Process and kinetics of order-order transition from bcc-sphere to hex-cylinder in polystyrene-block-polyisoprene-block-polystyrene: Time-resolved SAXS and TEM studies

We have studied the process and kinetics of the order-order phase transition (OOT) from spheres in a body-centered-cubic lattice (bcc-sphere) to hexagonally packed cylindrical microdomains (hex-cylinder) for a polystyrene-block-polyisoprene-block-polystyrene triblock copolymer, induced by abrupt temperature drops. In this study, time-resolved small-angle X-ray scattering (SAXS) measurements are conducted to investigate the OOT processes in situ and at real time. Transmission electron microscopy observations for specimens rapidly frozen below the glass transition temperature at particular times in the OOT processes are also conducted to visualize the transient structures developed during the OOT. We elucidated the following pieces of evidence. (I) The OOT proceeds via the nucleation and growth process as follows: After quenching the specimen, the system stays at a bcc-sphere state in the incubation period, t_i. After this period, (II) anisotropic grains of hex-cylinder are nucleated at the vicinity of grain boundaries of bcc sphere. (III) The growth of the grains appears to be faster along the cylindrical axis than along the direction perpendicular to it, on the contrary to the growth of hex-cylinder from the disordered phase. The OOT involves deformation of spherical domains toward a [111] direction of a bcc lattice, followed by coalescence and connection of them to cylindrical microdomains. (IV) The rate of OOT as observed by time-resolved SAXS was found to depend on quench depth, ΔT (≡T_OOT−T_cyl)=4-10 K, or thermodynamic driving force for the OOT, ε (≡ΔT/T_OOT)=0.0087-0.0217, where T_OOT is the OOT temperature between hex-cylinder and bcc-sphere: The larger ΔT or ε is, the shorter t_i is and the faster the transformation rate, R_T, is after the incubation time. (V) Consequently, the time change of a characteristic parameter as observed by SAXS at various ΔTs fall on to a master curve when real time is reduced with t_i, revealing that the following two intriguing conclusions: (i) t_i and have the same temperature dependence, and hence the system has only single time scale, and (ii) the transformation after the incubation period starts only when the characteristic parameter reaches a temperature independent critical value.     

Crystallization kinetics of some new olefinic block copolymers

Blocky ethylene-octene copolymers synthesized by chain-shuttling polymerization differ from statistical copolymers in their rapid rate of crystallization and in the formation of space-filling spherulites even when the crystallinity is as low as 7%. The bulk crystallization rate, measured with DSC, was rapid even in copolymers with a relatively large fraction of non-crystallizable soft block and only slowed somewhat as the amount of crystallizable hard block decreased from 100 to 18 wt%. As measured with the polarized optical microscope, the linear spherulite growth rate exhibited the same dependence on soft block content as the bulk crystallization rate. The fold surface energy was extracted from an analysis of the growth rate according to the Lauritzen-Hoffman theory. A gradual increase in the fold surface energy with soft block content reflected some increasing disorder of the fold surface. In contrast, even a small amount of statistically distributed comonomer was very effective in disrupting the fold surface regularity as demonstrated by the high fold surface energy.     

Can rheometry measure crystallization kinetics? A comparative study using block copolymers

The isothermal crystallization kinetics and the melting behavior of block copolymers of poly(ethylene oxide) and poly(1,2-butylene oxide) were studied by means of differential scanning calorimetry and rheometry to test the validity of rheological methods. The copolymers had different block lengths (hence different melt structures) and different block architectures (diblock EB and triblock EBE and BEB). For crystallization from disordered and lamellar melts, half-times for crystallization from rheometry were much shorter, and Avrami exponents were higher, than those from calorimetry. For more-highly structured melts (gyroid, hexagonal and cubic spheres), the half-times were comparable but the Avrami exponents from rheometry were still high compared to DSC. The differences between the rates of crystallization from calorimetry and rheometry are an artifact of the rheological measurements, at low crystallite volume fractions the rheology is directly proportional to the degree of crystallinity but at high crystalline volume fractions the proportionality is lost due to the changing connectivity of the crystals. The rates of crystallization ranked in order: lamellar>disordered≈gyroid>hexagonal?cubic spheres. Other things being equal, the effect of block architecture was insignificant.     

