Toward high-resolution 3D-printing of pharmaceutical implants - A holistic analysis of relevant material properties and process parameters.

In this work, filament-based 3D-printing, the most widely used sub-category of material extrusion additive manufacturing (MEAM), is presented as a promising manufacturing platform for the production of subcutaneous implants. Print nozzle diameters as small as 100 µm were utilized demonstrating MEAM of advanced porous internal structures at the given cylindrical implant geometry of 2 mm × 40 mm. The bottlenecks related to high-resolution MEAM of subcutaneous implants are systematically analyzed and the print process is optimized accordingly. Custom synthesized biodegradable phase-separated poly(ether ester) multiblock copolymers exhibiting appropriate melt viscosity at comparatively low printing temperatures of 135 °C and 165 °C were utilized as 3D-printing feedstock. The print process was optimized to minimize thermomechanical polymer degradation by employing print speeds of 30 mm∙s-1 in combination with a nozzle diameter of 150 µm at layer heights of 110 µm. These results portray the basis for further development of subcutaneous implantable drug delivery systems where drug release profiles can be tailored through the adaption of the internal implant structure, which cannot be achieved using existing manufacturing techniques.

Can Ferroelectricity Improve Organic Solar Cells?

Blends of semiconducting (SC) and ferroelectric (FE) polymers have been proposed for applications in resistive memories and organic photovoltaics (OPV). For OPV, the rationale is that the local electric field associated with the dipoles in a blend could aid exciton dissociation, thus improving power conversion efficiency. However, FE polymers either require solvents or processing steps that are incompatible with those required for SC polymers. To overcome this limitation, SC (poly(3-hexylthiophene)) and FE (poly(vinylidene fluoride-trifluoroethylene)) components are incorporated into a block copolymer and thus a path to a facile fabrication of smooth thin films from suitably chosen solvents is achieved. In this work, the photophysical properties and device performance of organic solar cells containing the aforementioned block copolymer consisting of poly(vinylidene fluoride-trifluoroethylene): P(VDF-TrFE), poly(3-hexylthiophene): P3HT and the electron acceptor phenyl-C61 -butyric acid methyl ester: [60]PCBM are explored. A decrease in photovoltaic performance is observed in blends of the copolymer with P3HT:[60]PCBM, which is attributed to a less favorable nanomorphology upon addition of the copolymer. The role of lithium fluoride (the cathode modification layer) is also clarified in devices containing the copolymer, and it is demonstrated that ferroelectric compensation prevents the ferroelectricity of the copolymer from improving photovoltaic performance in SC-FE blends.

Pronounced Surface Effects on the Curie Transition Temperature in Nanoconfined P(VDF-TrFE) Crystals.

Changes in the Curie transition temperature of nanoconfined poly(vinylidene fluoride-trifluoroethylene) P(VDF-TrFE) copolymers can have a severe impact on the electroactive behavior and the application range of these materials. Therefore, the origin of the change in the Curie transition temperature requires a profound understanding. In this work, block copolymer self-assembly into a spherical morphology proves to be a viable method to effectively confine P(VDF-TrFE) in three dimensions for studying the effect of nanoconfinement on the Curie transition. Using differential scanning calorimetry and wide-angle X-ray scattering, easily accessible experimental techniques, we follow the crystalline phase transitions, showing that confining P(VDF-TrFE) in a nonpolar polystyrene (PS) or poly(4-tert-butoxystyrene) (PtBOS) matrix results in an increase of the Curie transition upon cooling and heating. However, when a more polar matrix is used to nanoconfine P(VDF-TrFE), the Curie transition temperature is drastically reduced due to surface effects.

Electroactive materials with tunable response based on block copolymer self-assembly.

Ferroelectric polymers represent one of the key building blocks for the preparation of flexible electronic devices. However, their lack of functionality and ability to simply tune their ferroelectric response significantly diminishes the number of fields in which they can be applied. Here we report an effective way to introduce functionality in the structure of ferroelectric polymers while preserving ferroelectricity and to further tune the ferroelectric response by incorporating functional insulating polymer chains at the chain ends of ferroelectric polymer in the form of block copolymers. The block copolymer self-assembly into lamellar nanodomains allows confined crystallization of the ferroelectric polymer without hindering the crystallinity or chain conformation. The simple adjustment of block polarity leads to a significantly different switching behavior, from ferroelectric to antiferroelectric-like and linear dielectric. Given the simplicity and wide flexibility in designing molecular structure of incorporated blocks, this approach shows the vast potential for application in numerous fields.

Tailored Self-Assembled Ferroelectric Polymer Nanostructures with Tunable Response.

