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American Society for Testing and Materials

A mean-field phase diagram for conformationally symmetric diblock melts using the standard Gaussian polymer model is presented. Our calculation, which traverses the weak- to strong-segregation regimes, is free of traditional approximations. Regions of stability are determined for disordered (DIS) melts and for ordered structures including lamellae (L), hexagonally packed cylinders (H), body-centered cubic spheres (QIm3m), close-packed spheres (CPS), and the bicontinuous cubic network with Ia3d symmetry (QIa3d). The CPS phase exists in narrow regions along the order−disorder transition for χN ≥ 17.67. Results suggest that the QIa3d phase is not stable above χN ∼ 60. Along the L/QIa3d phase boundaries, a hexagonally perforated lamellar (HPL) phase is found to be nearly stable. Our results for the bicontinuous Pn3m cubic (QPn3m) phase, known as the OBDD, indicate that it is an unstable structure in diblock melts. Earlier approximation schemes used to examine mean-field behavior are reviewed, and compa...

Unifying Weak- and Strong-Segregation Block Copolymer Theories

Electrospun nanofibers are extensively studied and their potential applications are largely demonstrated. Today, electrospinning equipment and technological solutions, and electrospun materials are rapidly moving to commercialization. Dedicated companies supply laboratory and industrial-scale components and apparatus for electrospinning, and others commercialize electrospun products. This paper focuses on relevant technological approaches developed by research, which show perspectives for scaling-up and for fulfilling requirements of industrial production in terms of throughput, accuracy, and functionality of the realized nanofibers. A critical analysis is provided about technological weakness and strength points in combination with expected challenges from the market.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/mame.201200290

Industrial Upscaling of Electrospinning and Applications of Polymer Nanofibers: A Review

Introduction to physical polymer science

The electrospinning process was used successfully to fabricate nanofibers of poly(ethylene oxide) (PEO) in which multiwalled carbon nanotubes (MWCNT) are embedded. Initial dispersion of MWCNTs in water was achieved using amphiphiles, either as small molecules (sodium dodecyl sulfate, SDS) or as a high molecular weight, highly branched polymer (Gum Arabic). These dispersions provided separation of the MWCNTs and their individual incorporation into the PEO nanofibers by subsequent electrospinning. The focus of this work is on the development of axial orientations in these multicomponent nanofibers. A theoretical model is presented for the behavior of rodlike particles representing CNTs in electrospinning. Initially the rods are randomly oriented, but due to the sinklike flow in a wedge they are gradually oriented mainly along the stream lines, so that straight CNTs are almost oriented upon entering the electrospun jet. The degrees of orientation of polymer, surfactant, and MWCNT were studied using X-ray dif...

Carbon Nanotubes Embedded in Oriented Polymer Nanofibers by Electrospinning

As Macromolecules celebrates its 50th anniversary, we reflect on the impact of polymer chemistry and engineering on the advancement of synthetic polymer fibers. In this Perspective, we focus on two exemplary cases: (i) high performance fibers and (ii) ultrafine electrospun fibers. High performance in this context refers to fibers like Kevlar and Spectra, which emerged as a consequence of novel chemistry and processing innovations to convert synthetic polymers into fibers with exceptional specific stiffness and strength. More recently, the development of “ultrafine” (i.e., submicrometer diameter) fibers by technologies such as electrospinning has advanced dramatically, resulting in interesting, emergent structures and properties, such as surface and internal morphologies, electrical and mechanical properties, and growth applications like tissue engineering and sensors, which are subjects of current research. In both cases, challenges and opportunities exist in the development of polymer processes to advanc...