Influence of block lengths and symmetries of block copolymers on phase behavior of polymer A/polymer B/block copolymer ternary blends

Monte Carlo simulations were used to investigate the compatibilizing effects of diblock copolymers in A/B/A-B diblock copolymer ternary blends and triblock copolymers in A/B/triblock copolymer ternary blends, respectively. The volume fraction of homopolymer A was 19% and was the dispersed phase. The simulation results show that diblock copolymers with longer A-blocks are more efficient as compatibilizers, and symmetric triblock copolymers with a shorter middle block length are easily able to bridge each other through the association of the end blocks. This kind of triblock copolymers have relatively high ability to retard phase separation as compatibilizers.     

Oxidation effect on templating of metal oxide nanoparticles within block copolymers

Amphiphilic norbornene-b-(norbornene dicarboxylic acid) diblock copolymers with different block ratios were prepared as templates for the incorporation of iron ions using an ion exchange protocol. The disordered arrangement of iron oxide particles within these copolymers was attributed to the oxidation of the iron ions and the strong interactions between iron oxide nanoparticles, particularly at high iron ion concentrations, which was found to affect the self-assembly of the block copolymer morphologies.     

Time-resolved GISAXS and cryo-microscopy characterization of block copolymer membrane formation

Time-resolved grazing-incidence small-angle X-ray scattering (GISAXS) and cryo-microscopy were used for the first time to understand the pore evolution by copolymer assembly, leading to the formation of isoporous membranes with exceptional porosity and regularity. The formation of copolymer micelle strings in solution (in DMF/DOX/THF and DMF/DOX) was confirmed by cryo field emission scanning electron microscopy (cryo-FESEM) with a distance of 72 nm between centers of micelles placed in different strings. SAXS measurement of block copolymer solutions in DMF/DOX indicated hexagonal assembly with micelle-to-micelle distance of 84–87 nm for 14–20 wt% copolymer solutions. GISAXS in-plane peaks were detected, revealing order close to hexagonal. The d-spacing corresponding to the first peak in this case was 100–130 nm (lattice constant 115–150 nm) for 17 wt% copolymer solutions evaporating up to 100 s. Time-resolved cryo-FESEM showed the formation of incipient pores on the film surface after 4 s copolymer solution casting with distances between void centers of 125 nm.     

Effect of block compositions of amphiphilic block copolymers on the physicochemical properties of polymeric micelles

Amphiphilic block copolymers with various chain lengths of poly(n-butyl methacrylate) blocks (PBMA) and poly(N-acryloylmorpholine) blocks (PAM) were prepared by RAFT polymerization. Packing parameter of block polymers in water (β < 0.2) indicated the formation of core-corona structures, which was further confirmed from a difference between core- and corona-forming chain surface areas. Hydrodynamic micellar size was related with the numbers of BMA (N_BMA) and AM (N_AM), and their ratios (N_BMA/N_AM). With increasing N_BMA/N_AM value, the polymer aggregation numbers and inner core sizes increased, while the critical micelle concentrations, the corona thickness, and the second virial coefficient of block copolymer micelles decreased. These properties changed with increasing N_BMA/N_AM value resulted in a linear increase in corona chain unit density (ρ_AM) that limited chain mobility. Thus, the interaction between the micelles and serum protein at low ρ_AM disappeared at a higher value. Consequently, both micellar properties and biocompatible effect can be regulated by tailoring the block compositions of amphiphilic polymers.     

