Formation of gold@polymer core-shell particles and gold particle clusters on a template of thermoresponsive and pH-responsive coordination triblock copolymer

Template synthesis of various morphological gold colloidal nanoparticles using a thermoresponsive and pH-responsive coordination triblock copolymer of poly(ethylene glycol)-b-poly(4-vinylpyridine)-b-poly(N-isopropylacrylamide) is studied. The template morphology of the thermoresponsive and pH-responsive coordination triblock copolymer, which can be tuned by simply changing the pH or temperature of the triblock copolymer aqueous solution, ranges from single chains to core-corona micelles and further to micellar clusters. Various morphological gold colloidal nanoparticles such as discrete gold nanoparticles, gold@polymer core-shell nanoparticles, and gold nanoparticle clusters are synthesized on the corresponding template of the triblock copolymer by first coordination with gold ions and then reduction by NaBH4. All three resultant gold colloidal nanoparticles are stable in aqueous solution, and their sizes are 2, 10, and 7 nm, respectively. The gold@polymer core-shell nanoparticles are thermoresponsive. The gold nanoparticle cluster has a novel structure, and each one holds about 40 single gold nanoparticles.     

Formation of ordered microphase-separated pattern during spin coating of ABC triblock copolymer

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.     

Morphology,thermo-mechanical properties and surface hydrophobicity of nanostructured epoxy thermosets modified with PEO-PPO-PEO triblock copolymer

In this paper, we report on the effect of amphiphilic poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymer (TBCP) on the miscibility, phase separation, thermomechanical properties and surface hydrophobicity of diglycidyl ether of bisphenol-A (DGEBA)/4,4'-diaminodiphenylmethane (DDM) system. The blends were nanostructured. The phase separation occurred via self-assembly of PPO blocks followed by the reaction induced phase separation of PEO blocks. The surface roughness increased with increase in concentration of TBCP due to increased phase separation of PEO blocks at higher concentration. The phase separated PEO blocks formed the crystalline phase in the amorphous crosslinked epoxy matrix. The TBCP has a strong plasticizing effect on the matrix and decreased the glass transition temperature (T_g) and modulus of the thermoset. The incorporation of TBCP improved impact strength and tensile properties and 5 phr TBCP content was found to be optimum to achieve balanced mechanical performance. Moreover, the thermal stability of the epoxy system was retained while hydrophobicity was improved in the presence of TBCP.     

Effect of laponite clay particles on thermal and rheological properties of Pluronic triblock copolymer

The high concentration 17 wt% triblock copolymer poly(ethylene oxide)₁₀₀–poly(propylene oxide)₆₅–poly(ethylene oxide)₁₀₀ Pluronic F127 aqueous solutions with the addition of laponite is investigated as a novel temperature-sensitive hydrogel system. The critical micelle temperature (cmt) and the sol-to-gel transition were characterized by rheological experiments and differential scanning calorimetry. Experimental results showed that laponite particles have no significant influence on the cmt. On the other hand, viscoelastic measurements have highlighted an increase of the sol-to-gel transition temperature for mixtures with 2 and 3 wt% of laponite particles. This additive can be used to adjust the gelation temperature close to physiological temperature in medical applications.     

Formation of nanostructured materials via coalescence of amphiphilic hollow particles

A new, simplified route to amphiphilic core-shell nanotubes, microfibers, and microrods has been developed that does not involve the traditional utilization of well-defined block copolymers. Thus, amphiphilic graft copolymers (PEI-g-PMMA) are prepared by an aqueous free radical polymerization that self-assemble in situ to form uniform core-shell nanoparticles. The hydrophobic homopolymer (PMMA) that is also formed is incorporated in the cores. Slight cross-linking of the shells followed by extraction of the homopolymer results in hollow nanoparticles that coalesce to form nanotubes. When the shells are not cross-linked, the hollow particles coalesce to form microrods and microfibers. The sizes and shapes of the micromaterials can be controlled by varying the experimental conditions.     

