymer T _g ’s and T _g breadths by ellipsometry is given, examining the impact of nanophase-segregated copolymer structure on ellipsometric measurements of glass transition. The results show that, while the technique is effective in detecting the two T _g ’s expected in certain block copolymer systems, the details of the glass transition can become suppressed in ellipsometry measurements of a rubbery minor phase under conditions where the matrix is glassy; meanwhile, both transitions are easily discernible by differential scanning calorimetry. Finally, broad glass transition regions were measured in gradient copolymers, yielding in some cases extraordinary T _g breadths of 69- 71^° C , factors of 4-5 larger than the T _g breadths of related homopolymers and random copolymers. Surprisingly, one gradient copolymer demonstrated a slightly narrower T _g breadth than the S/nBMA random copolymers with the highest nBMA content. This highlights the fact that nanoheterogeneity relevant to the glass transition response in selected statistical copolymers can be comparable to or exceed that observed in moderately phase-segregated gradient copolymers.     

Smart Nanovalves with Thermoresponsive Amphiphilic Triblock Copolymer Brushes

Nanochannels modified with stimuli-responsive copolymer brushes offer a smart nanovalve mechanism. The potential application of these special nanovalves is wide-ranging and includes the areas of drug delivery and signal transduction, as well as molecular machines. In this study, molecular dynamics simulations were performed to study nanovalve systems that use thermo-responsive amphiphilic triblock copolymer brushes grafted onto the surface of the nanochannel. Varying the system temperature facilitated the extension/collapse transition of the copolymer brushes, which resulted in the opening/closing of the nanochannels. The results of the investigation of the effect of the grafting density and the composition of the copolymers on the conformational transition behavior showed that the composition of copolymer has a significant influence on the nanovalve system. A remarkable result is the effectiveness of the use of intermediate or relatively low grafting density in obtaining an ideal controlling effect on the nanochannels. Our work provides a fundamental understanding of nanovalves that utilize thermo-responsive copolymers, and guidance for the design of a smart nanochannel.     

On the electronic structure and conduction properties of polymeric quasi-one-dimensional model superlattices: Study of Type I and Type II-staggered superlattices

The electronic spectrum of the various quasi-one-dimensional model compositional superlattices (copolymers) (A_mB_n)_x belonging to class of Type I and Type II-staggered superlattices have been calculated in the tight binding approximation using the direct numerical approach. The trends in their electronic structure and conduction properties as a function of (i) composition (m/n), (ii) block sizes m and n and (iii) arrangement of the blocks in the copolymer chain are discussed. The results obtained are important guidelines for designing copolymers with tailor made conduction properties.     

Structure of colloidal complexes obtained from neutral/poly- electrolyte copolymers and oppositely charged surfactants

We report on the phase behavior and scattering properties of colloidal complexes made from block copolymers and surfactants. The copolymer is poly(sodium acrylate)-b-poly(acrylamide), hereafter abbreviated as PANa-PAM, with molecular weight 5000 g/mol for the first block and 30000 g/mol for the second. In aqueous solutions and neutral pH, poly(sodium acrylate) is a weak polyelectrolyte, whereas poly(acrylamide) is neutral and in good-solvent conditions. The surfactant is dodecyltrimethylammonium bromide (DTAB) and is of opposite charge with respect to the polyelectrolyte block. Combining dynamical light scattering and small-angle neutron scattering, we show that in aqueous solutions PANa-PAM diblocks and DTAB associate into colloidal complexes. For surfactant-to-polymer charge ratios Z lower than a threshold (Z(C) approximately 0.3), the complexes are single surfactant micelles decorated by few copolymers. Above the threshold, the colloidal complexes reveal an original core-shell microstructure. We have found that the core of typical radius 100-200 A is constituted from densely packed surfactant micelles connected by the polyelectrolyte blocks. The outer part of the colloidal complex is a corona and is made from the neutral poly(acrylamide) chains. Typical hydrodynamic sizes for the whole aggregate are around 1000 A. The aggregation numbers expressed in terms of numbers of micelles and copolymers per complex are determined and found to be comprised between 100-400, depending on the charge ratio Z and on the total concentration. We have also shown that the sizes of the complexes depend on the exact procedure of the sample preparation. We propose that the driving mechanism for the complex formation is similar to that involved in the phase separation of homopolyelectrolyte/surfactant systems. With copolymers, the presence of the neutral blocks prevents the macroscopic phase separation from occurring.     

Thermal behavior of vinylidene chloride—methyl acrylate copolymers

The thermal behavior of random copolymers of vinylidene chloride-methyl acrylate (VDC-MA) was monitored with differential scanning calorimetry. The effects of composition, annealing, and heating rate on the copolymer melting process were studied. Increasing levels of comonomer decreased the crystalline melting point and percent crystallinity of the copolymers. A combination of information obtained from heating rate and small-angle x-ray scattering studies led to a model of the melting behavior of PVDC and its copolymers. Apparently a simultaneous melting/recrystallization phenomenon occurs in these materials during heating.     

Effects of compositional asymmetry in phase behavior of ABA triblock copolymer melts from Monte Carlo simulation

We simulate ABA triblock copolymer melts using a lattice Monte Carlo method, known as cooperative motion algorithm, probing various degrees of compositional asymmetry. Selected order-disorder transition lines are determined in terms of the segment incompatibility, quantified by product χN , and the triblock asymmetry parameters, α and β. We correlate the results of the simulation with the self-consistent field theory and an experimental study of polyisoprene-polystyrene-polyisoprene triblock melt by Hamersky and coworkers. In particular, we confirm the mean-field prediction that for highly asymmetric triblocks the short A -block is localized in the middle of the B -domain due to an entropic advantage. This results in the middle block relaxation and is consistent with the experimental data indicating that as the relatively short A -blocks are grown into AB diblock, from the B -block side, the order-disorder transition temperature is considerably depressed.