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Polymer microspheres have been widely investigated because of their applications in areas such as drug delivery, latex diagnostics, and affinity bioseparators. The effect of annealing on polymer microspheres, however, has been rarely studied. In this work, we demonstrate the morphology transformation of polystyrene (PS) microspheres annealed thermally on poly(methyl methacrylate) (PMMA) films. During the annealing process, the PS microspheres gradually sink into the PMMA films and transform into PS hemispheres, driven by the reduction of the surface and interfacial energies. The effect of the film thicknesses on the morphology transformation is also studied. In addition, porous PMMA films or PS hemispheres can be obtained by removing the PS or the PMMA domains of the polymer composites using cyclohexane or acetic acid, respectively.

The Plateau–Rayleigh instability is a phenomenon driven by the reduction of the surface energies, in which a liquid cylinder transforms to a series of droplets with distinct spacing. This instability phenomenon is also applied broadly for the transformation of cylindrical materials to spherical particles in homogeneous environments. The demonstration of the instability in heterogeneous environments, however, has been less studied. Here, we study the Plateau–Rayleigh instability of electrospun polystyrene (PS)/poly(methyl methacrylate) (PMMA) core–shell fibers annealed on n-octadecyltrichlorosilane (ODTS)-modified glass substrates with toluene vapors. After the annealing procedures, the PS/PMMA core–shell fibers transform to anisotropic sunny-side-up egg-shaped polymer structures, driven by the reduction of the total surface and interfacial energies. Quantitative analyses are performed on the sizes of the structures. Fluorescent fibers are also prepared by electrospinning and annealed on the ODTS-modified ...

Electrospinning has emerged as a powerful strategy to develop controlled release drug delivery systems but the effects of post-fabrication solvent vapor annealing on drug-loaded electrospun fibers have not been explored to date. In this work, electrospun poly(ε-caprolactone) (PCL) fibers loaded with the hydrophobic small-molecule spironolactone (SPL) were explored. Immediately after fabrication, the fibers are smooth and cylindrical. However, during storage the PCL crystallinity in the fibers is observed to increase, demonstrating a lack of stability. When freshly-prepared fibers are annealed with acetone vapor, the amorphous PCL chains recrystallize, resulting in the fiber surfaces becoming wrinkled and yielding shish-kebab like structures. This effect does not arise after the fibers have been aged. SPL is found to be amorphously dispersed in the PCL matrix both immediately after electrospinning and after annealing. In vitro dissolution studies revealed that while the fresh fibers show a rapid burst of SPL release, after annealing more extended release profiles are observed. Both the rate and extent of release can be varied through changing the annealing time. Further, the annealed formulations are shown to be stable upon storage.

Electrospun polymer fibers have attracted great attention in recent years because of their unique properties and applications in various areas such as tissue engineering and drug delivery. It remains a great challenge, however, to understand the morphology and property changes of electrospun polymer fibers induced by post-treatment, especially thermal annealing. In this work, we investigate the morphology evolution of electrospun polystyrene (PS) fibers thermally annealed on poly(vinyl alcohol) (PVA) films. Driven by the surface and interfacial tensions, the PS fibers transform to a series of regularly aligned anisotropic particles embedded in the PVA films via a Rayleigh instability-type transformation. From the in-situ observed optical microscopy (OM) images, higher growth rates of undulated amplitude can be obtained for thinner PVA films, revealing the effect of the underlying glass substrates.

Electrospun polymer core–shell fibers have gained much attention because of their promising applications in areas such as electronic devices, drug delivery, and tissue engineering. The morphology transformation of polymer core–shell fibers, however, has been rarely investigated. Here, we study the effect of thermal annealing on the morphology transformation of electrospun polystyrene (PS)/poly(methyl methacrylate) (PMMA) core–shell fibers on PMMA films. Two types of transformation processes are discovered. In the first type of the transformation process (type I), the PS cores transform to hemispherical particles after the annealing process; in the second type of the transformation process (type II), the PS cores transform to spherical particles after the annealing process. The measured sizes of the hemispherical and spherical PS domains fall into two classified regions, as predicted for the two different types of transformation processes. It is also observed that the growth rates of the undulated amplitud...