Structure of microemulsion-ABA triblock copolymer networks

Structural equilibrium properties of transient networks formed by microemulsion droplets and ABA triblock copolymers in solution have been studied by Monte Carlo simulation. The droplets were represented by soft spheres, and the polymers were represented by junctions connected by harmonic bonds with an angular potential regulating the intrinsic chain stiffness. The interaction parameters were selected such that the end A-blocks were localized inside the droplets and the middle B-block in the continuous phase. The influence of (i) the polymer concentration, (ii) the polymer stiffness, and (iii) the contour length of the middle B-block on the formation and the structure of the microemulsion-polymer network were investigated using polymer end-to-end separation probability distribution functions, droplet radial distribution functions, droplet-droplet nearest-neighbor probability distribution functions, and network connectivity indicators. An increase of the polymer-droplet number ratio had a strong impact on the network formation. Under typical conditions and at an intermediate polymer-droplet number ratio, (i) the fraction of polymers forming bridges between droplets increased from essentially zero to unity and (ii) the fraction of polymers that were forming loops decreased as the ratio of the polymer end-to-end separation and the surface-to-surface separation between neighboring droplets for a hypothetical homogeneous droplet distribution was increased from 0.5 to 2. For long and flexible polymers, a mesoscopic segregation triggered by a depletion attraction between droplets appeared, and, furthermore, for sufficiently stiff chains, only bridge conformations occurred. The percolation probability could be represented as a function of the average droplet cluster size only, across all systems.     

Effects of a PPO-PEO-PPO triblock copolymer on micellization and gelation of a PEO-PPO-PEO triblock copolymer in aqueous solution

The effects of a PPO-PEO-PPO triblock copolymer (25R4, PO(19)-EO(33)-PO(19)) on thermoreversible micellization and gelation properties of a PEO-PPO-PEO triblock copolymer (F108, EO(133)-PO(50)-EO(133)) in water were studied by means of micro-DSC and rheology. A complete, mirror-image like thermoreversible behavior has been observed for all of the samples with various molar ratios of 25R4 to F108. At a given concentration of F108, the addition of 25R4 results in the salt-out like effect on the primary micellization of F108; that is, the critical micellization temperature (CMT) of F108 shifts to lower temperatures with increasing the content of 25R4. The enthalpy changes for micellization are a linear function of the 25R4/F108 molar ratio at a fixed F108 concentration. Beyond the primary peak for the micellization of F108, a secondary peak or shoulder is observed in the DSC curves for the samples with the higher 25R4/F108 molar ratios, due to the formation of the hydrophobic aggregates from both the PPO blocks of F108 and those (i.e., PPO blocks) of 25R4. Furthermore, as an example, the dynamic viscoelastic properties of 18 wt % F108 solutions with various contents of 25R4 have been examined. It is found that, when the 25R4/F108 molar ratio < or =1, 25R4 does not affect the gelation of F108 notably. When the ratio is greater than 1, however, the formation of the 25R4-bridged micellar aggregates delays the gelation of F108 significantly. A schematic model has been proposed to explain the mechanism for the 25R4-influenced micellization and gelation of F108.     

Rheological studies of thermosensitive triblock copolymer hydrogels

Hydrogel formation by physical cross-linking is a developing area of research toward materials suitable for pharmaceutical and biomedical applications. Polymers exhibiting lower critical solution temperature (LCST) behavior in aqueous solution are used in this study to prepare hydrogels. Four triblock copolymers (ABA) with thermosensitive poly(N-(2-hydroxypropyl) methacrylamide lactate) A-blocks and a hydrophilic poly(ethylene glycol) B-block have been synthesized. The molecular weight of the hydrophilic PEG block was fixed at 10 kDa, whereas the molecular weight of the pHPMAm-lactate block was varied between 10 and 20 kDa. The rheological characteristics of these polymer hydrogels were studied as a function of temperature, concentration, and the length of the thermosensitive blocks. Gelation occurred rapidly upon increasing the temperature to 37 degrees C, which makes this system suitable as an injectable formulation. The gels became stronger with increasing temperature and concentration, and moreover they behaved as critical gels, which means that G' and G' ' follow power laws over the entire frequency range. Surprisingly, with increasing length of the thermosensitive blocks, weaker hydrogels were formed. This trend can be explained by the cross-link density of the physical network, which increases with decreasing length of the thermosensitive blocks.     

Equilibrium behavior of confined triblock copolymer films

Using a two-dimensional self-consistent field calculation, we determine the equilibrium morphology of thin films of ABC triblock copolymers confined between hard, smooth plates. The B segment is chosen to be the central block and all the blocks are incompatible. The chains microphase-segregate into a lamellar phase, with the stripes either perpendicular or parallel to the walls. When all the monomer-surface interactions are identical, the perpendicular orientation has the lowest free energy. When a repulsion is introduced between the surface and the A and C monomers. The surface interactions further stabilize the perpendicular orientation. At strong surface interactions, the morphology of the perpendicular structure is controlled by the overall thickness of the molten layer. In comparing diblocks to triblocks as candidates for forming laterally patterned films, our work indicates that triblocks possess distinct advantages over diblocks. First, no special effort needs to be taken to establish neutral surfaces. Second, the film does not have to be confined between two substrates. Thus, triblocks can be used to fabricate patterned polymer surfaces, which can be used for novel optical or electronic applications.     

