Diblock Copolymer Solutions Research Articles

A Computer Simulation Study on Deposition Patterns of Cyclic Diblock Copolymer Solution Nanodroplets: Influence of Polymer Length and Concentration

A Computer Simulation Study on Deposition Patterns of Cyclic Diblock Copolymer Solution Nanodroplets: Influence of Polymer Length and Concentration

Pronounced Cold Crystallization and Hydrogen Bonding Distortion of Water Confined in Microphases of Double Zwitterionic Block Copolymer Aqueous Solutions.

Advanced materials leveraging water control are garnering considerable interest, with the state of water emerging as a critical aspect of material design. This study explored the impact of microphase separation on water using aqueous solutions of double zwitterionic diblock copolymers, specifically poly(carboxybetaine methacrylate) and poly(sulfobetaine methacrylate) (PCB2-b-PSB4). These copolymers form a mesoscale periodic ordered lattice structure consisting of two distinct aqueous phases. Through differential scanning calorimetry and X-ray emission spectroscopy, it was found that water in these PCB2-b-PSB4 aqueous solutions exhibits pronounced cold crystallization and subtle distortions in hydrogen-bonding configurations.

Deposition patterns formed by the evaporation of linear diblock copolymer solution nanodroplets on solid surfaces.

The evaporation-induced deposition pattern of the linear diblock copolymer solution has attracted attention in recent years. Given its critical applications, we study deposition patterns of the linear diblock copolymer solution nanodroplet on a solid surface (the wall) by molecular dynamics simulations. This study focuses on the influence of the nonbonded interaction strength, including the interaction between the wall and polymer blocks (ɛAW and ɛBW), the interaction between the solvent and the wall (ɛSW), and the interaction between polymer blocks (ɛAB). Conditions leading to diverse deposition patterns are explored, including the coffee-ring and the volcano-like structures. The formation of the coffee-ring structure is attributed to receding interfaces, the heterogeneity inside the droplet, and the self-assembly of polymer chains. This study contributes to the establishment of guidelines for designing deposition patterns of the linear diblock copolymer solution nanodroplet, which facilitates practical applications such as inkjet printing.

Synthesis of pH/redox-double-responsive ferrocene-containing diblock copolymers and their application in controlled release

A novel pH/redox-double-responsive ferrocene-containing diblock copolymer of poly(ethylene glycol)-block-poly[2-(2-((2-ferrocenyl ethyl ester) (methyl) amino) ethoxy) ethyl methacrylate] [mPEG113-b-P(Fe–N-EOMA)] was synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. mPEG113-b-P(Fe–N-EOMA) is amphiphilic with PEG as hydrophilic block and the part containing ferrocene as hydrophobic block. For comparison, three other diblock copolymers were prepared by changing the molecular weight of the hydrophilic block and the microstructure of the hydrophobic block. The diblock copolymers have a critical pH in solution and increases with the increase of the hydrophilicity of the copolymers. The redox-response was confirmed by the shift of characteristic peak of ferrocene in the UV/vis absorption spectrum after adding FeCl3/VC. The self-assembly behavior of these diblock copolymers in solution were then investigated. It shows that they have low critical micelle concentration (cmc), and the cmc decreases as the hydrophobicity of copolymers increases. Their morphology is varied, including sphere, lamella, aggregated sphere, and can be reversible changed by the stimulation of pH and redox. Finally, mPEG113-b-P(Fe–N-EOMA) was applied to the release of Nile Red (NR), which showed a good release efficiency. The prepared diblock copolymers have sensitive and reversible response properties, which provided ideas for the design of multistimuli-responsive polymers, and have good application prospects in drug-release.

Synthesis and Thermo-Responsive Behavior of Poly(N-isopropylacrylamide)-b-Poly(N-vinylisobutyramide) Diblock Copolymer.