Correlation between crystallization kinetics and melt phase behavior of crystalline-amorphous block copolymer/homopolymer blends

We show that the phase behavior of the strongly segregated blend consisting of a crystalline-amorphous diblock copolymer (C-b-A) and an amorphous homopolymer (h-A), which depends on the degree of wetting of A blocks by h-A, can be probed by the crystallization kinetics of the C block. A lamellae-forming poly(ethylene oxide)-block-polybutadiene (PEO-b-PB) was blended with PB homopolymers (h-PB) of different molecular weights to yield the blends exhibiting ‘wet brush’, ‘partially dry brush’, and ‘dry brush’ phase behavior in the melt state. The crystallization rate of the PEO blocks upon subsequent cooling, as manifested by the freezing (crystallization) temperature (T_f), was highly sensitive to the morphology and spatial connectivity of the microdomains governed by the degree of wetting of PB blocks. As the weight fraction of h-PB reached 0.48, for instance, T_f experienced an abrupt rise as the system entered from the wet-brush to the dry-brush regime, because the crystallization in the PEO cylindrical domains in the former required very large undercooling due to a homogeneous nucleation-controlled mechanism while the process could occur at the normal undercooling in the latter since PEO domains retained lamellar identity with extended spatial connectivity. Our results demonstrate that as long as the C block is present as the minor constituent the melt phase behavior of C-b-A/h-A blends can also be probed using a simple cooling experiment operated under differential scanning calorimetry (DSC).     

Controlling the phase behavior of block copolymers via sequential block growth

Block copolymers remain one of the most extensively investigated classes of polymers due to their abilities to self-organize into various nanostructures and modify polymer/polymer interfaces. Despite fundamental and technological interest in these materials, only a handful of experimental phase diagrams exist due to the laborious task of preparing such diagrams. In this work, two copolymer series are each synthesized from a single macromolecule via sequential living anionic polymerization to yield molecularly asymmetric diblock and triblock copolymers systematically varying in composition. The phase behavior and morphology of these copolymers are experimentally interrogated and quantitatively compared with predictions from mean-field theories, which probe copolymer phase behavior beyond current experimental conditions.     

Polarized optical microscopy study on the superstructures of oxyethylene/oxybutylene block copolymers

The superstructures of oxyethylene/oxybutylene block copolymers with different compositions and architectures (E_mB_n, B_nE_mB_n and E_mB_nE_m) were studied using polarized optical microscopy (POM). Several novel superstructures, such as fibril crystals and different frontiers of spherulites and crystallized regions, have been observed. It is found that the ability of forming spherulites is reduced with the decrease in the volume fraction of the crystallizable block. The unfavorable interaction between the blocks, which can be indicated by order-disorder transition temperature (T_ODT), also affects the formation of superstructure. The B_nE_mB_n triblock copolymers exhibit the strongest ability of organization into spherulites, whereas the E_mB_nE_m triblock copolymers show the weakest ability of organization into spherulites.     

Nanoporous materials from stable and metastable structures of 1,2-PB-b-PDMS block copolymers

Experimental procedures used at the preparation and characterization stages of nanoporous materials (NPM) from 1,2-polybutadiene-b-polydimethylsiloxane (1,2-PB-b-PDMS) block copolymers are presented. The NPM were obtained from self-assembled block copolymers after firstly cross-linking 1,2-PB (the matrix component) and secondly degrading PDMS (the expendable component). Depending on the temperature of the cross-linking reaction different morphologies can be ‘frozen’ from the same block copolymer. Starting with a block copolymer precursor of lamellar morphology at room temperature, the gyroid structure or a metastable structure showing hexagonal symmetry (probably HPL) were permanently captured by cross-linking the precursor at 140 °C or at 85 °C, respectively. PDMS was degraded by reaction with tetrabutylamonium fluoride; considerations on the mechanism of cleaving reaction are presented. The characterization of the materials at different stages of preparation includes gravimetry, infrared spectroscopy, small angle x-ray scattering, electron microscopy and isothermal nitrogen adsorption experiments.     

