A new approach in the study of tethered diblock copolymer surface morphology and its tethering density dependence

A poly(l-lactic acid)-block-polystyrene-block-poly(methyl methacrylate) (PLLA-b-PS-b-PMMA) triblock copolymer was synthesized with a crystalline PLLA end block. Single crystals of this triblock copolymer grown in dilute solution could generate uniformly tethered diblock copolymer brushes, PS-b-PMMA, on the PLLA single crystal substrate. The diblock copolymer brushes exhibited responsive, characteristic surface structures after solvent treatment depending upon the quality of the solvent in relation to each block. The chemical compositions of these surface structures were detected via the surface enhanced Raman scattering technique. Using atomic force microscopy, the physical morphologies of these surface structures were identified as micelles in cyclohexane and “onion”-like morphologies in 2-methoxyethanol, especially when the PS-b-PMMA tethered chains were at low tethering density.     

Effect of miscibility on migration of third component in star‐like co‐continuous and disperse‐within‐disperse mixed brushes

Novel ternary mixed‐brush single crystals were designed with disperse‐within‐disperse and star‐like co‐continuous morphologies based on poly(ethylene glycol) (PEG)‐b‐polystyrene (PS)/PEG‐b‐poly(methyl methacrylate) (PMMA)/PEG‐b‐polyaniline (PANI) and PEG‐b‐PS/PEG‐b‐PMMA/PEG‐b‐(poly(?‐caprolactone) (PCL) or poly(l ‐lactide) (PLLA)) block copolymers, respectively. In the disperse‐within‐disperse ternary mixed brushes, PANI nanorods were dispersed within the matrix (PS)–dispersed (PMMA) amorphous brushes. The flexibility and rigidity of brushes mainly affected the ultimate morphology and arrangement of amorphous coiled brushes in the vicinity of PANI nanorods. In addition, the migration of PCL and PLLA crystallizable brushes was evident into PMMA phases dispersed in the PS matrix, leading to star‐like co‐continuous patterns of PCL and PLLA brushes. This phenomenon was related to the miscibility of crystallizable PCL and PLLA brushes with the PMMA phase. The migration of crystallizable PCL and PLLA brushes increased the size of PMMA domains in the star‐like co‐continuous patterns. Despite the larger osmotic pressure of PLLA brushes, their higher miscibility with PMMA chains reflected the greater PMMA dispersal and wider PLLA star‐like branches. © 2017 Society of Chemical Industry     

Low frequency viscosities of PS/PMMA/PS-b-PMMA blends

Assuming that the viscosimetric behaviour at low frequencies is mainly determined by the behaviour of the continuous phase, it becomes possible to explain the behaviour of PS/PMMA blends from a limited number of hypotheses. The main hypothesis is that the PMMA layer next to the interface gelifies, while the PS layer next to the interface slips under the influence of a hydrodynamical field. The explanation concurs with all the experimental data which we obtained, regardless of the concentration of PS or PMMA. Moreover the effect of adding a block copolymer PS-b-PMMA can be explained.     

Perpendicular lamellae induced at the interface of neutral self-assembled monolayers in thin diblock copolymer films

We obtained perpendicular lamellar orientations in thin films of symmetric polystyrene-block-poly(methyl methacrylate), PS-b-PMMA, on self-assembled monolayers (SAMs) of 3-(p-methoxyphenyl)propyltrichlorosilane (MPTS) prepared on silicon wafers. In contrast to completely parallel lamellae on silicon wafers having a native oxide layer, perpendicular lamellae at the MPTS interface with parallel lamellae at the air interface were directly observed by transmission electron microscopy (TEM) in cross-sectional view. The perpendicular lamellae at the MPTS interface were attributed to the non-preferential (neutral) MPTS-covered substrate to both PS and PMMA blocks. The neutrality of the SAMs of MPTS was confirmed by the similar interfacial tension values of the SAMs of MPTS with PS and PMMA, estimated by contact angle measurements.     