Thermo-responsive diblock copolymer, poly(N-isopropylacrylamide)-block-poly(N-vinylisobutyramide) was synthesized via switchable reversible addition-fragmentation chain transfer (RAFT) polymerization and its thermal transition behavior was studied. Poly(N-vinylisobutyramide) (PNVIBA), a structural isomer of poly(N-isopropylacrylamide) (PNIPAM) shows a thermo-response character but with a higher lower critical solution temperature (LCST) than PNIPAM. The chain extension of the PNVIBA block from the PNIPAM block proceeded in a controlled manner with a switchable chain transfer reagent, methyl 2-[methyl(4-pyridinyl)carbamothioylthio]propionate. In an aqueous solution, the diblock copolymer shows a thermo-responsive behavior but with a single LCST close to the LCST of PNVIBA, indicating that the interaction between the PNIPAM segment and the PNVIBA segment leads to cooperative aggregation during the self-assembly induced phase separation of the diblock copolymer in solution. Above the LCST of the PNIPAM block, the polymer chains begin to collapse, forming small aggregates, but further aggregation stumbled due to the PNVIBA segment of the diblock copolymer. However, as the temperature approached the LCST of the PNVIBA block, larger aggregates composed of clusters of small aggregates formed, resulting in an opaque solution.

Deposition Patterns Induced by the Evaporation of the Cyclic Diblock Copolymer Solution Droplet

Deposition Patterns Induced by the Evaporation of the Cyclic Diblock Copolymer Solution Droplet

Two-dimensional (2D) quasi-living crystallization-driven self-assembly of polyethylene-b-hyperbranched polyglycidol diblock copolymers in solution.

This paper presents a systematic investigation of the crystalline nucleation, micellization, two-dimensional (2D) growth of polyethylene-b-hyperbranched polyglycidol (PE-b-hbPG) copolymers in solutions during cooling and isothermal crystallization. As a result, lozenge-shaped monolayer or multilayer lamellar crystals were prepared by optimizing the "self-nucleation" conditions. The effect of crystallization temperatures (Tc), critical micelle temperature (CMT), selective solvents, and the topology of block copolymers (BCPs) on the growth of 2D lozenge-shaped crystals is extensively explored using TEM, AFM and in situ DLS techniques. The results demonstrate that the formation of a perfect lozenge-shaped monolayer crystal is contingent upon the relationship between CMT and Tc of the BCPs (CMT < Tc), as well as the isothermal crystallization temperature Tiso (CMT < Tiso < Tc). This significant finding provides a feasibility programme for the preparation of 2D lamellar crystals using the "self-nucleation" approach from an alternative viewpoint of the corona topology.

Influence of Polymer Chain Length and Concentration on the Deposition Patterns of Linear Diblock Copolymer Solution Nanodroplets

We perform molecular dynamics simulations to study deposition patterns of the linear diblock copolymer solution nanodroplet on the solid surface (the wall). The current work mainly investigates the influence of...

Nanostructure Scaling in Semi‐Dilute Triblock Copolymer Gels

AbstractThere is a considerable body of work that describes the scaling of diblock copolymer micelle dimensions in dilute and semi‐dilute solution based upon block degrees of polymerization and copolymer concentration. However, there is a lack of analogous information for semi‐dilute ABA triblock copolymer gels, which consist of ABA triblock copolymer dissolved in midblock‐selective (B‐selective) solvent. The present study uses small angle X‐ray scattering to extract micelle dimensions for numerous triblock copolymer gels that vary in copolymer identity (and hence block lengths) and copolymer concentration, as well as gels that contain various ratios of two unique triblock copolymers. Analysis of micelle structural data subsequently translates to universal scaling expressions for the micelle core radius – rA ≈ NA0.53NB−0.14ϕABA0.16 where NA and NB are the endblock and midblock degrees of polymerization, respectively, and ϕABA is the volume fraction of triblock copolymer in the gel – and for the intermicelle spacing – lAA ≈ NA0.09NB0.29ϕABA−0.35. Each scaling expression describes the full collection of experimental data very well. Additionally, these scaling expressions are partially in line with expectations from semi‐dilute diblock copolymer solution theory.