A delicate ionizable-group effect on self-assembly and thermogelling of amphiphilic block copolymers in water

A carboxyl-capped PLGA-PEG-PLGA block copolymer (PLGA: poly(d,l-lactic acid-co-glycolic acid), PEG: poly(ethylene glycol)) was synthesized, and its self-assembly and thermogelling behaviors in water were studied at different pH values. While the aqueous solution of the virgin PLGA-PEG-PLGA block copolymer with the composition in this paper did not undergo sol-gel transition, that of the end-capped derivative exhibited four macroscopic states, sol, turbid sol, physical gel, and precipitate, dependent upon temperature and pH. Especially between pH 4.5 and 5.0, a concentrated aqueous system underwent sol-gel-(turbid sol)-precipitate transitions upon increase of temperature. Complex of dissociation constant pK_a of weak-acid groups on the micelle surfaces was illustrated. Dynamic light scattering, hydrophobic dye solubilization, transmission electron microscopy, NMR, and potentiometric titration were used to examine the relationship between ionization of the end groups of the polymer chains on the molecular level, micellization of the amphiphilic block copolymers on the supermolecular level, and physical gelation on the macroscopic level. The present research reveals the complex of the multi-scale self-assembly of amphiphilic polymer ionomers in a selective solvent.     

Effect of solvents on closed-loop phase behavior of block copolymers

We studied the effect of solvent selectivity on the closed-loop phase behavior of a polystyrene-block-poly(n-pentyl methacrylate) copolymer. It was found that the lower disorder-to-order transition temperature (LDOT) and upper order-to-disorder transition temperature (UODT) consisting of the closed-loop were very sensitive to the selectivity of the solvent. With the addition of very small amounts of non-selective solvents such as di-n-octyl phthalate and dimethyl phthalate, the LDOT increased rapidly, whereas the UODT decreased dramatically; thus, the immiscibility loop was shrunk greatly. On the other hand, both the LDOT and UODT decreased with increasing amount of dodecanol, a highly selective solvent to poly(n-pentyl methacrylate) block. However, the decrease in the LDOT was greater than that of the UODT, leading to an increased immiscibility loop.     

Toward a toolbox of functional block copolymers via free-radical addition of mercaptans

This work demonstrates the applicability of the free-radical addition of ω-functional mercaptans onto 1,2-polybutadienes as a modular synthetic pathway toward a toolbox of diverse functional block copolymers. Functional groups included, for instance electrolytes (carboxylic acid and amine), l-amino acid, and fluorocarbon. The number of functional groups attached to the polymer was lower than that of double bonds reacted (degree of functionalization=50–85%, typically 70–80%) due to cyclization of two neighboring units, but the narrow molecular-weight distribution of the parent (co)polymer was always maintained.     

Photoresponsive liquid crystalline block copolymers: From photonics to nanotechnology

Being one of the most fascinating multi-functional materials, photoresponsive liquid crystalline block copolymers (PLCBCs) have attracted much attention because of their light controllable properties of supramolecularly self-assembled structures. These originate from their unique features combining the advanced function of photoresponsive liquid crystalline polymers (PLCPs) with the inherent property of microphase separation of block copolymers (BCs). Benefiting from recent progresses in materials chemistry, diverse PLCBCs have been designed and synthesized by controlled polymerization using different synthetic routes and strategies. Generally, PLCBCs show different performance depending on their self-organization and molecular composition, with the PLCP blocks in the minority phase or in the majority phase. One of the most important properties of PLCBCs is supramolecular cooperative motion, resulted from the interactions between liquid crystalline elastic deformation and microphase separation, which enables them to self-assemble into regularly ordered nanostructures in bulk films with high reliability. These nanostructures contribute to improving the optical performance of polymer films by eliminating the scattering of visible light, in favor of their photonic applications. With the help of liquid crystal alignment techniques, both parallel and perpendicular patterning of nanostructures has been fabricated in macroscopic scale with excellent reproducibility and mass production, which provides nanotemplates and nanofabrication processes for preparing varieties of nanomaterials. Recent findings about PLCBCs including their synthesis, diagram of microphase separation, structure-property relationship, precise control of nanostructure as well as their applications in photonics to nanotechnology are reviewed.     