Corona structure on demand: Tailor-made surface compartmentalization in worm-like micelles via random cocrystallization

We present a straightforward approach to well-defined 1D patchy particles utilizing crystallization-induced self-assembly. A polystyrene-block-polyethylene-block-poly(methyl methacrylate) (PS-b-PE-b-PMMA) triblock terpolymer is cocrystallized in a random fashion with a corresponding polystyrene-block-polyethylene-block-polystyrene (PS-b-PE-b-PS) triblock copolymer to yield worm-like crystalline-core micelles (wCCMs). Here, the corona composition (PMMA/PS fraction) can be easily adjusted via the amount of PS-b-PE-b-PMMA triblock terpolymer in the mixture and opens an easy access to wCCMs with tailor-made corona structures. Depending on the PMMA fraction, wCCMs with a mixed corona, spherical PMMA patches embedded in a continuous PS corona, as well as alternating PS and PMMA patches of almost equal size can be realized. Micelles prepared by cocrystallization show the same corona structure as those prepared from neat triblock terpolymers at identical corona composition. Thus, within a certain regime of desired corona compositions the laborious synthesis of new triblock terpolymers for every composition can be circumvented.     

Temperature-composition phase diagrams of binary blends of block copolymer and homopolymer

The temperature-composition phase diagrams for six pairs of diblock copolymer and homopolymer are presented, putting emphasis on the effects of block copolymer composition and the molecular weight of added homopolymers. For the study, two polystyrene-block-polyisoprene (SI diblock) copolymers having lamellar or spherical microdomains, a polystyrene-block-polybutadiene (SB diblock) copolymer having lamellar microdomains, and a series of polystyrene (PS), polyisoprene (PI), and polybutadiene (PB) were used to prepare SI/PS, SI/PI, SB/PS, and SB/PB binary blends, via solvent casting, over a wide range of compositions. The shape of temperature-composition phase diagram of block copolymer/homopolymer blend is greatly affected by a small change in the ratio of the molecular weight of added homopolymer to the molecular weight of corresponding block (M_H,A/M_C,A or M_H,B/M_C,B) when the block copolymer is highly asymmetric in composition but only moderately even for a large change in M_H,A/M_C,A ratio when the block copolymer is symmetric or nearly symmetric in composition. The boundary between the mesophase (M₁) of block copolymer and the homogeneous phase (H) of block copolymer/homopolymer blend was determined using oscillatory shear rheometry, and the boundary between the homogeneous phase (H) and two-phase liquid mixture (L₁+L₂) with L₁ being disordered block copolymer and L₂ being macrophase-separated homopolymer was determined using cloud point measurement. It is found that the addition of PI to a lamella-forming SI diblock copolymer or the addition of PB to a lamella-forming SB diblock copolymer gives rise to disordered micelles (DM) having no long-range order, while the addition of PS to a lamella-forming SB diblock copolymer retains lamellar microdomain structure until microdomains disappear completely. Thus, the phase diagram of SI/PI or SB/PB blends looks more complicated than that of SI/PS or SB/PS blends.     

Study on crystalline morphology of poly(l-lactide)-poly(ethylene glycol) diblock copolymer

Crystallization behavior, structural development and morphology evolution in a series of diblock copolymers of poly(l-lactide)-block-poly(ethylene glycol) (PLLA-b-PEG) were investigated via differential scanning calorimetry, wide-angle X-ray diffraction, polarized optical microscopy and atomic force microscopy. In these copolymers, both blocks are crystallizable and biocompatible. It was interesting that these PLLA-b-PEG diblock copolymers could form spherulites with banded textures, which was undercooling dependent. Single crystals with an abundance of screw dislocations were also observed via AFM. Such results indicated that these ringed spherulites and single crystals were formed during the crystallization of the PLLA blocks.     