Morphological Diversity in Diblock Copolymer Solutions: A Molecular Dynamics Study

Coarse-grained molecular dynamics simulations that incorporate explicit water-mediated hydrophilic/hydrophobic interactions are employed to track spatiotemporal evolution of diblock copolymer aggregation in initially homogeneous solutions. A phase portrait of the observed morphologies and their quantitative geometric features such as aggregation numbers, packing parameters, and radial distribution functions of solvent/monomers are presented. Energetic and entropic measures relevant to self-assembly such as specific solvent accessible surface area (SASA) and probability distribution functions (pdfs) of segmental stretch of copolymer chains are analyzed. The simulations qualitatively capture experimentally observed morphological diversity in diblock copolymer solutions. Topologically simpler structures predicted include spherical micelles, vesicles (polymersomes), lamellae (bilayers), linear wormlike micelles, and tori. More complex morphologies observed for larger chain lengths and nearly symmetric copolymer compositions include branched wormlike micelles with Y-shaped junctions and cylindrical micelle networks. For larger concentrations, vesicle strands, held together by hydrogen bonds, and “giant” composite aggregates that consist of lamellar, mixed hydrophobic/hydrophilic regions and percolating water cores are predicted. All structures are dynamic and exhibit diffuse domain boundaries. Morphology transitions across topologically simpler structures can be rationalized based on specific SASA measurements. PDFs of segmental stretch within vesicular assemblies appear to follow a log-normal distribution conducive for maximizing configuration entropy.

Formation and Transformation of Polystyrene-block-poly(2-vinylpyridine) Hexasomes in the Solvent Exchange.

The generation of inverse micellar nanostructures, especially those with open channels, using commercially available diblock copolymers (BCP), is vital for their wide applications in drug delivery and catalyst templating. However, the rigid requirements for forming inverse morphologies, such as the highly asymmetric molecular structures, the semicrystalline motifs, and concentrated solutions of diblock copolymers, represent obstacles to the development of successful strategies. In this study, the inverse polystyrene-block-poly(2-vinylpyridine) (PS30K-b-P2VP8.5K) micelles, i.e., the hexasomes with p6mm lattice, were generated through a modified solvent exchange via adding d-tartaric acid (d-TA) in the nonsolvent. Various intermediate morphologies have been identified with the change of d-TA concentration. Interestingly, in the high d-TA concentration (∼20 mg/mL), the hexasomes with close-packed hoops changed to mesoporous spheres with regularly packed perpendicular cylindrical channels (VD-TA: VBCP 6:100), and further to the mesoporous spheres with gyri-like open pores (VD-TA: VBCP > 15:100) with the increasing acidity in the mixed solvent. This study presents a simple and economical pathway for fabricating PS30K-b-P2VP8.5K hexasomes and first demonstrates these hexasomes can be modified to the morphology with open channels that will benefit their further applications.

Properties of Solutions of Amphiphilic Diblock and Random Copolymers of 2-Perfluorohexylethyl Methacrylate and 2-Hydroxyethyl Methacrylate and Coatings Based on Them

Properties of Solutions of Amphiphilic Diblock and Random Copolymers of 2-Perfluorohexylethyl Methacrylate and 2-Hydroxyethyl Methacrylate and Coatings Based on Them

Self-assembly of hydrophobic–amphiphilic diblock copolymers in solution

Thermoresponsive polymers are usually characterized by a locally amphiphilic chain structure and their self-assembly in solution is controlled, in particular, by the surface activity of the monomer units or side chains. We theoretically study the condensed state of a single diblock copolymer molecule consisting of a hydrophobic block and amphiphilic block with hydrophobic groups in the backbone and pendant polar groups. The equilibrium parameters of the polymer globules of different shapes are determined using the mean-field approach to determine the most favorable structure. Morphological diagrams of condensed macromolecules are presented depending on the chain length, amphiphilic block fraction, interaction parameters, and pendant volume and length. The diagrams are compared with those of a copolymer molecule with the same fraction of amphiphilic monomer units which are regularly distributed along the chain. The diblock copolymer molecule is found to form a single spherical or flattened particle, with the core from the hydrophobic block, or a granular micelle consisting of spherical or nearly spherical particles, in agreement with the experimental data in the literature. The optimal chain parameters for self-assembly into a stable single core–shell particle are predicted.

In Situ GISAXS Observation and Large Area Homogeneity Study of Slot-Die Printed PS-b-P4VP and PS-b-P4VP/FeCl3 Thin Films.

