Thin film confinement of a spherical block copolymer via forced assembly co-extrusion

Burt, Tiffani M.; Monemian, Seyedali; Jordan, Alex M.; Korley, LaShanda T. J.

doi:10.1039/c3sm27797f

Cited by 9 publications

(10 citation statements)

References 32 publications

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“…SI-4). Contrary to what was observed by Burt et al [10,12,43], SAXS patterns do not show any significant change, probably due to the lack of mobility of the copolymer at this temperature (T g,PMMA + 15 • C).…”

Section: Resultscontrasting

confidence: 95%

Controlling the order of triblock copolymer via confinement induced by forced self-assembly

Roland

Miquelard‐Garnier

Gervais

et al. 2016

Materials Today Communications

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We report the making of multilayered self-assembled films by coextrusion, composed of alternated layers of confining polycarbonate and confined poly(styrene-b-butadiene-b-methyl methacrylate), whose blocks are chemically different from the confining polymer, and presenting a self-assembled morphology directly after extrusion. The triblock copolymer layers thicknesses was varied from few hundreds to few tens of nanometers. As the triblock layer thickness is decreased and the draw ratio is increased, the triblock morphology is constrained into a preferential orientation and higher long-range order is observed by transmission electron microscopy and small angle X-ray scattering. This one-step and industrially scalable method allowing long-range ordering of the nanodomains is of interest for many engineering applications for which producing large quantity of materials is necessary.

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Section: Resultscontrasting

confidence: 95%

Controlling the order of triblock copolymer via confinement induced by forced self-assembly

Roland

Miquelard‐Garnier

Gervais

et al. 2016

Materials Today Communications

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“…Their work also showed that the packing of the cylinders was improved with the reduction of the layer thickness, especially after long times annealing [42e44]. A last article showed similar results for a spherical triblock (SEBS) extruded above T odt [46]. Nanolayer coextrusion has been developed in our lab [47e50] and also used recently to confine an asymmetric BCP poly(styreneb-butadiene-b-methyl methacrylate) (SBM) with an incompatible matrix (polycarbonate PC) [51].…”

Section: Introductionsupporting

confidence: 57%

“…Long-range order within the confined layers is achieved (and can be to some extent controlled via the processing parameters) on large scales of material through an industrially relevant process, similar to previous studies [42e44, 46,51]. More surprisingly and rarely observed experimentally (and to the best of our knowledge for the first time in a materials engineering context), it is shown that nanolayer coextrusion favors through shearing and "soft" confinement a cylindrical morphology over a lamellar one more thermodynamically favored.…”

Section: Introductionmentioning

confidence: 60%

From equilibrium lamellae to out-of-equilibrium cylinders in triblock copolymer nanolayers obtained via multilayer coextrusion

Montana

Roland

Richaud

et al. 2018

Polymer

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is an open access repository that collects the work of Arts et Métiers ParisTech researchers and makes it freely available over the web where possible. b s t r a c tMultilayer coextrusion was used to obtain nanolayered films of self-assembled commercial triblock copolymer poly(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate) (MAM) confined by poly(methyl methacrylate) (PMMA). The MAM layer thickness was varied from 30 nm to 500 nm (i.e. roughly 1 to 15e20 nanodomains) by changing either the number of multiplying elements or the chill roll draw ratio. The as-extruded triblock morphology within the layers was identified as cylindrical using transmission electronic microscopy (TEM) and small-angle X-ray scattering (SAXS). Surprisingly, this differs from the lamellar morphology identified at equilibrium in bulk and thin films for this triblock. Moreover, as the triblock layer thickness is decreased, the triblock morphology is constrained into a preferential orientation. Slightly different packings were observed on films with similar layer thicknesses but achieved with different processing routes. This one-step and industrially scalable method allowing long-range control of the self-assembly is of interest for engineering applications with large quantity of materials needed.

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“…Recent innovations in multilayer coextrusion − have utilized this scalable, melt-processing strategy to manufacture polymer composites containing distributed domains of micro- and nanoscale fibers. , Extruded composites of rectangular PCL fibers in a PEO matrix have been investigated for relevance in biomedical applications. Uniaxial PCL/PEO composite drawing and subsequent removal of the PEO matrix yielded PCL fiber scaffolds with tunable mechanics, high surface area, and nanoscale dimensions. , Functional coextruded PCL fibers were also achieved by Kim et al via surface modification using “click” chemistry, imparting gradient density modification and multifunctionality to enhance cellular proliferation and direct differentiation along the fiber scaffolds. − Although these extruded PCL fiber mats have potential in a range of biomedical applications, one can envision that this manufacturing platform may address key challenges in the development of fiber-reinforced hydrogels with synergistic mechanics due to the structural organization of these fiber/matrix coextruded composites with a distributed microscale PCL fiber architecture throughout the “sacrificial” PEO matrix.…”

Section: Introductionmentioning

confidence: 99%

In Situ Fabrication of Fiber Reinforced Three-Dimensional Hydrogel Tissue Engineering Scaffolds

Jordan

Kim

Voorde

et al. 2017

ACS Biomater. Sci. Eng.

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Hydrogels are an important class of biomaterials, but are inherently weak; to overcome this challenge, we report an in situ manufacturing technique to fabricate mechanically robust, fiber-reinforced poly(ethylene oxide) (PEO) hydrogels. Here, a covalent PEO cross-linking scheme was implemented to derive poly(ε-caprolactone) (PCL) fiber reinforced PEO hydrogels from multilayer coextruded PEO/PCL matrix/fiber composites. By varying PCL fiber loading between ∼0.1 vol % and ∼7.8 vol %, hydrogel stiffness was tailored from 0.69 ± 0.04 MPa to 1.94 ± 0.21 MPa. The influence of PCL chain orientation and enhanced mechanics via uniaxial drawing of PCL/PEO composites revealed a further 225% increase in hydrogel stiffness. To further highlight the robust nature of this manufacturing process, we also derived rigid poly(l-lactic acid) (PLLA) fiber-reinforced PEO hydrogels with a stiffness of 8.71 ± 0.21 MPa. Fibroblast cells were injected into the hydrogel volume, which displayed excellent ingrowth, adhesion, and proliferation throughout the fiber reinforced hydrogels. Finally, the range of mechanical properties obtained with fiber-reinforced hydrogels directed differentiation pathways of MC3T3-E1 cells into osteoblasts. This innovative manufacturing approach to achieve randomly aligned, well-distributed, micrometer-scale fibers within a hydrogel matrix with tunable mechanical properties represents a significant avenue of pursuit not only for load-bearing hydrogel applications, but also targeted cellular differentiation.

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Thin film confinement of a spherical block copolymer via forced assembly co-extrusion

Cited by 9 publications

References 32 publications

Controlling the order of triblock copolymer via confinement induced by forced self-assembly

Controlling the order of triblock copolymer via confinement induced by forced self-assembly

From equilibrium lamellae to out-of-equilibrium cylinders in triblock copolymer nanolayers obtained via multilayer coextrusion

In Situ Fabrication of Fiber Reinforced Three-Dimensional Hydrogel Tissue Engineering Scaffolds

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