In this work, a novel method to fabricate polymer spheres encapsulated in polymer films by breaking embedded electrospun fibers (BEEF) was developed. Polymer fibers were first prepared by electrospinning and embedded in other polymer films using a three-layer deposition method. After thermal annealing, the electrospun fibers transform into individual spheres with regular spacing and sizes. Poly(methyl methacrylate) (PMMA) and polystyrene (PS) are both used as the fiber or film materials. The transformation process can be observed in-situ by optical microscope (OM) and is similar to the Plateau–Rayleigh instability. The growth rates of the surface undulation of the fibers are calculated, and higher growth rates are observed at higher annealing temperatures. The sizes of the encapsulated polymer spheres agree well with the theoretical predictions. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016

We develop a simple and feasible method to fabricate polymer nanoparticles by annealing polymer films in a uniform environment. Different from the conventional methods, no extra additive or emulsifier is needed in the preparation processes. Poly(methyl methacrylate) (PMMA) films are used as a model system and annealed at elevated temperatures in ethylene glycol, which provides a uniform three-dimensional annealing environment and acts as stabilizers once the nanoparticles are formed. After the annealing process, PMMA nanoparticles with monodisperse diameters are formed. By examining the remaining films after the annealing process, the formation mechanism, which involves surface undulation and detachment of polymer nanoparticles, is proposed. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 2471–2475

Anisotropic polymer particles have attracted great attention because of their unique properties and potential applications in various areas, such as microelectronics, drug delivery, and medical imaging. The fabrication and morphology control, especially the shape recovery, of anisotropic polymer particles, however, remains a challenging task. In this work, we develop a novel strategy to fabricate anisotropic polymer particles by thermally stretching poly(vinyl alcohol) (PVA) films embedding polystyrene (PS) microspheres using a weight. Depending on the preannealing condition, anisotropic PS particles with two different shapes, sharp-headed and blunt-headed PS particles, can be obtained. The PVA films can be selectively removed by isopropanol/water, releasing the anisotropic PS particles. By adding tetrahydrofuran (THF), a good solvent for PS, into the PS particle-containing solutions, the anisotropic particles gradually transform back to spheres to reduce the total interfacial energies. The shape recovery rates of the polymer particles can be controlled by the amount of the added THF. This work not only provides a simple and feasible route to fabricate anisotropic polymer particles but also contributes to a deeper understanding in the solvent-induced shape recovery process from anisotropic polymer particles to polymer spheres.

Designing anisotropic particles of various shapes draws great attention to scientists nowadays. We develop a facile and simple method to fabricate anisotropic polymer particles from spherical polymer particles. Poly(vinyl alcohol) (PVA) films spin-coated with polystyrene (PS) microspheres are confined on both sides using binder clips and are heated above the glass-transition temperatures of the polymers. During the thermal annealing process, the PS particles sink into the PVA films and transform to anisotropic particles. Depending on the distances to the bound regions, oblate spheroid PS particles or prolate spheroid particles with different aspect ratios can be obtained. The transformation of the particles is mainly driven by the stretching forces and the squeezing forces. The main advantage of this method is that anisotropic particles with different shapes can be fabricated simultaneously on a single film. We expect that this novel method can be helpful to various fields including colloids science, suspension rheology, and drug delivery.

In this work, nanofibers based on hydrophilic poly(vinylpyrrolidone) (PVP) and hydrophobic ethyl cellulose (EC) were generated via electrospinning. A model antibiotic, ciprofloxacin (CIF), was also incorporated into the fibers. Fibers were collected on both a foil substrate and a commercial gauze, the latter in the interests of developing a smart fabric. Electron microscopy images revealed that the fibers collected on both foil and fabric were homogeneous and cylindrical. Infrared spectroscopy, X-ray diffraction and differential scanning calorimetry demonstrated that CIF was successfully loaded into the fibers and present in the amorphous physical form. In vitro drug release tests were conducted to simulate drug release from the formulations into a wound site, and as expected the hydrophilic fibers showed much faster release than their hydrophobic analogues. CIF was released through a combined mechanism of polymer erosion and drug diffusion, and the EC nanofibers displayed close to zero-order release over three days. Fibroblast cells are able to grow and proliferate on the fibers. Finally, inhibition zone assays revealed that the growth of both Gram positive and Gram negative bacteria could be effectively inhibited as a result of the presence of CIF in the fibers. There were no marked differences between the fibers collected on foil and on gauze, and electrospinning can be performed directly onto a gauze substrate to prepare a smart fabric.