Preparation and properties of semifluorinated block copolymers of 2-(dimethylamino)ethyl methacrylate and fluorooctyl methacrylates

Semifluorinated block copolymers of poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and poly(fluorooctyl methacrylates) (PFOMA) were prepared using group transfer polymerisation via sequential monomer addition. Wide ranges of copolymers were obtained with good control over both molecular weight and composition by adjusting the monomers/initiator ratio. The micellar characteristics of the copolymers in water and chloroform were investigated by quasi-elastic light scattering and transmission electron microscopy. The size and morphologies of micelles were greatly influenced by copolymer composition, pH, and temperature. In addition, the solubility of copolymers and the formation of water-in-carbon dioxide (W/C) microemulsions were described in terms of the cloud points. The block copolymers exhibited the excellent ability of stabilizing W/C microemulsions.     

Directed self-assembly of block copolymers by chemical or topographical guiding patterns: Optimizing molecular architecture,thin-film properties,and kinetics

Patterning strategies based on directed self-assembly (DSA) of block copolymers, as one of the most appealing next-generation lithography techniques, have attracted abiding interest. DSA aims at fabricating defect-free geometrically simple patterns on large scales or irregular device-oriented structures. Successful application of DSA requires to control and optimize multiple process parameters related to the bulk morphology of the block copolymer, its interaction with the chemical or topographical guiding pattern, and the kinetics of structure formation. Most studies have focused on validating DSA patterning techniques using PS-b-PMMA block copolymers as a prototypical material. As the development of DSA techniques advances, recent efforts have been devoted to extending the materials selection in order to fabricate more complex geometric patterns or patterns with smaller characteristic dimensions. How to select appropriate polymer materials in a vast parameter space is a critical but also challenging step. In this review, we discuss recent progress in the research of DSA of block copolymers focusing on three aspects: (i) screening the block copolymer materials, (ii) controlling the film properties, and (iii) tailoring the phase separation kinetics.     

Effects of neutral solvent addition on the body-centered cubic spheres of block copolymers

We employ self-consistent mean-field (SCMF) theory in studying the body-centered cubic (bcc) spheres of block copolymers in the presence of a neutral solvent. First we examine the accuracy of the dilution approximation then analyze the dependence of the bcc structural sizes with copolymer volume fraction ?, the interaction parameter χ_AB, and degree of copolymerization N. Our results reveal that both distribution of each component and the micro-structural length scales are greatly influenced by each parameter ?, χ_AB, and N. As expected, with decreasing ?, more solvent distributes non-uniformally in the segregated domains, therefore deviation from the dilution approximation increases. This also suggests that when the effective segregation parameter ?χ_ABN is fixed, a larger deviation is expected as χ_ABN increases (i.e. ? decreases). Although when both χ_ABN and ? are fixed, decreasing N (i.e. increasing χ_AB) enlarges the deviation from the dilution approximation. Furthermore, this solvent non-uniformity behavior is so significant that it even affects the dependence of the domain spacing L^* and the matrix length Λ^* with respect to (χ_AB)_effN=?χ_ABN near the ODT. When the systems are in molten state and/or in the concentrated regime, both L^* and Λ^* exhibit a sharp increase behavior as ODT is approached, due to many of the minority blocks being pulled from the spherical domains and swelling the matrix. With increasing solvent amount and/or χ_ABN, we observe that the increase of the degree for the minority blocks pulled from the spheres into the matrix near the ODT is not as significant as that in the melt. As such, the sharp increase behavior in L^* as well as Λ^* near the ODT smoothens and even disappears.     

Structural change with blending of crystalline/amorphous block copolymers having different types of microphase separations

Two kinds of polystyrene/polyethylene diblock copolymers exhibiting bicontinuous and spherical microphase separations were blended at different ratios. Initial films were prepared by hot xylene dissolution, followed by casting and drying. The obtained films were melted and isothermally crystallized at various temperatures. Differential scanning calorimetry melting peak temperatures for the isothermally crystallized films suggested that characteristic crystal growth occurred at critical bicontinuous/spherical blend ratios of 90/10 and 85/15. The crystalline structure consisted of interior pure crystals and exterior defective crystals. Transmission electron microscopy observations of these blended films indicated the progressive isolation of the amorphous phase with increases in the spherical component. Specifically, the mixed morphologies of both the bicontinuous and spherical structures were obtained for the above critical blend ratios. Analysis implied that this unique morphology was formed as a result of the combination of the crystal nucleus effect and the competitive growth effect.