Water-induced morphology evolution of block copolymer micellar thin films

Morphology evolution of diblock copolymer polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) micellar thin film in the presence of water was investigated. Surface holes with nanoscale cavities in hexagonal order could be induced by water treatment for certain periods. The nanoscale surface cavities could be transformed into isolated nanospheres in a dry environment or back to protruding densely packed spheres by toluene (a selective solvent for PS coronae) treatment. The morphology evolution of micellar thin film strongly depended on the slow evaporation of toluene solvent, the swelling of P4VP cores in the humid environment, and the subsequent movement of PS chains induced by air and toluene. The incompatibility between solvent and block, and that between the unlike blocks also played an important role in the morphology evolution.     

Formation of conductive polyaniline nanoarrays from block copolymer template via electroplating

Nanostructured thin films have drawn extensive attention because of their unique properties resulting from nanoscale features. One of the convenient ways to generate nanostructured thin films is to use pattern with nanoscale texture as a template for the reactions carrying out within the template. In this study, nanoporous thin film template was obtained from the self-assembly of degradable block copolymer, polystyrene-b-poly(l-lactide) (PS-PLLA) with PLLA cylinder nanostructure, at which the PLLA block can be hydrolyzed to form the nanopatterns with cylinder nanopores on conductive substrate (i.e., ITO substrate). The nanoporous PS thin film template was stabilized by modification of substrate using hydroxyl terminated PS so as to enhance the adhesion with substrate for following electroplating process. Combining a pulse electroplating method with the control of micro current, polyanilines can be successfully synthesized within the template to fabricate well-defined of conductive polymer nanoarrays.     

Self‐assembled structures in blends of disordered and lamellar block copolymers: SAXS,SANS and TEM study

BACKGROUND: The phase behaviour of copolymers and their blends is of great interest due to the phase transitions, self‐assembly and formation of ordered structures. Phenomena associated with the microdomain morphology of parent copolymers and phase behaviour in blends of deuterated block copolymers of polystyrene (PS) and poly(methyl methacrylate) (PMMA), i.e. (dPS‐block‐dPMMA)₁/(dPS‐block‐PMMA)₂, were investigated using small‐angle X‐ray scattering, small‐angle neutron scattering and transmission electron microscopy as a function of molecular weight, concentration of added copolymers and temperature. RESULTS: Binary blends of the diblock copolymers having different molecular weights and different original micromorphology (one copolymer was in a disordered state and the others were of lamellar phase) were prepared by a solution‐cast process. The blends were found to be completely miscible on the molecular level at all compositions, if their molecular weight ratio was smaller than about 5. The domain spacing D of the blends can be scaled with M_n by D ～ M_n^2/3 as predicted by a previously published postulate (originally suggested and proved for blends of lamellar polystyrene‐block‐polyisoprene copolymers). CONCLUSIONS: The criterion for forming a single‐domain morphology (molecularly mixed blend) taking into account the different solubilization of copolymer blocks has been applied to explain the changes in microdomain morphology during the self‐assembling process in two copolymer blends. Evidently the criterion, suggested originally for blends of lamellar polystyrene‐block‐polyisoprene copolymers, can be employed to a much broader range of block copolymer blends. Copyright © 2008 Society of Chemical Industry     

Single crystals morphology of biodegradable double crystalline PLLA-b-PCL diblock copolymers