Phase behavior of SEBS triblock copolymer gels

Dynamic density functional theory calculations were performed for thermoplastic elastomer gels composed of an ABA triblock copolymer immersed in a B‐attractive solvent. The triblock copolymer model was parameterized for poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] (SEBS), while the solvent model was parameterized for the hydrocarbon oil tetradecane. The effect of the solvent concentration and S‐EB interaction on the morphology was investigated, where complementary experimental data was used to validate results at χ_ABN ≈ 100. Agreement was observed at solvent volume fractions of 0.2, 0.4, and 0.6, which correspond to the cylindrical, spherical, and spherical phases, respectively. Qualitative agreement was observed for 0.8 volume fraction solvent, where a core‐shell spherical micelle morphology was found. For a 50/50 vol % mixture of polymer/solvent, the effect of solvent molecular weight on the morphology was considered, where a transition between micro and macrophase separation was predicted at a critical solvent molecular weight. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1479–1491, 2011     

ABA triblock copolymer containing two crystallizable components

A triblock copolymer of the ABA type in which both components were crystallizable was synthesized. The A block was poly(ethylene oxide), PEO, and the B block, poly(dimethyl siloxane), PDMS. Upon cooling from the melt to liquid nitrogen temperature, the PEO block crystallized at around 40°C. When the copolymer was heated from ?170°C after quenching, glass transition, crystallization and melting of the PDMS middle block were identified in the thermogram at ?117°C, ?74°C and ?42°C, respectively. The degree of crystallinity of the PDMS block was estimated from the heat of fusion to be about 27%. The growth rates of the PEO spherulites were reduced by the presence of the middle block.     

Synthesis and self-assembly behavior of thermoresponsive triblock copolymer

Block copolymers comprising thermosensitive poly(N-isopropylacrylamide) (PNIPAM) and hydrophobic poly(n-butyl acrylate) (PBA) blocks, were synthesized using the reversible addition-fragmentation chain transfer polymerization (RAFT), their thermosensitive behavior was studied by ultraviolet spectrophotometer (UV) and dynamic light scattering (DLS). The lower critical solution temperature (LCST) was strongly correlated to the hydrophobic/hydrophilic ratio of the copolymers. Their micellization and self-assembly behavior in dilute aqueous solution were studied by surface tension (SFT), DLS and TEM. The resulting block copolymers reversibly formed or deformed micellar assemblies during their LCSTs. The critical micelle concentration (CMC) was controlled by the composition of PBA and PNIPAM, indicating the successful formation of the block copolymers.     

Supramolecular association of a triblock copolymer in water

Solutions of a poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) triblock copolymer, Pluronic F(68), were investigated in isothermal and isopleth mode. Surface tension, sigma, dynamic shear viscosity, n(omega), QELS experiments, and volumetric, colligative, and refractive index measurements characterize the system behavior in a wide range of compositions and temperatures. The thermodynamic properties associated with micelle formation, above the critical micellar temperature, were determined by different experimental methods. The large entropic contributions to the system stability are ascribed to significant dehydration of the oxypropylene portion in the copolymer, consequent to micelle formation. Temperature has a pronounced effect on the association features of F(68). It gives rise to abrupt changes in QELS and rheological properties when the critical micellar temperature is approached. Such effects are explained in terms of thermally driven micellization processes and interconnection between micelles.     

Fddd network phase in ABA triblock copolymer melts

Using self‐consistent field theory, we investigate the stability of the orthorhombic Fddd network phase (O⁷⁰) in ABA triblock copolymer melt systems. Consistent with previous findings, we observe that the gross topology of phase behavior is unchanged with varying chain asymmetry. However, the mean field critical point is displaced from the diblock copolymer value of f_A = 0.5 (f_A is the A segment volume fraction) to larger values as the triblock copolymer symmetry is broken with unequal A block lengths. This deviation significantly shifts the order‐order phase boundaries, resulting in an appreciable region of O⁷⁰ stability in the phase diagram of asymmetric ABA triblock copolymers. More importantly, the stability of the O⁷⁰ phase extends to the intermediate segregation regime for select chain asymmetries. Both features are desirable for achieving a synthetic realization of the phase in binary AB block copolymer systems. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1112–1117     

Comparative analysis of nanostructured diblock copolymer films

Nanostructured polymer films of poly(styrene-block-paramethylstyrene) diblock copolymers P(Sd-b-pMS) on silicon substrates with a native oxide layer are investigated. Resulting from a storage under toluene vapor, a surface structure is installed. The early stages, characterized by the creation of a host structure out of an initially continuous film, are addressed. Grazing incidence small-angle X-ray scattering (GISAXS) experiments were performed as a function of exposure time. Results are compared to modelling of the scattering pattern and other experimental techniques, such as grazing incidence small-angle neutron scattering (GISANS) and atomic force microscopy (AFM) data. Possibilities and limits of the techniques are discussed.     