Mesoporous hematite (α-Fe2O3) thin films with high surface-to-volume ratios show great potential as photoelectrodes or electrochemical electrodes in energy conversion and storage. In the present work, with the assistance of an up-scalable slot-die coating technique, locally highly ordered α-Fe2O3 thin films are successfully printed based on the amphiphilic diblock copolymer poly(styrene-b-4-vinylpyridine) (PS-b-P4VP) as a structure-directing agent. Pure PS-b-P4VP films are printed under the same conditions for comparison. The micellization of the diblock copolymer in solution, the film formation process of the printed thin films, the homogeneity of the dry films in the lateral and vertical direction as well as the morphological and compositional information on the calcined hybrid PS-b-P4VP/FeCl3 thin film are investigated. Because of convection during the solvent evaporation process, a similar dimple-type structure of vertically aligned cylindrical PS domains in a P4VP matrix developed for both printed PS-b-P4VP and hybrid PS-b-P4VP/FeCl3 thin films. The coordination effect between the Fe3+ ions and the vinylpyridine groups significantly affects the attachment ability of the P4VP chains to the silicon substrate. Accordingly, distinct feature sizes and homogeneity in the lateral direction, as well as the thicknesses in the perpendicular direction, are demonstrated in the two printed films. By removing the polymer template from the hybrid PS-b-P4VP/FeCl3 film at high temperature, a locally highly ordered mesoporous α-Fe2O3 film is obtained. Thus, a facile and up-scalable printing technique is presented for producing homogeneous mesoporous α-Fe2O3 thin films.

Self-assembly of gradient copolymers in a selective solvent. New structures and comparison with diblock and statistical copolymers

We perform comparative studies of self-assembly of equivalent statistical, diblock and gradient AB copolymers in a selective solvent using dissipative particle dynamics simulations. Both effects of the fraction of soluble and insoluble groups, selectivity of the solvent and degree of immiscibility of A and B groups on self-assembled structures are studied. With a simplified model of the statistical copolymer we predict macroscopic phase segregation, when non-aggregated chains coexist with precipitate. The later can be dense or swollen (physical gel) depending on degree of immiscibility of the A and B groups. For the case of diblock copolymer solutions, we predict thermodynamic stability of few structures: spherical and worm-like micelles, rings, vesicles and precipitate. We develop a simple theory, which allows calculating free energies of worms and rings (closed worms) and explaining transition between the structures. A number of diagrams of states is constructed. In case of gradient copolymers, two scenarios of self-assembly are predicted. The spherical micelles of gradient copolymer can aggregate with each other forming worms, rings and vesicles through aggregation of coronae (so-called sticky corona), which contain insoluble groups, if the fraction of insoluble groups per chain is not high. Herewith, the core of the assembled structures remains multidomain despite a high interfacial tension. The second (“diblock-like”) scenario is realized when the fraction of insoluble groups is high enough. In this case the core of worms, rings and vesicles is practically a monodomain, however, solvophilic groups can be intercalated into the core due to the primary structure of the copolymer. A new structure of a multi-compartment vesicle on the basis of gradient copolymers is predicted.

Evaluation of Loco-Regional Skin Toxicity Induced by an In Situ Forming Depot after a Single Subcutaneous Injection at Different Volumes and Flow Rates in Göttingen Minipigs.

The present study aims to investigate the loco-regional tolerability and injection parameters (i.e., flow rate and administration volume) of an in situ forming depot (ISFD) in Göttingen minipigs, to secure both the therapeutic procedure and compliance in chronic medical prescriptions. The ISFD BEPO® technology (MedinCell S.A.) is investigated over 10 days, after a single subcutaneous injection of test item based on a DMSO solution of diblock and triblock polyethylene glycol-polylactic acid copolymers. Injection sites are systematically observed for macroscopic loco-regional skin reactions as well as ultrasound scanning, enabling longitudinal in vivo imaging of the depot. Observations are complemented by histopathological examinations at 72 h and 240 h post-injection. Overall, no treatment-emergent adverse effects are macroscopically or microscopically observed at the subcutaneous injection sites, for the tested injection flow rates of 1 and 8 mL/min and volumes of 0.2 and 1 mL. The histopathology examination confirms an expected foreign body reaction, with an intensity depending on the injected volume. The depot morphology is similar irrespective of the administration flow rates. These results indicate that the ISFD BEPO® technology can be considered safe when administered subcutaneously in Göttingen minipigs, a human-relevant animal model for subcutaneous administrations, in the tested ranges.