The morphology of solution grown single crystals of a series of double crystalline diblock copolymers derived from l-lactide and ?-caprolactone has been investigated by means of transmission electron microscopy. The copolymers had a variable composition with a poly(l-lactide) weight percentage that ranged between 81 and 10%. All samples had a low polydispersity index (1.4-1.1) and a similar number average molecular weight (20,000-35,000 g/mol).Bulk crystallization and melting behaviour of diblock copolymers were evaluated by DSC and the results demonstrated the double crystalline nature of the samples. Fractionated crystallization clearly occurred in copolymers having an intermediate composition.Isothermal crystallizations were performed in dilute n-hexanol solutions at temperatures that ranged between 80 and 50 °C. Crystal morphologies were dependent on the crystallization temperature and even on the composition. Thus, the inability of poly(?-caprolactone) (PCL) blocks to crystallize between 80 and 70 °C rendered lozenge, truncated and spindle-shaped crystals associated to the poly(l-lactide) (PLLA) block. These usually had thicker edges due to PLLA overgrowths that mainly took place in their periphery. However, an overgrowth of irregular PCL crystals during subsequent cooling and crystallization at room temperature was also detected. Complex morphologies constituted by lamellar crystals of both PCL and PLLA blocks were developed at intermediate temperatures (70-65 °C), whereas elongated hexagonal morphologies mainly associated to the PCL block were detected at the lowest crystallization temperature. In general, electron diffraction patterns showed for all samples’ reflections associated to both poly(?-caprolactone) and poly(l-lactide) (α-form) crystals. The relative intensity between the two types of reflections varied according to the copolymer composition.     

A study of the versatile micropatterns of diblock copolymer micelles: the effect of copolymer concentration, substrate, film thickness and micelles morphology

We report the novel use of polystyrene-block-poly(acrylic acid) (PS-b-PAA) diblock copolymer micelles as the nano-building blocks in fabricating orderly aligned three-dimensional micropatterns with high regularity through a one-step evaporation-induced cracking process. Crack patterns of square, rectangular, stripe-like and mesh-like structures in micron scale were obtained. The effect of the concentration of diblock copolymer, the properties of the substrates, the thickness of the drying layer, and the morphology of the micelles on the regularity of the crack patterns was studied. By regulating the above factors, we achieved micropatterns of various structures. We further developed a cheap, fast, and simple method for fabricating micromolded structures using the crack patterns as templates.     

Thermal behavior and properties of polystyrene/poly(methyl methacrylate) blends

The thermal behavior and properties of immiscible blends of polystyrene (PS) and poly(methyl methacrylate) (PMMA) with and without PS‐b‐PMMA diblock copolymer at different melt blending times were investigated by use of a differential scanning calorimeter. The weight fraction of PS in the blends ranged from 0.1 to 0.9. From the measured glass transition temperature (T_g) and specific heat increment (ΔC_p) at the T_g, the PMMA appeared to dissolve more in the PS phase than did the PS in the PMMA phase. The addition of a PS‐b‐PMMA diblock copolymer in the PS/PMMA blends slightly promoted the solubility of the PMMA in the PS and increased the interfacial adhesion between PS and PMMA phases during processing. The thermogravimetric analysis (TGA) showed that the presence of the PS‐b‐PMMA diblock copolymer in the PS/PMMA blends afforded protection against thermal degradation and improved their thermal stability. Also, it was found that the PS was more stable against thermal degradation than that of the PMMA over the entire heating range. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 609–620, 2004     

Compatibilisation of PPE/SAN blends by triblock terpolymers: Correlation between block terpolymer composition, morphology and properties

Immiscible blends of poly(2,6-dimethyl-1,4-phenylene ether) (PPE) and poly(styrene-co-acrylonitrile) (SAN) with a weight composition of 60/40 were compatibilised by polystyrene-block-polybutadiene-block-poly(methyl methacrylate) triblock terpolymers (SBM) using a two-stage melt-processing approach. In order to investigate the influence of the SBM composition on the compatibilisation efficiency, the block lengths of the triblock terpolymers were systematically varied. The resulting morphological features of the blend systems as function of SBM composition and processing parameters are correlated with the resulting thermal and thermo-mechanical properties. In the ideal case, SBM should be located at the interface as PS is miscible with PPE while PMMA is miscible with SAN. The elastomeric middle block as an immiscible component should remain at the interface. This particular morphological arrangement is known as the ‘raspberry morphology’. A detailed TEM analysis of the blend morphologies following initial extrusion-compounding revealed a high compatibilisation efficiency of the SBM types with equal lengths of the end blocks and, furthermore, the desired raspberry morphology was achieved. In contrast, high PS contents in comparison to the other blocks led to a pronounced micelle formation in the PPE phase. Further evaluation of the blend structures following injection-moulding indicated that the morphologies remain relatively stable during this second melt-processing step. A detailed thermal analysis of all blend systems supports the interpretation of the observed morphological features. The fundamental correlation between SBM composition and blend morphology established in this study opens the door for the controlled development of interfacial properties of such compatibilised PPE/SAN blends during melt-processing.     