Electrospinning is one of the most common methods to prepare polymer fibers with sizes ranging from several nanometers to hundreds of micrometers. In most studies of electrospun polymer fibers, the properties and morphologies of polymer fibers are controlled by changing the electrospinning conditions. Few studies focus on the post-treatments of polymer fibers, which are critical for many fiber-based applications. In this work, we investigate the morphology transformation of electrospun polystyrene (PS) fibers annealed on top of poly(methyl methacrylate) (PMMA) film-coated glass substrates. In situ optical microscopy and stimulated Raman scattering (SRS) microscopy are used to observe the transformation process, which is driven by the Rayleigh instability, the surface tensions, and the interfacial tensions of polymers. Depending on the thickness of the underlying PMMA films, the electrospun PS fibers may transform into hemispheres or disks. The growth rates of the undulating amplitude are also affected by the film thickness.

Electrospun core-shell fibers have great potentials in many areas, such as tissue engineering, drug delivery, and organic solar cells. Although many core-shell fibers have been prepared and studied, the morphology transformation of core-shell fibers have been rarely studied. In this work, the morphology evolution of electrospun core-shell polymer fibers driven by the Plateau-Rayleigh instability is investigated. Polystyrene/poly(methyl methacrylate) (PS/PMMA) core-shell fibers are first prepared by using blend solutions and a single axial electrospinning setup. After PS/PMMA core-shell fibers are annealed on a PS film, the fibers undulate and sink into the polymer film, forming core-shell hemispheres. The evolution process, which can be observed in situ by optical microscopy, is mainly driven by achieving lower surface and interfacial energies. The morphologies of the transformed structures can be confirmed by a selective removal technique, and polymer microbowls can be obtained.

Electrospinning has been widely used to prepare polymer fibers with diameters ranging from a few nanometers to micrometers. While most studies focus on controlling the sizes and morphologies of electrospun polymer fibers by changing electrospinning conditions, the effect of post-treatments such as thermal annealing on the properties of electrospun polymer fibers has been less studied. Here, we investigate the effect of thermal annealing on the morphology changes of electrospun polystyrene (PS) fibers on substrates. Different from annealing the fibers in a uniform environment, annealing the fibers on substrates results in a substrate-dependent morphology transformation. When the electrospun PS fibers are annealed on a glass substrate, wetting of the fibers on the glass substrate occurs. When the electrospun PS fibers are annealed on a poly(methyl methacrylate) (PMMA)-coated substrate, a Rayleigh-instability-driven morphology transformation is observed. The polymer fibers transform into hemispherical polyme...

Fibrillar materials have gained much attention recently because of their unique properties and potential applications. Although many methods have been developed to fabricate materials, it remains challenging to prepare fibrillar materials containing multicomponent materials or even with complex structures. Here, a facile strategy is developed to fabricate bamboo-shaped fibers by treating electrospun polymer core-shell fibers with solvent vapor annealing. Electrospun polystyrene (PS)/poly(methyl methacrylate) (PMMA) core-shell fibers are first prepared by electrospinning PS/PMMA blend solutions via a phase separation process. When the PS/PMMA core-shell fibers are annealed with the vapor of cyclohexane, which swells and delocalizes the PS domains selectively, the fibers transform into bamboo-shaped structures. The bamboo-shaped structures can be further examined by swelling and delocalizing the PMMA domains selectively, revealing the undulated PS structures. The thermal insulation properties of the fibers with bamboo-shaped structures are observed to be enhanced compared with the original polymer core-shell fibers.

The fabrication of electrospun polymer fibers is demonstrated with anisotropic cross-sections by applying a simple pressing method. Electrospun polystyrene or poly(methyl methacrylate) fibers are pressed by flat or patterned substrates while the samples are annealed at elevated temperatures. The shapes and morphologies of the pressed polymer fibers are controlled by the experimental conditions such as the pressing force, the pressing temperature, the pressing time, and the surface pattern of the substrate. At the same pressing force, the shape changes of the polymer fibers can be controlled by the pressing time. For shorter pressing times, the deformation process is dominated by the effect of pressing and fibers with barrel-shaped cross-sections can be generated. For longer pressing times, the effect of wetting becomes more important and fibers with dumbbell-shaped cross-sections can be obtained. Hierarchical polymer fibers with nanorods are fabricated by pressing the fibers with porous anodic aluminum oxide templates.