Improved Polypropylene Thermoformability through Polyethylene Layering.

Due to its low cost, stiffness, and recyclability, isotactic polypropylene (iPP) is an excellent candidate for packaging applications. However, iPP is notoriously difficult to thermoform due to its low melt strength. The addition of just 10 thin layers of high-molecular-weight, linear low-density polyethylene (LLDPE) into iPP sheets by coextrusion significantly increased extensional viscosity and reduced sag. Both LLDPE and iPP were metallocene-catalyzed with excellent adhesion as measured in our previous work. We performed a series of hot tensile tests and sheet sag measurements to determine the properties of the iPP sheet and the multilayer sheet between 130 and 180 °C. To evaluate the thermoformability of these multilayer sheets, truncated conical cups were positive vacuum formed at different temperatures and heating times, and the crush strength was measured. Cups that released easily from the mold with good shape retention and a crush strength within 80% of the maximum value were used to define a temperature-time thermoformability window. We estimated the maximum stress that occurred during the thermoforming process to be 5 MPa. Layer thicknesses before and after thermoforming were used to estimate an average strain of 0.78. The thin LLDPE layers decreased the yield stress below 5 MPa. This enabled thermoforming at sheet temperatures as low as 150 °C. The immiscible LLDPE interfaces increased extensional viscosity, which decreased sag in the multilayer sheets compared to iPP. This broadened the thermoforming range to temperatures as high as 180 °C and allowed longer heating times. These highly thermoformable, layered sheets may be recycled as iPP since they contain only 8% of LLDPE.

Semibatch monomer addition as a general method to tune and enhance the mechanics of polymer networks via loop-defect control.

Controlling the molecular structure of amorphous cross-linked polymeric materials is a longstanding challenge. Herein, we disclose a general strategy for precise tuning of loop defects in covalent polymer gel networks. This "loop control" is achieved through a simple semibatch monomer addition protocol that can be applied to a broad range of network-forming reactions. By controlling loop defects, we demonstrate that with the same set of material precursors it is possible to tune and in several cases substantially improve network connectivity and mechanical properties (e.g., ∼600% increase in shear storage modulus). We believe that the concept of loop control via continuous reagent addition could find broad application in the synthesis of academically and industrially important cross-linked polymeric materials, such as resins and gels.

Living Additive Manufacturing: Transformation of Parent Gels into Diversely Functionalized Daughter Gels Made Possible by Visible Light Photoredox Catalysis.

Light-initiated additive manufacturing techniques typically rely on layer-by-layer addition or continuous extraction of polymers formed via nonliving, free radical polymerization methods that render the final materials "dead" toward further monomer insertion; the polymer chains within the materials cannot be reactivated to induce chain extension. An alternative "living additive manufacturing" strategy would involve the use of photocontrolled living radical polymerization to spatiotemporally insert monomers into dormant "parent" materials to generate more complex and diversely functionalized "daughter" materials. Here, we demonstrate a proof-of-concept study of living additive manufacturing using end-linked polymer gels embedded with trithiocarbonate iniferters that can be activated by photoinduced single-electron transfer from an organic photoredox catalyst in solution. This system enables the synthesis of a wide range of chemically and mechanically differentiated daughter gels from a single type of parent gel via light-controlled modification of the parent's average composition, strand length, and/or cross-linking density. Daughter gels that are softer than their parent, stiffer than their parent, larger but with the same modulus as their parent, thermally responsive, polarity responsive, healable, and weldable are all realized.

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

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.

Drawing in poly(ε-caprolactone) fibers: tuning mechanics, fiber dimensions and surface-modification density.

Uniaxial drawing of melt-coextruded poly(ε-caprolactone) (PCL) microfibers was investigated to understand impact on topological, mechanical, and chemical properties of the fibrous scaffolds. Fibers were uniaxially elongated up to 7-fold to observe polymer chain orientation and crystal structure. Crystallinity and orientation of crystal domains were investigated by DSC and X-ray scattering. Polymer physical properties were directly correlated to bulk fiber properties. Furthermore, the drawn fibers were modified photochemically with functionalized benzophenones. The results of these studies allowed for comparison between fiber dimension/surface area, mechanical properties, and photochemical reaction yield for surface modification. As drawing increased, the modulus and tensile strength of the fibers increased as did the surface area of the scaffolds. By contrast, increased drawing led to a decrease in the ability to undergo photochemical reaction at the polymer surface. This fundamental investigation provides a predictive framework to understand how post-processing impacts three critical parameters for coextruded fibrous biomaterial scaffolds.

Processing and surface modification of polymer nanofibers for biological scaffolds: a review.

Polymeric fibrous constructs possess high surface area-to-volume ratios when compared with solid substrates and are quite commonly used as tissue engineering and cell growth scaffolds. An overview of important design and material considerations for fibrous scaffolds as well as an outline of both established and emerging solution- and melt-based fabrication techniques is provided. Innovative post-process surface modification avenues using "click" chemistry with both single and dual active cues as well as gradient cues, which maintain the fibrous structure are described. By combining process parameters with post-process surface modification, researchers have been able to selectively tune cellular response after seeding and culturing on fibrous constructs.