Modified interfacial tensions measured in situ in ternary polymer blends demonstrating partial wetting

An in situ Neumann triangle-focused ion beam-atomic force microscopy (NT-FIB-AFM) method has been used to measure modified PS/HDPE interfacial tensions in ternary PS/PP/HDPE blends prepared by melt mixing and demonstrating partial wetting. The ternary blend was modified with SEB, SB and SEBS copolymers. Results related to the position of the PS droplet at the interface show that a symmetrical diblock copolymer is somewhat more efficient in decreasing the interfacial tension compared to an asymmetrical one of similar molecular weight, while the SEBS triblock copolymer appears to have no effect at all. Using the NT-FIB-AFM method, the lowest modified PS/HDPE interfacial tension is 3.0 ± 0.4 mN/m for the symmetric diblock, compared to 4.2 ± 0.6 mN/m (N = 34) for the unmodified interface. This corresponds to an apparent areal density in SEB copolymer equal to 0.16 ± 0.03 molecules/nm², which is near reported saturation values. By varying the concentration of the copolymer, an emulsification curve reporting the value of the PS/HDPE modified interfacial tension as a function of the apparent areal density of the copolymer at the PS/HDPE interface has been obtained. The interfacial tension values obtained by the NT-FIB-AFM approach are significantly higher than the 0.5 ± 0.2 mN/m (N = 3) result obtained by using the classical breaking thread method with the same materials. This discrepancy does not appear to be due to a poor migration of the copolymer to the PS/HDPE interface, but could instead be attributed to the interfacial elasticity of the compatibilized interface, a phenomena that has not been accounted for so far in experimental studies on the morphology of compatibilized multicomponent polymer blends.     

Nanostructures and nanoporosity in thermoset epoxy blends with an amphiphilic polyisoprene-block-poly(4-vinyl pyridine) reactive diblock copolymer

Nanostructured thermoset blends were prepared based on a bisphenol A-type epoxy resin and an amphiphilic reactive diblock copolymer, namely polyisoprene-block-poly(4-vinyl pyridine) (PI-P4VP). Infrared spectra revealed that the P4VP block of the diblock copolymer reacted with the epoxy monomer. However, the non-reactive hydrophobic PI block of the diblock copolymer formed a separate microphase on the nanoscale. Ozone treatment was used to create nanoporosity in nanostructured epoxy/PI-P4VP blends via selective removal of the PI microphase and lead to nanoporous epoxy thermosets; disordered nanopores with the average diameter of about 60 nm were uniformly distributed in the blend with 50 wt% PI-P4VP. Multi-scale phase separation with a distinctly different morphology was observed at the air/sample interface due to the interfacial effects, whereas only uniform microphase separated morphology at the nanoscale was found in the bulk of the blend.     

The effect of polystyrene-block-poly(4-vinylpyridine) prepared by a RAFT method in the dispersion polymerization of MMA

The dispersion polymerization of methyl methacrylate (MMA) has been carried out using polystyrene-block-poly(4-vinylpyridine) copolymer [P(S-b-4VP)], which was prepared by a reversible addition-fragmentation chain transfer (RAFT) method, as a steric stabilizer in an alcohol media. The stable polymer particles were obtained when the block copolymer concentrations increased from 1 to 10 wt% relative to the monomer and the average particle sizes decreased from 5.3 to 3.4 μm with the increasing concentration of the block copolymer. In particular, the incorporation of 2 wt% polystyrene-block-poly(4-vinylpyridine) produced 4.3 μm of monodisperse PMMA particles with 2.14% of C_v. Thus, the P(S-b-4VP) block copolymer prepared by the RAFT method is working not only as a steric stabilizer, but also in providing monodisperse micron-sized PMMA particles.     

