Effect of the nature of annealing solvent on the morphology of diblock copolymer blend thin films

The morphologies and structures for the thin film of blend systems consisting of two asymmetric polystyrene-block-polybutadiene (SB) diblock copolymers induced by annealing in the vapor of different solvents, namely, cyclohexane, benzene, and heptane, which have different selectivity or preferential affinity for a certain block, were investigated by tapping mode atomic force microscopy (AFM) and transmission electron microscopy (TEM). The results revealed that even a slight preferential affinity of good solvent for one block would strongly alter the morphology of the blend thin film.

Solvent-induced Morphology of the Binary Mixture of Diblock Copolymer in Thin Film: The Block Length and Composition Dependence of Morphology

A series of binary SB blend samples with various overall volume fraction of PS (Phi(PS)) and different discrete distribution of the block length (denoted as d(PS) or d(PB)) were prepared by mixing various asymmetric poly(styrene)-block-poly(butadiene) (SB) block copolymers with a symmetric SB block copolymer. The influences of the external solvent field, composition, and the block length distribution on the morphologies of the blends in the thin films were investigated by atomic force microscopy (AFM) and transmission electron microscopy (TEM). The experimental results revealed that after solvent annealing, the interface of the blend thin films depended mainly on the cooperative effects of the annealing solvent and the inherently interfacial curvature of the blends. Upon exposure to the saturated vapor of cyclohexane, which has preferential affinity for the PB block, a "threshold" of Phi(PS) (approximate 0.635-0.707) was found. Below such threshold, the influence of the annealing solvent played an important role on the interfacial curvature of the blend thin film.

Crystalline morphology of poly(L-lactic acid) thin films

Crystalline morphologies of spin-coated poly(L-lactic acid) (PLLA) thin films under different conditions are investigated mainly with atomic force microscopy (AFM) technique. When PLLA concentration in chloroform is varied from 0.01 to 1% gradually, disordered structure, rod-shape and larger spheres aggregates are observed in thin films subsequently. Under different annealing temperature, such as at 78, 102, 122 degrees C, respectively, we can find most rod-like crystalline aggregates. Interestingly, we observed that nucleation sites locate at the edge of the holes at the original crystalline stage. Then, these holes developed to form chrysanthemum-like and rods subsequently with annealing time meanwhile the size and the shape of crystalline aggregate are changed. In addition. effect of substrate and solvent on morphology is also discussed. On the other hand, the possible mechanism of crystalline morphology evolution is proposed.

Evolution of phase morphology of high impact polypropylene particles upon thermal treatment

Solvent fractionation and differential scanning calorimetry (DSC) results show that high impact polypropylene (hiPP) produced by a multistage polymerization process consists of PP homopolymer, amorphous ethylene-propylene random copolymer (EPR), and semicrystalline ethylene-propylene copolymer. For the original hiPP particles obtained right after polymerization, direct transmission electron microscopy (TEM) observation reveals a fairly homogeneous morphology of the ethylene-propylene copolymer (EP) phase regions inside, while the polyethylene-rich interfacial layer observed between the EP region and the iPP matrix supports that EP copolymers form on the subglobule surface of the original iPP particles. Compared with that in original hiPP particles, the dispersed EP domains in pellets have much smaller average size and relatively uniform size distribution, indicating homogenization of the EP domains in the hiPP by melt-compounding. Upon heat-treatment, phase reorganization occurs in hiPP, and the dispersed EP domains can form a multiple-layered core-shell structure, comprising a polyethylene-rich core, an EPR intermediate layer and an outer shell formed by EP block copolymer, which accounts to some extent for the good toughness-rigidity balance of the material.

Thermal stability, crystallization, structure and morphology of syndiotactic 1,2-polybutadiene/organoclay nanocomposite

Syndiotactic 1,2-polybutadiene/organoclay nanocomposites were prepared and characterized by thermogravimetry analysis (TGA), X-ray diffraction (XRD), polarized optical microscopy (POM), and differential scanning calorimetry (DSC), respectively. The XRD shows that exfoliated nanocomposites are formed dominantly at lower clay concentrations (less than 2%), at higher clay contents intercalated nanocomposites dominate. At the same time, the XRD indicates that the crystal structures of sPB formed in the sPB/organoclay nanocomposites do not vary, only the relative intensity of the peaks corresponding to (0 1 0) and (2 0 0)/(1 1 0) crystal planes, respectively, varies. The DSC and POM indicate that organoclay layers can improve cooling crystallization temperature, crystallization rate and reducing the spherulite sizes of sPB. TGA shows that under argon flow the nanocomposites exhibit slight decrease of thermal stability, while under oxygen flow the resistance of oxidation and thermal stability of sPB/organoclay nanocomposites were significantly improved relative to pristine sPB. The primary and secondary crystallization for pristine sPB and sPB/organoclay (2%) nanocomposites were analyzed and compared based on different approaches.