Surface Modification of Melt Extruded Poly(ε-caprolactone) Nanofibers: Toward a New Scalable Biomaterial Scaffold.

A photochemical modification of melt-extruded polymeric nanofibers is described. A bioorthogonal functional group is used to decorate fibers made exclusively from commodity polymers, covalently attach fluorophores and peptides, and direct cell growth. Our process begins by using a layered coextrusion method, where poly(ε-caprolactone) (PCL) nanofibers are incorporated within a macroscopic poly(ethylene oxide) (PEO) tape through a series of die multipliers within the extrusion line. The PEO layer is then removed with a water wash to yield rectangular PCL nanofibers with controlled cross-sectional dimensions. The fibers can be subsequently modified using photochemistry to yield a "clickable" handle for performing the copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction on their surface. We have attached fluorophores, which exhibit dense surface coverage when using ligand-accelerated CuAAC reaction conditions. In addition, an RGD peptide motif was coupled to the surface of the fibers. Subsequent cell-based studies have shown that the RGD peptide is biologically accessible at the surface, leading to increased cellular adhesion and spreading versus PCL control surfaces. This functionalized coextruded fiber has the advantages of modularity and scalability, opening a potentially new avenue for biomaterials fabrication.

Structural evolution during mechanical deformation in high-barrier PVDF-TFE/PET multilayer films using in situ X-ray techniques.

Poly(vinylidene fluoride-co-tetrafluoroethylene) (PVDF-TFE) is confined between alternating layers of poly(ethylene terephthalate) (PET) utilizing a unique multilayer processing technology, in which PVDF-TFE and PET are melt-processed in a continuous fashion. Postprocessing techniques including biaxial orientation and melt recrystallization were used to tune the crystal orientation of the PVDF-TFE layers, as well as achieve crystallinity in the PET layers through strain-induced crystallization and thermal annealing during the melt recrystallization step. A volume additive model was used to extract the effect of crystal orientation within the PVDF-TFE layers and revealed a significant enhancement in the modulus from 730 MPa in the as-extruded state (isotropic) to 840 MPa in the biaxially oriented state (on-edge) to 2230 MPa in the melt-recrystallized state (in-plane). Subsequently, in situ wide-angle X-ray scattering was used to observe the crystal structure evolution during uniaxial deformation in both the as-extruded and melt-recrystallized states. It is observed that the low-temperature ferroelectric PVDF-TFE crystal phase in the as-extruded state exhibits equatorial sharpening of the 110 and 200 crystal peaks during deformation, quantified using the Hermans orientation function, while in the melt-recrystallized state, an overall increase in the crystallinity occurs during deformation. Thus, we correlated the mechanical response (strain hardening) of the films to these respective evolved crystal structures and highlighted the ability to tailor mechanical response. With a better understanding of the structural evolution during deformation, it is possible to more fully characterize the structural response to handling during use of the high-barrier PVDF-TFE/PET multilayer films as commercial dielectrics and packaging materials.

Acute and chronic effects of diphenhydramine and sertraline mixtures in Ceriodaphnia dubia.

Ceriodaphnia dubia were tested to evaluate the acute and chronic interactive effects of diphenhydramine and sertraline. Observed effects were compared with 2 reference toxicity models, the concentration addition model and the independent action model. Results indicate that the 2 drugs exhibit additive toxicity in C. dubia. In some cases, individually sublethal concentrations of the chemicals resulted in 100% mortality when combined, demonstrating the potentially severe impact of trace environmental contaminants.

Toward anisotropic materials via forced assembly coextrusion.

Multilayer coextrusion offers a diverse platform to examine layer dependent confinement effects on self-assembling nanomaterials via conventional extrusion technology. A triblock copolymer (BCP) with a cylindrical microstructure was processed via "forced assembly" to elucidate the effect of microdomain orientation on the mechanical behavior of multilayer films. The mechanical response was investigated in both the extrusion (ED) and transverse directions (TD) of the multilayer systems, revealing an influence of both cylinder-orientation and the interface on the mechanical response with decreasing layer thickness. The stress-strain curves for samples with the stress field along the cylinder axis revealed a sharp yielding phenomenon, while curves for specimens with the stress field applied perpendicular to the axis exhibited weak yielding behavior. The extensibility of the multilayer films stressed in the ED increases with decreasing layer thickness, but remains constant when deformed along the TD. Coextrusion technology allows for tunable mechanical toughness in industrial grade polymers via a continuous process. By altering the layer thickness of the two polymeric materials, we can tune the mechanics from strong, brittle behavior to a tough, ductile response by manipulation of the hierarchical structure. The enabling technology provides a unique platform to couple the inherent mechanical response of dissimilar polymers and allows for the design of composite materials with tailored mechanics.