Morphology prediction and the effect of core‐shell structure on the rheological behavior of PP/EPDM/HDPE ternary blends

In this work, the morphologies of polypropylene (PP)/ethylene‐propylene‐diene (EPDM) rubber/high density polyethylene (HDPE) 70/20/10 blends were studied and compared with the predictions of the spreading coefficient and minimum free energy models. The interfacial tension of PP/HDPE, PP/EPDM, and HDPE/EPDM blends were obtained by fitting the experimental dynamic storage modulus data to Palierne's theory. The prediction results showed core‐shell morphology (core of HDPE and shell of EPDM) in PP matrix. The PP/EPDM/HDPE blends were respectively prepared by direct extrusion and lateral injection method. Core‐shell morphology (core of HDPE and shell of EPDM) could be obtained with direct extrusion corresponding to the predicted morphology. The morphology of PP/EPDM/HDPE blends could be effectively controlled by lateral injection method. For PP/EPDM/HDPE blend prepared by lateral injection method, HDPE and EPDM phase were dispersed independently in PP matrix. It was found that the different morphology of PP/EPDM/HDPE blends prepared by two methods showed different rheological behavior. When the core‐shell morphology (core of HDPE and shell of EPDM) appeared, the EPDM shell could confine the deformation of HDPE core significantly, so the interfacial energy contribution of dispersed phase on the storage modulus of blends would be weaken in the low frequency region. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Effect of block copolymers of various molecular architecture on the phase morphology and tensile properties of LDPE rich (LDPE/PS) blends

The emulsification efficiency of three different block copolymers consisting of hydrogenated polybutadiene (HPB) and polystyrene (PS), i.e. a pure diblock , a tapered diblock and a triblock copolymer has been compared in low density polyethylene/polystyrene (LDPE/PS) blends rich in polyethylene. The comparison relies upon the ability of these potential interfacial agents to stabilize fine phase dispersion and to promote good interfacial adhesion. Based on the phase morphology, the ultimate tensile properties and the dynamic viscosity of the modified blends, the tapered diblock copolymer is clearly the most efficient emulsifier. For instance a plateau is observed in the property-copolymer content dependence when 2 wt% tapered diblock are used compared to ca. 5 wt% in case of the pure diblock. In contrast, no plateau is observed when the triblock copolymer is used. This is assumed to result from a less quantitative localization of these two copolymers i.e. the pue diblock or the triblock at the LDPE/PS interface.     

Tuned phase behavior of weakly interacting polystyrene-block-poly(n-pentyl methacrylate) by selective solvent

We investigated, via small angle X-ray scattering, depolarized light scattering, rheometry, and transmission electron microscopy, the phase behavior of the mixture of a symmetric polystyrene-block-poly(n-pentyl methacrylate) copolymer (PS-b-PnPMA) showing the closed-loop phase behavior and excellent baroplasticity, and dodecanol, a PnPMA-selective solvent. We found that the addition of a selective solvent is simple, but very effective to obtain various microdomains including hexagonally packed cylinders and gyroids. Also, with increasing temperature, the mixtures showed multiple ordered-to-ordered transitions (OOTs) in addition to upper ordered-to-disordered transition (UODT). The first observation of gyroid microdomains in PS-b-PnPMA is very important, although they have been widely reported in many block copolymers, for instance, PS-block-polyisoprene copolymer (PS-b-PI) and PS-block-poly(d,l-lactide) copolymer (PS-b-PLA). Since the gyroid microdomains of PS-b-PnPMA show excellent baroplasticity, external pressure instead of temperature could easily change the microdomains.