A facile ferroelectric nanostructures preparation method is developed based on the self-assembly of poly(2-vinylpyridine)-b-poly(vinylidene fluoride-co-trifluoroethylene)-b-poly(2-vinylpyridine) triblock copolymers (P2VP-b-P(VDF-TrFE)-b-P2VP), and the effect of morphological characteristics of the block copolymers on the ferroelectric response has been investigated for the first time. By simple adjustment of the ratio between the blocks, lamellar, cylindrical, and spherical morphologies are obtained in the melt and preserved upon crystallization of P(VDF-TrFE). However, at high P(VDF-TrFE) content, crystallization becomes dominant and drives the self-assembly of block copolymers. The crystallization study of the block copolymers reveals the preservation of the high degree of crystallinity inside the confined nanodomains as well as the reduction of the crystalline size and the Curie transition temperature with the confinement level. Only a small difference in the coercive field and the shape of the hysteresis loop is observed for block copolymers with a lamellar morphology produced either by crystallization-driven self-assembly or by confinement inside preformed lamellar domains. In contrast, delayed spontaneous polarization or the absence of dipole switching is demonstrated for the confinement of ferroelectric crystals inside both isolated cylindrical and spherical domains, exemplifying the influence of dimensionality on the critical size for ferroelectric order.

Polymer-based multiferroic nanocomposites via directed block copolymer self-assembly.

The existence of ferroelectricity and ferromagnetism in multiferroic materials and their coupling enables the manipulation of the electric polarization with applied magnetic field and vice versa, opening many doors for the practical applications. However, the preparation of polymeric multiferroic nanocomposites is often accompanied with aggregation of magnetic particles inside the ferroelectric polymeric matrix. To overcome this issue, we developed a simple and straightforward method to obtain multiferroic nanocomposites with an exceptional and selective dispersion of magnetic nanoparticles, using self-assembly of poly(vinylidene fluoride) (PVDF)-based block copolymers. Magnetic cobalt ferrite nanoparticles modified with gallic acid are selectively incorporated within poly(2-vinylpyridine) (P2VP) domains of the lamellar block copolymer due to strong hydrogen bond formation between the ligand and the P2VP block. Using this approach, phase separation between the blocks is improved, which leads to an increase in the degree of crystallinity, whereas the selective dispersion of nanoparticles inside amorphous domains prevents changes in the crystalline phase of the ferroelectric block. The obtained nanocomposites demonstrate both ferroelectric and magnetic properties without large conductive losses at high electric field, making them good candidates for improved multiferroic devices.

Hierarchical Self-Assembly of Supramolecular Double-Comb Triblock Terpolymers.

Involving supramolecular chemistry in self-assembling block copolymer systems enables design of macromolecular architectures that are challenging to obtain through conventional all-covalent routes. In this work we present supramolecular double-comb triblock terpolymers in which both outer blocks are able to interact with a surfactant via hydrogen bonding and thereby form a comb-shaped architecture upon complexation. While the neat triblock terpolymer only formed a triple lamellar morphology, multiple hierarchical structures were observed in these supramolecular comb-coil-comb triblock terpolymers by simply adjusting the surfactant concentration. Structures included spheres on tetragonally packed cylinders-in-lamellae and spheres on double parallel lamellae-in-lamellae, as evidenced by electron microscopy and X-ray scattering. Incorporation of a middle coil block thus allowed an even higher macromolecular complexity than the previously reported double-comb diblock copolymers.

Nanoconfinement-Induced ß-Phase Formation Inside Poly(vinylidene fluoride)-Based Block Copolymers.

The electroactive properties of poly(vinylidene fluoride) (PVDF) are a direct consequence of its crystalline phases. Although poorly understood, nanostructuring PVDF in confined geometries can drastically change its crystallization behavior. Therefore, we synthesized a variety of PVDF-based triblock copolymers to gain a better understanding of the melt crystallization and explore how crystallization is affected by the morphology and chemical nature of the amorphous block. Differential scanning calorimetry, small-/wide-angle X-ray scattering, and transmission electron microscopy gave us excellent insights into the morphology and the corresponding crystalline phases. We find that crystallization of PVDF inside spherical nanodomains occurs via a homogeneous nucleation mechanism leading to a large undercooling and the formation of the thermodynamically favorable ferroelectric ß-phase. On the contrary, when confined crystallization occurs inside a lamellar morphology, or in the case of breakout crystallization, a heterogeneous nucleation process leads to the formation of the nonferroelectric α-phase. Furthermore, favorable melt interactions between both blocks induce crystallization into the polar γ-phase at moderate cooling rates.