Study of controllable aggregation morphology of ABA amphiphilic triblock copolymer in dilute solution by changing the solvent property

We have studied, both experimentally and theoretically, the aggregation morphology of the ABA amphiphilic triblock copolymer in dilute solution by changing the solvent property. Experimental results showed that the micellar morphology changed from spheres to rods and then to vesicles by changing the common solvent from N-N-dimethylformamide (DMF) to dioxane and then to tetrahydrofuran (THF). These controllable aggregates were also obtained by Monte Carlo simulation. The simulative results showed that the solvent property is a key factor that determines the copolymer aggregation morphology. The morphology changed from spheres to rods and then to vesicles by increasing the solvent solubility, corresponding to the change of stretched of the copolymer chains in the micellar cores. This result is in good agreement with the experimental one. Moreover, the simulative results revealed that the end-to-end distant of the ABA triblock copolymer in the vesicle was larger than that in the spheres and rods, indicating that the copolymer chains were more stretched in vesicles than in the spheres and rods. Furthermore, we gave the distribution of the fraction of the chain number with the end-to-end distance. The results indicated that the amount of folded chains is almost the same as that of stretched chains in the vesicle. Although most chains were folded, stretched chains could be found in the rod and sphere micelles.

Morphology of electrodeposited poly(3,4-ethylenedioxythiophene)/poly(4-styrene sulfonate) films

Poly(4-styrene sulfonate)-doped poly(3,4-ethylenedioxythiophene) (PEDOT/PSS) films with ring-, arrow-, and bubble-like microstructures have been electrochemically generated simply by a one-step cyclic voltammetry in an aqueous media. Influences of applied potentials and surfactant/dopant-PSS on morphology of the resulting film were investigated, and a gas bubble template mechanism has been proposed. The result confirmed a well-doping of PSS in the PEDOT film. Electrochemical property and conductivity of the micro-structured PEDOT/PSS film were investigated further. Similar preparation with potential applications in fabrication of microdevices and micro-sensors can be extended to other micro-structured conducting polymers.

Synthesis and morphology of polyethylene chains grafted onto the surface of crosslinked polystyrene microspheres

The bifunctional comonomer 4-(3-butenyl) styrene was used to synthesize crosslinked polystyrene microspheres (c-PS) with pendant butenyl groups on their surface via suspension copolymerization. Polyethylene chains were grafted onto the surface of c-PS microspheres (PS-g-PE) via ethylene copolymerizing with the pendant butenyl group on the surface of the c-PS microspheres under the catalysis of metallocene catalyst. The composition and morphology of the PS-g-PE microspheres were characterized by means of Fourier transform infrared spectroscopy, Fourier transform Raman spectroscopy, X-ray photoelectron spectroscopy, and field-emission scanning electron microscopy. It is possible to control the content of PE grafted onto the surface of c-PS microspheres by varying the polymerization time or the initial quantity of pendant butenyl group on the surface of c-PS microspheres. Investigation on the morphology and crystallization behavior of grafted PE chains showed that different surface patterns could be formed under various crystallization conditions. Moreover, the crystallization temperature of PE chains grafted on the surface of c-PS microspheres was 6 degrees C higher than that of pure PE. The c-PS microspheres decorated by PE chains had a better compatibility with PE matrix.

Crystallization and ring-banded spherulite morphology of poly(ethylene oxide)-block-poly(epsilon-caprolactone) diblock copolymer

The crystallization behavior of crystalline-crystalline diblock copolymer containing poly(ethylene oxide) (PEO) and poly(epsilon-caprolactone) (PCL), in which the weight fraction of PCL is 0.815, has been studied via differential scanning calorimeter (DSC), wide-angle X-ray diffraction (WAXD), and polarized optical microscopy (POM). DSC and WAXD indicated that both PEO and PCL blocks crystallize in the block copolymer. POM revealed a ring-banded spherulite morphology or the PEO-b-PCL diblock copolymer.