50th Anniversary Perspective: Advanced Polymer Fibers: High Performance and Ultrafine

Multiaxial (triaxial/coaxial) electrospinning is utilized to fabricate block copolymer (poly(styrene-b-isoprene), PS-b-PI) nanofibers covered with a silica shell. The thermally stable silica shell allows post-fabrication annealing of the fibers to obtain equilibrium self-assembly. For the case of coaxial nanofibers, block copolymers with different isoprene volume fractions are studied to understand the effect of physical confinement and interfacial interaction on self-assembled structures. Various confined assemblies such as co-existing cylinders and concentric lamellar rings are obtained with the styrene domain next to the silica shell. This confined assembly is then utilized as a template to guide the placement of functional nanoparticles such as magnetite selectively into the PI domain in self-assembled nanofibers. To further investigate the effect of interfacial interaction and frustration due to the physically confined environment, triaxial configuration is used where the middle layer of the self-assembling material is sandwiched between the innermost and outermost silica layers. The results reveal that confined block-copolymer assembly is significantly altered by the presence and interaction with both inner and outer silica layers. When nanoparticles are incorporated into PS-b-PI and placed as the middle layer, the PI phase with magnetite nanoparticles migrates next to the silica layers. The migration of the PI phase to the silica layers is also observed for the blend of PS and PS-b-PI as the middle layer. These materials not only provide a platform to further study the effect of confinement and wall interactions on self-assembly but can also help develop an approach to fabricate multilayered, multistructured nanofibers for high-end applications such as drug delivery.

Confined assembly of asymmetric block-copolymer nanofibers via multiaxial jet electrospinning.

Many types of consumer-grade packaging can be used in material extrusion additive manufacturing processes, providing a high-value output for waste plastics. However, many of these plastics have reduced mechanical properties and increased warpage/shrinkage compared to those commonly used in three-dimensional (3D) printing. The addition of reinforcing materials can lead to stiffer parts with reduced distortion. This paper presents work in the reinforcement of recycled polypropylene using cellulose waste materials to generate a green composite feedstock for extrusion-based polymer additive manufacturing. Recycled polypropylene/waste paper, cardboard, and wood flour composites were made using a solid-state shear pulverization process. Fourier transform infrared and thermogravimetric analysis were utilized to qualitatively analyze the amount of filler incorporated into the 3D-printed materials. Recycled polymer composites had increased levels of filler incorporated in the printed parts compared to the virgin polymer composites based on the thermal gravimetric analysis. The dynamic mechanical analysis showed a ca. 20-30% increase in storage modulus with the addition of cellulose materials. Tensile strength was not significantly increased with the addition of 10 wt % cellulose, but the elastic modulus increased 38% in virgin polypropylene. The analysis of fracture surfaces revealed that failure initiates at the interface, suggesting that the interfacial strength is weaker than the filler strength.

https://pubs.acs.org/doi/pdf/10.1021/acsomega.9b01564

Recycled Cellulose Polypropylene Composite Feedstocks for Material Extrusion Additive Manufacturing.

Stiff, strong and tough ultrafine polyethylene fibers that rival the best high performance fibers, but with diameters less than one micron, are fabricated for the first time by “gel-electrospinning.” In this process, solution concentration and process temperatures are chosen to induce the formation of gel filaments “in flight,” which are subsequently drawn at high rates as a consequence of the whipping instability. The resulting submicron-diameter fibers exhibited Young’s moduli of 73 ± 13 GPa, yield strengths of 3.5 ± 0.6 GPa, and toughnesses of 1.8 ± 0.3 GPa, on average. Among the smallest fibers examined, one with a diameter of 490 ± 50 nm showed a Young’s modulus of 110 ± 16 GPa, ultimate tensile strength of 6.3 ± 0.9 GPa, and toughness of 2.1 ± 0.3 GPa, a combination of mechanical properties that is unparalleled among polymer fibers to date. The correlation of stiffness, strength and toughness with fiber diameter is attributed to high crystallinity and crystallite orientation, combined with fewer defects and enhanced chain slip associated with small diameter and high specific surface area. Gel-electrospinning improves the prospects for production of such fibers at scale.

Jay Hoon Park

Papers

50th Anniversary Perspective: Advanced Polymer Fibers: High Performance and Ultrafine

Confined assembly of asymmetric block-copolymer nanofibers via multiaxial jet electrospinning.

Recycled Cellulose Polypropylene Composite Feedstocks for Material Extrusion Additive Manufacturing.

Ultrafine high performance polyethylene fibers

Ultrafine high performance polyethylene fibers