3D bicontinuous diamond-like morphologies in thin films of soluted block copolymers.

As shown theoretically earlier via both weak segregation and self-consistent field theories, ordering of confined molten di- and tri-block copolymer morphologies in the presence of a proper 1D patterned substrate could induce the formation of 3D bicontinuous (in particular, diamond-like) morphologies (DLMs). The purpose of the present paper is to study, unlike the previous studies, how the stable DLMs are formed not in a melt but in a solution of symmetric diblock copolymers with a nonselective solvent that wets the thin film on the patterned substrate. It is shown, via a straightforward self-consistent field calculation of the total solution free energy for various competing phases, that the DLM could be formed in the solutions (with the solvent volume fraction of 0.5), which provides much faster thermodynamic equilibration of the solution as compared to the melt. The last circumstance can ease the production of stable DLMs in thin films of copolymers. The phase diagram describing the stable phases on the plane "the pattern period-the film thickness" is built.

Study of Segregation in Non-Dilute Solutions of Linear Diblock Copolymers and Symmetric Miktoarm (or Janus Star) Polymers Using Monte Carlo Simulations with the Bond Fluctuation Model

The bond fluctuation model was employed to characterize the approach to the mesophase separation transition of pure linear AB copolymers and symmetric miktoarms, also called Janus, star polymers, Af/2Bf/2, where f = 6 or 12 is the total number of arms, in a common good solvent. We consider a concentration sufficiently high to mimic the melting behavior and also a lower concentration. The segregation between A and B units is represented by a repulsive interaction parameter, ε. Different total numbers of units are also considered. Results for different properties, such as the molecular size, the asphericity and orientational correlation of blocks, or arms, of different compositions are obtained as a function of the segregation parameter. We also calculate scattering structure factors. The initial effect of segregation on the scattering with opposite contrast factors between the A and B blocks can be explained with a common description based on the random phase approximation for both the linear copolymers and the f = 6 miktoarms, once the numerical form factors of the different molecules in their particular systems are considered. However, the results for f = 12 clearly deviate from this description probably due to some degree of ordering in the position of highly armed molecules.

Thermodynamically Consistent Algorithms for Models of Diblock Copolymer Solutions Interacting with Electric and Magnetic Fields

We derive thermodynamically consistent models for diblock copolymer solutions coupled with the electric and magnetic field, respectively. These models satisfy the second law of thermodynamics and are therefore thermodynamically consistent. We then design a set of 2nd order, linear, semi-discrete schemes for the models using the energy quadratization method and the supplementary variable method, respectively, which preserve energy dissipation rates of the models. The spatial discretization is carried out subsequently using 2nd order finite difference methods, leading to fully discrete, energy-dissipation-rate preserving algorithms that are thermodynamically consistent. Convergence rates are numerically confirmed through mesh refinement tests and several numerical examples are given to demonstrate the role of mobility in pattern formation, defect removing effect of both electric and magnetic fields as well as the hysteresis effect with respect to applied external fields in copolymer solutions.

Thermodynamically consistent algorithms for models of incompressible multiphase polymer solutions with a variable mobility

We present a general strategy for developing structure and property preserving numerical algorithms for thermodynamically consistent models of incompressible multiphase polymer solutions with a variable mobility. We first present a formalism to derive thermodynamically consistent, incompressible, multiphase polymer models. Then, we develop the general strategy, known as the supplementary variable method, to devise thermodynamically consistent numerical approximations to the models. We illustrate the numerical strategy using newly developed models of incompressible diblock copolymer solutions coupled with an electric and a magnetic field, respectively. Mesh refinement is conducted to verify convergence rates of the developed schemes. Some numerical examples are given to exhibit underlying dynamics absent from and driven by the external fields, respectively, highlighting differences between models with the variable and constant mobilities.