Effects of molecular weight, solvent and substrate on the dewetting morphology of polystyrene films

Surface morphology of polystyrene (PS) films on different substrates by spin-coating before and after annealing was observed using atomic force microscopy (AFM). The effects of polymer molecular weight, substrates, solvents, and annealing conditions on the morphology of the films were investigated. Before annealing, the grain height decreases, and simultaneously the grain diameter increases with molecular weight (M-w) within the measured molecular weight. After annealing. the situation is opposite, i.e., the grain height increases while the grain diameter decreases with M-w. Furthermore, after annealing the smaller surface roughness (Ra) was obtained. It was also found that film surface roughness (Ra) depends on the vapor pressure and dipole moment of different used solvents as well as the substrates. The experimental results show that when the used solvents have similar dipole moment but different vapor pressure, the Ra of PS film decreased with the decreasing vapor pressure of solvents whether on silicon or on mica. And when the used solvents have close vapor pressure but different dipole moment, the Ra decreased with the increasing of solvent dipole moments on both substrates.

Morphology of polyimide fibers derived from 3,3 ',4,4 '-biphenyltetracarboxylic dianhydride and 4,4 '-oxydianiline

As one member of high performance fibers, aromatic polyimide fibers possess many advantages, such as high strength, high modulus, high and low temperature resistance, and radiation resistance. However, the preparation of the high performance fibers is so difficult that the commercial fibers have not been produced except P84 with good flame retardancy. In this report, a polyimide was synthesized from 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 4,4'-oxydianiline (ODA) and the fibers were prepared from its solution by a dry-jet wet-spinning process. The formation of the as-spun fibers in different coagulation bath composition was discussed. Scanning electron microscope (SEMI) was employed to study the morphology of the as-spun fibers. As a result, the remnant solvent existed in the as-spun fibers generated from coagulation bath of alcohol and water. There were many fibrils and microvoids with the dimension of tens of nanometers in the fibers. One could observe the obvious fibrillation and the drawn fibers.

Molecular weight effects on the phase morphology of PS/P4VP blend films on homogeneous SAM and heterogeneous SAM/Au substrates

The effects of the molecular weight of polystyrene (PS) component on the phase separation of PS/poly(4-vinylpyridine) (PS/P4VP) blend films on homogeneous alkanethiol self-assembled monolayer (SAM) and heterogeneous SAM/Au substrates have been investigated by means of atomic force microscopy (AFM). For the PS (22.4k)/P4VP (60k) system, owing to the molecular weight of PS component is relatively small, the well-aligned PS and P4VP stripes with good thermal stability are directed by the patterned SAM/Au surfaces. With the increase of the molecular weight of PS component (for the PS (582k)/P4VP (60k) system), the diffusion of P4VP is hindered by the high viscosity of PS during the fast spin-coating process. The phase separation behavior of PS/P4VP on the SAM/Au patterned substrates is similar to that on the homoueneous SAM and cannot be easily directed by the patterned SAM surfaces even though the characteristic length of the lateral domain morphology is commensurate with the stripe width.

Study of the synthesis, crystallization, and morphology of poly(ethylene glycol)-poly(is an element of-caprolactone) diblock copolymers

Poly(ethylene glycol) -poly(epsilon-caprolactone) diblock copolymers PEG-PCL were synthesized by ring-opening polymerization of c-caprolactone using monomethoxy poly(ethylene glycol) as the macroinitiator and calcium ammoniate as the catalyst. Obvious mutual influence between PEG and PCL crystallization was studied by altering the relative block length. Fixing the length of the PEG block (M-n = 5000) and increasing the length of the PCL block, the crystallization temperature of the PCL block rose gradually from I to about 35 degreesC while that of the PEG block dropped from 36 to -6.6 degreesC. Meanwhile, the melting temperature of the PCL block went up from 30 to 60 degreesC, while that of the PEG block declined from 60 to 41 degreesC. If the PCL block was longer than the PEG block, the former would crystallize first when cooling from a molten state and led to obviously imperfect crystallization of PEG and vice versa. And they both crystallized at the same temperature, if their weight fractions were equal. We found that the PEG block could still crystallize at -6.6 degreesC even when its weight fraction is only 14%. A unique morphology of concentric spherulites was observed for PEG5000-PCL5000.