Morphology of ABC triblock copolymer/homopolymer blend systems

Morphological variations of ABC triblock copolymers through the blending of B or A/C homopolymers, all with short chain lengths, were studied experimentally. The samples were symmetric ISP triblock copolymers, where I, S, and P denote polyisoprene, polystyrene, and poly(2‐vinylpyridine), and component homopolymers. Microphase‐separated structures of the solvent‐cast films were observed with transmission electron microscopy and small‐angle X‐ray scattering. For an ISP/S system, the lattice constant of the tricontinuous gyroid structure (G‐structure) increased with an increase in the volume fraction of S (?_s) if the amount of added homopolymer was small, but it reached a certain limit, reflecting the fact that the midblock chain had a limit for chain stretching. For I/ISP/P blends, on the contrary, the lattice constant of the G‐structure continued increasing with decreasing ?_s. This result shows that the I and P domains did not have a limit for chain stretching because the two end blocks had free ends. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1135–1141, 2002     

Morphology and mechanical properties of binary triblock copolymer blends

The influence of the morphology on the mechanical properties of binary styrene–butadiene (SB) triblock copolymer blends of a thermoplastic block copolymer and a thermoplastic elastomer (TPE) with different molecular architectures was studied with bulk samples prepared from toluene. Both block copolymers contained SB random copolymer middle blocks, that is, the block sequence S–SB–S. The two miscible triblock copolymers were combined to create a TPE with increased tensile strength without a change in their elasticity. The changes in the equilibrium morphology of the miscible triblock copolymer blends as a function of the TPE content (lamellae, bicontinuous morphology, hexagonal cylinders, and worms) resulted in a novel morphology–property correlation: (1) the strain at break and Young's modulus of blends with about 20 wt % TPE were larger than those of the pure thermoplastic triblock copolymer; (2) at the transition from bicontinuous structures to hexagonal structures (～35 wt % TPE), a change in the mechanical properties from thermoplastic to elastomeric was observed; and (3) in the full range of wormlike and hexagonal morphology (60–100 wt % TPE), elastomeric properties were observed, the strength greatly increasing and high‐strength elastomers resulting. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 429–438, 2005     

Formation mechanism of nanostructured Ag films from Ag2O particles using a sonoprocess

Nanostructured Ag films composed of nanoparticles and nanorods can be formed by the ultrasonication of ethanol solutions containing Ag₂O particles. The present work examined the formation process of these films from ethanol solutions by two different agitation methods, including ultrasonication and mechanical stirring. The mass-transfer process from Ag₂O particles to ethanol solvent is accelerated by the mechanical effects of ultrasound. Ag⁺ ions and intermediately reduced Ag clusters were released into the ethanol. These Ag⁺ ions and Ag clusters provide absorption bands at 210, 275 and 300 nm in UV-vis spectra. These bands were assigned to the absorption of Ag⁺, Ag ₄ ²⁺ and Ag_n (n?≈?3). The Ag_n clusters that readily grow to become Ag nanoparticles were formed due to the surface reaction of Ag₂O particles with ethanol under ultrasonication. The reactions of Ag⁺ ions in ethanol to form Ag nanomaterials (through the formation of Ag ₄ ²⁺ clusters) were also accelerated by ultrasonication.     

Thermoresponsive triblock copolymer aggregates investigated by laser light scattering

Narrowly distributed polystyrene-b-poly(N-isopropylacrylamide)-b-polystyrene (PS-b-PNIPAM-b-PS) triblock copolymer with trithiocarbonate group in the middle of PNIPAM block was synthesized by using reversible addition fragmentation chain transfer (RAFT) polymerization. Such copolymer chains form a micelle-like aggregate with PNIPAM interlocking rings and associating PS blocks as the core and PNIPAM rings as the corona. The hydrolysis of the trithiocarbonate group leads the rings in the corona to be cut into open linear coils. Using laser light scattering, we have investigated the temperature-induced collapse of the aggregates with the rings and coils in the corona. Our results reveal that the former shrink much less than the latter due to the topological effect of PNIPAM blocks in the corona. On the other hand, the aggregates with long coils exhibit a sharper collapse transition than those with shorter coils.